CN106315910A - Method for treating waste water of titanium dioxide - Google Patents
Method for treating waste water of titanium dioxide Download PDFInfo
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- CN106315910A CN106315910A CN201510388879.6A CN201510388879A CN106315910A CN 106315910 A CN106315910 A CN 106315910A CN 201510388879 A CN201510388879 A CN 201510388879A CN 106315910 A CN106315910 A CN 106315910A
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Abstract
TThe invention provides a method for treating waste water of titanium dioxide. The method comprises the following steps: (1) quicklime is added into waste water of titanium dioxide by a sulfuric acid method for carrying out neutralizing treatment and aeration; (2) a flocculating agent is added into the waste water after aeration, dispersible impurities in the waste water are aggregated and coagulated, larger impurities are precipitated in a buffer pool, other impurities along with the waste water enter an ultrafilter membrane pool, colloid, insoluble substances, microorganisms and the like in the waste water are filtered by a waste water ultrafilter membrane, turbidity of the waste water is reduced to 0.2NTU or below, in order to form inorganic salt waste water; (3) the inorganic salt waste water is pressurized by a high pressure pump and enters into a reverse osmosis membrane component in order to remove inorganic salt in the waste water, and qualified industrial water is formed. The produced water can completely satisfy requirements of industrial water, integrated recovery rate of the water treatment system=ultrafiltration recovery rate x reverse osmosis recovery rate=90%x70%=63%, and the water recovery rate is high.
Description
Technical field
The present invention relates to a kind of method of wastewater treatment, produced acid waste water waste water after neutralizing through quick lime during particularly relating to a kind of Titanium White Production By Sulfuric Acid Process, through the method that reprocessing produces acceptable industrial water.
Background technology
Titanium dioxide is a kind of important inorganic chemical product, usually used as a kind of Chinese white, owing to having the advantages such as stable chemical performance, high index of refraction and even particle size distribution, extensively applies in fields such as coating, plastics papermaking.
The most domestic titanium white production technique mainly has sulfuric acid process and chloridising etc..Sulfuric acid process is simple due to process, and can be used for processing the Ore that taste is relatively low, is widely adopted the most at home.But sulfuric acid method titanium pigment production technology exists the problem that the three wastes discharge amounts such as waste water,waste gas and industrial residue are big, the only discharge capacity of acid waste water just reaches 100～150 ton/ton titanium dioxides.Wastewater processing technology has become a pendulum urgent need to solve the problem in face of titanium white production enterprise.
From the point of view of the current most of titanium powder plants process technique to titanium dioxide wastewater, technology is more ripe, run relatively stable process technique is quick lime neutralisation, also have what this technique was carried out to be partially improved and in depths, such as Chinese patent CN100575276C and CN101962239B, but after using neutralisation to process, obtained water still contains high salinity and float, use the distinct disadvantage that traditional water treatment technology deep processing exists technological process length, floor space is big, consumption of chemical agent is big, poor for single titanium white production producer exploitativeness.Prior, the water using said method to prepare still can not fully meet the water for industrial use requirement to water quality.
In sulfuric acid method titanium pigment production, produced high salinity wastewater processing technology still needs to the most perfect.
Summary of the invention
Present invention aims to sulfate process titanium dioxide waste water high salinity, the objective circumstances of high suspended matter content, a kind of titanium dioxide wastewater processing method being suitable for use with after quick lime neutralizes is provided, make up to the requirement of water for industrial use, and have that technological process is short, floor space is little, automaticity is high, produce water quality advantages of higher, specifically realized by techniques below scheme:
The processing method of a kind of titanium dioxide wastewater, specifically includes following steps: 1), sulfate process titanium dioxide waste water through add quick lime neutralisation treatment, aeration；2) waste water, crossed by above-mentioned aeration adds flocculant, make the dispersibility accumulation of impurities in waste water, coagulation, bigger impurity can precipitate in buffering pond, remaining together enters ultrafiltration membrane pool with waste water, waste water after waste water hyperfiltration membrane filtration, having removed colloid therein, insoluble matter and microorganism etc., turbidity of wastewater is reduced to below 0.2NTU, forms inorganic salt waste water；3), described inorganic salt waste water enters reverse osmosis membrane assembly removal inorganic salt therein through high-pressure pump pressurization thus forms acceptable industrial water.
The processing method of described titanium dioxide wastewater, its further design is: step 1) adds quick lime, aeration, and quick lime generates CaSO with the acid neutralization in waste water4, acid titanium dioxide wastewater is neutralized, part CaSO4Precipitation so that the pH value of waste water is in 6 ~ 9, concentration of suspension is 45 ~ 55mg/L, turbidity is 10 ~ 20NTU, CODcr concentration be 30 mg/L, Mg2+ ion concentrations be 100 ~ 150 mg/L, Ca2+ ion concentrations be 500 ~ 600 mg/L, SO42-concentration be 6000 ~ 8000 mg/L, TDS be 7000～8000 mg/L, total hardness be 1000～1500 mg/L.
The processing method of described titanium dioxide wastewater, its further design be: step 2) described in flocculant be polymerization aluminum chloride.
The processing method of described titanium dioxide wastewater, its further design is: step 2) use submerged hollow fiber ultrafilter membrane dead-end filtration mode to carry out ultrafiltration membrance filter, wherein said ultrafilter membrane aperture is between 0.001～0.1 μm；Ultrafiltration membrance filter technology is to utilize Screening theory to the separation film of the impurity such as the antibacterial retaining in solution, thermal source, virus and colloidal particles, protein, larger molecular organics.Ultrafiltration technology as an alternative can simplify tradition water and process the technological process of huge coagulation, clarification, filter plant and complexity；Waste water after ultrafiltration membrance filter, has removed colloid, insoluble matter and the microorganism etc. of the overwhelming majority, and turbidity of wastewater is reduced to below 0.2NTU.Now, the main component in waste water is various inorganic salts.This waste water, after cartridge filter filters and may affect the insoluble impurities that reverse osmosis membrane works, enters reverse osmosis membrane assembly through high-pressure pump pressurization.
The processing method of described titanium dioxide wastewater, its further design is: in the forward direction waste water of step 3) waste water entrance reverse osmosis membrane assembly, addition antisludging agent and sodium sulfite are as reducing agent, remove the chlorine residue in water while stoping above salinity crystallization deposition.
The processing method of described titanium dioxide wastewater, its further design be: step 3) makes to be in 6 ~ 9 through the waste water pH value of reverse-osmosis treated, turbidity≤mg/L, SO42-concentration≤50, mg/L, Ca2+ ion concentration≤100, mg/L, Mg2+ ion concentration≤50,2NTU, CODcr concentration≤30 mg/L, TDS≤200mg/L, total hardness≤200mg/L, forms acceptable industrial water.
The water produced matter of the present invention fully meets water for industrial use requirement, and the comprehensive recovery of this water treatment system=ultrafiltration response rate × reverse osmosis response rate=90% × 70%=63%, has higher Water Sproading rate.
Accompanying drawing explanation
Figure-1 is embodiments of the invention process chart.
Detailed description of the invention
Below in conjunction with Figure of description and embodiment, the present invention is further described.
Shown in Fig. 1, sulfate process titanium dioxide waste water titanium dioxide wastewater after quick lime neutralisation treatment makes the pH value of waste water be in 6 ~ 9, concentration of suspension is 45 ~ 55mg/L, turbidity is 10 ~ 20NTU, CODcr concentration be 30 mg/L, Mg2+ ion concentrations be 100 ~ 150 mg/L, Ca2+ ion concentrations be 500 ~ 600 mg/L, SO42-concentration be 6000 ~ 8000 mg/L, TDS be 7000～8000 mg/L, total hardness be 1000～1500 mg/L.Squeezing into buffer tank after adding flocculant poly aluminum chloride in waste water, arrange filter, filter out the impurity of larger particles between primer pump and buffer tank, the effect of flocculant is float less in water to be flocculated, precipitate, be beneficial to ultra-filtration and separation.Water in buffer tank is squeezed into the membrane cisterna containing ultrafiltration membrane elements by membrane cisterna feed pump, and in membrane cisterna, ultrafiltration membrane elements can use the membrane component of the most all kinds of maturation.Now illustrate in submerged hollow fiber ultrafilter membrane dead-end filtration mode: aspirate bottom membrane component with vacuum pump (i.e. producing water/backwashing pump), driving force is provided for ultrafiltration, make clear liquid pass through ultrafiltration fenestra multiparity water pump and send into ultrafiltration product water tank, it is trapped within ultrafiltration membrane pool more than the float in ultrafilter membrane aperture, colloid, microorganism etc., becomes dense water.For preventing ultrafiltration fenestra to be blocked, can be at certain product water week after date, use ultrafiltration to produce water and ultrafiltration membrane filaments is carried out backwash, compressed air purge nozzle also can be set bottom membrane component, every certain product water time, cleaning film silk by compressed air, general backwash and compressed air are cleaned and are carried out simultaneously, according to different membrane modules, produce water 15-30min and can be compressed air purging and anti-cleaning.Along with producing being continuously increased of water time, dense water is constantly enriched with, and can will arrange after a certain time, the most again carry out producing water outside dense water.Outside dense water, row's cycle is according to different membrane components and water quality, substantially at about 1-1.5 days.For preventing the pollution to ultrafiltration membrane filaments such as colloid, float, microorganism, at certain product water week after date, film silk should be carried out dosing cleaning, conventional medicament such as sodium hypochlorite (main wash microorganism pollution) and citric acid (cleaning alkaline matter to pollute).
Its turbidity of water entering ultrafiltration product water tank has been lowered to below 0.2NTU, but salinity and titanium dioxide wastewater are substantially quite (ultrafilter membrane does not has sieving actoion to salt ion).Use reverse osmosis feed pump that ultrafiltration is produced water to squeeze into reverse osmosis membrane assembly and carry out desalting processing.The arrangement mode of reverse osmosis membrane assembly can be to be the modes such as one-level two sections, multistage multistage, and concrete determines according to treating capacity and water quality requirement.The form that dense water section refluxes can also be used to put forward high yield water water quality (as shown in figure-1).For reaching the high pressure of reverse osmosis requirement, can produce before water enters reverse osmosis membrane assembly in ultrafiltration and pressurize with high-pressure pump, if using one-level two sections or the reverse osmosis membrane assembly arrangement mode of one-level multistage, may select and booster pump is set intersegmental.Reverse osmosis produced water is delivered to reverse osmosis produced water tank by collector pipe, and this product water meets the index request of water for industrial use, can be routed directly at service water.Reverse osmosis concentrated water then outer row.
It is to be noted, if reverse osmosis membrane materials is aromatic polyamides, due to aromatic polyamides not chlorine-resistant, for preventing the chlorine in titanium dioxide wastewater from reverse osmosis membrane causing irreversible destruction, Ying Shui adds the reducing agents such as sodium sulfite before entering reverse osmosis membrane assembly, remove the chlorine residue in water.Prior, owing in titanium dioxide wastewater, salinity is the highest, especially in dense water side, salinity is enriched with further, calculates certain typical sulfur acid system titanium dioxide wastewater through simulation as follows in the saturation of each salinity in reverse osmosis membrane dense water side: CaCO3Be 150%, CaSO4Be 550%, BaSO4Be 1200%, CaF2Be 5000%, Ca3(PO4)2It is 95%.
Can significantly find out, titanium dioxide wastewater is easily formed crystal deposition on reverse osmosis membrane surface at reverse osmosis concentrated water side pole, blocks reverse osmosis fenestra, and then reduces the aquifer yield of reverse osmosis membrane, improves reverse osmosis pressure, and the serious reverse osmosis membrane that will cause is scrapped.In consideration of it, antisludging agent should be added before titanium dioxide wastewater enters reverse osmosis membrane assembly, stop above salinity crystallization deposition.Excellent antisludging agent through screening can ensure reverse osmosis membrane assembly long-period stable operation under the response rate of 70%.Final waste water pH value is in 6 ~ 9, turbidity≤mg/L, SO42-concentration≤50, mg/L, Ca2+ ion concentration≤100, mg/L, Mg2+ ion concentration≤50,2NTU, CODcr concentration≤30 mg/L, TDS≤200mg/L, total hardness≤200mg/L, forms acceptable industrial water.
Claims (6)
1. the processing method of a titanium dioxide wastewater, it is characterised in that comprise the steps: 1), sulfate process titanium dioxide waste water through add quick lime neutralisation treatment, aeration；2) waste water, crossed by above-mentioned aeration adds flocculant, make the dispersibility accumulation of impurities in waste water, coagulation, bigger impurity can precipitate in buffering pond, remaining together enters ultrafiltration membrane pool with waste water, waste water after waste water hyperfiltration membrane filtration, having removed colloid therein, insoluble matter and microorganism etc., turbidity of wastewater is reduced to below 0.2NTU, forms inorganic salt waste water；3), described inorganic salt waste water enters reverse osmosis membrane assembly removal inorganic salt therein through high-pressure pump pressurization thus forms acceptable industrial water.
The processing method of titanium dioxide wastewater the most according to claim 1, it is characterised in that: step 1) add make after quick lime, aeration the pH value of waste water be in 6 ~ 9, concentration of suspension be 45 ~ 55mg/L, turbidity be 10 ~ 20NTU, CODcr concentration be 30 mg/L, Mg2+Ion concentration is 100 ~ 150 mg/L, Ca2+Ion concentration is 500 ~ 600 mg/L, SO4 2-Concentration be 6000 ~ 8000 mg/L, TDS be 7000～8000 mg/L, total hardness be 1000～1500 mg/L.
The processing method of titanium dioxide wastewater the most according to claim 1, it is characterised in that: step 2) described in flocculant be polymerization aluminum chloride.
The processing method of titanium dioxide wastewater the most according to claim 1, it is characterised in that: step 2) use submerged hollow fiber ultrafilter membrane dead-end filtration mode to carry out ultrafiltration membrance filter, wherein said ultrafilter membrane aperture is between 0.001～0.1 μm.
The processing method of titanium dioxide wastewater the most according to claim 1, it is characterized in that: in the forward direction waste water of step 3) waste water entrance reverse osmosis membrane assembly, addition antisludging agent and sodium sulfite are as reducing agent, remove the chlorine residue in water while stoping above salinity crystallization deposition.
The processing method of titanium dioxide wastewater the most according to claim 5, it is characterised in that: step 3) makes to be in 6 ~ 9 through the waste water pH value of reverse-osmosis treated, turbidity≤2NTU, CODcr concentration≤30 mg/L, Mg2+Ion concentration≤50 mg/L, Ca2+Ion concentration≤100 mg/L, SO4 2-Concentration≤50 mg/L, TDS≤200mg/L, total hardness≤200mg/L, form acceptable industrial water.
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| CN201510388879.6A CN106315910A (en) | 2015-07-06 | 2015-07-06 | Method for treating waste water of titanium dioxide |
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| CN201510388879.6A CN106315910A (en) | 2015-07-06 | 2015-07-06 | Method for treating waste water of titanium dioxide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650629A (en) * | 2019-01-21 | 2019-04-19 | 浙江菲尔特过滤科技股份有限公司 | A kind of zero-discharge treatment process for industrial wastewater and processing system |
| CN110813098A (en) * | 2019-11-18 | 2020-02-21 | 上海安赐环保科技股份有限公司 | Sulfuric acid method titanium dioxide production method and cleaning method of membrane equipment |
| CN112028368A (en) * | 2020-09-16 | 2020-12-04 | 广东益诺欧环保股份有限公司 | Treatment system and method for waste hydrochloric acid and waste brine in titanium dioxide chloride production |
| JP2023509228A (en) * | 2020-11-20 | 2023-03-07 | 成都千砺金科技創新有限公司 | Complete resource recycling method for wastewater from sulfuric acid titanium white production |
-
2015
- 2015-07-06 CN CN201510388879.6A patent/CN106315910A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109650629A (en) * | 2019-01-21 | 2019-04-19 | 浙江菲尔特过滤科技股份有限公司 | A kind of zero-discharge treatment process for industrial wastewater and processing system |
| CN110813098A (en) * | 2019-11-18 | 2020-02-21 | 上海安赐环保科技股份有限公司 | Sulfuric acid method titanium dioxide production method and cleaning method of membrane equipment |
| CN110813098B (en) * | 2019-11-18 | 2022-03-08 | 上海安赐环保科技股份有限公司 | Sulfuric acid method titanium dioxide production method and cleaning method of membrane equipment |
| CN112028368A (en) * | 2020-09-16 | 2020-12-04 | 广东益诺欧环保股份有限公司 | Treatment system and method for waste hydrochloric acid and waste brine in titanium dioxide chloride production |
| CN112028368B (en) * | 2020-09-16 | 2024-01-23 | 广东益诺欧环保股份有限公司 | System and method for treating waste hydrochloric acid and waste brine in production of titanium dioxide chloride |
| JP2023509228A (en) * | 2020-11-20 | 2023-03-07 | 成都千砺金科技創新有限公司 | Complete resource recycling method for wastewater from sulfuric acid titanium white production |
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