CN113912234B - Sewage treatment method for producing titanium dioxide by using chlorination process - Google Patents

Sewage treatment method for producing titanium dioxide by using chlorination process Download PDF

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Publication number
CN113912234B
CN113912234B CN202111254012.3A CN202111254012A CN113912234B CN 113912234 B CN113912234 B CN 113912234B CN 202111254012 A CN202111254012 A CN 202111254012A CN 113912234 B CN113912234 B CN 113912234B
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China
Prior art keywords
lime milk
waste liquid
preparation tank
producing titanium
titanium dioxide
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CN202111254012.3A
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Chinese (zh)
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CN113912234A (en
Inventor
张建林
和奔流
刘峰
祝永红
刘红星
赵冠杰
张军丽
张燕平
李俊
王丽艳
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Longbai Lufeng Titanium Industry Co ltd
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Longbai Lufeng Titanium Industry Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Water Treatments (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention belongs to the technical field of waste liquid treatment, and particularly relates to a sewage treatment method for producing titanium dioxide by a chlorination method, wherein alkaline waste liquid produced by titanium dioxide is input into a titanium dioxide lime milk preparation tank, ammonia nitrogen in lime milk is discharged in a nitrogen form through aeration, and then mixed liquid is input into a neutralization tank to neutralize metal chloride waste water, so that the alkaline waste liquid is treated under the condition of no need of triple effect evaporation; the alkaline waste liquid is alkaline, so that the metal chloride waste water can be neutralized, the consumption of the carbide mud is reduced, and the cost is further reduced; and the alkaline waste liquid reacts with ammonia nitrogen in lime milk to generate nitrogen, so that the total ammonia nitrogen in the neutralized waste water is reduced, and the eutrophication of water is reduced.

Description

Sewage treatment method for producing titanium dioxide by using chlorination process
Technical Field
The invention belongs to the technical field of waste liquid treatment, and particularly relates to a sewage treatment method for producing titanium dioxide by a chlorination process.
Background
When the upper deslagging boiling chlorination furnace is adopted in the production of titanium white, dust slag discharged from the chlorination furnace is subjected to cyclone dust collection and then is pulped by water, dust slurry is subjected to filter pressing, fine powder petroleum coke and titanium slag are contained in filter residues, and the filter residues are recycled through subsequent washing; the filtrate is metal chloride wastewater, and the filtrate is acidic; at present, lime cream prepared from the carbide mud is used for neutralizing metal chloride wastewater, ammonia nitrogen in the carbide mud is higher, and the prepared lime cream can cause higher ammonia nitrogen in the wastewater after neutralizing the metal chloride.
Sodium hypochlorite can react with ammonia nitrogen in a liquid phase, hypochlorous acid or hypochlorite ions can react with the ammonia nitrogen in various ways, and can produce several intermediate products, such as: monochloramine, dichloramine, trichloroammonia and the like, and finally ammonia nitrogen is converted into nitrogen to be released into the air, wherein the process is called break point chlorination, and the related reaction formula is as follows:
NaClO+H 2 O＝HClO+NaOH
NH 3 +HClO＝NH 2 Cl+H 2 O
NH 2 Cl+HClO＝NHCl 2 +H 2 O
NHCl 2 +H 2 O＝NOH+2Cl - +2H +
NHCl 2 +NOH＝N 2 ↑+HClO+H + +Cl –
the general reaction formula is: 2NH 3 +3NaClO＝N 2 ↑+3H 2 O+3NaCl
At present, the tail gas washing in the titanium chloride production process adopts sodium hydroxide alkali liquor for washing, and the generated waste liquid is mainly sodium hypochlorite; the waste liquid is alkaline, the concentration of sodium hypochlorite is low, the iron content is high, the waste liquid is not suitable for takeaway, sodium chloride needs to be treated and recovered through triple effect evaporation, a triple effect evaporation system has certain requirements on the concentration of raw materials, and the triple effect evaporation system is high in cost and is not beneficial to energy conservation.
Disclosure of Invention
The invention provides a sewage treatment method for producing titanium dioxide by a chlorination process, which aims to solve the technical problems that the cost is high and the energy conservation is not facilitated in a mode of treating and recycling sodium chloride by triple-effect evaporation.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a sewage treatment method for producing titanium dioxide by a chlorination process comprises the following steps:
step 1: adding water to slurry the carbide sludge to form lime milk;
step 2: mixing alkaline waste liquid generated in the production of titanium chloride white with lime milk;
step 3: aerating the mixture in the step 2 by compressed air to fully react the sodium hypochlorite with ammonia nitrogen in lime milk;
step 4: the mixture produced after stirring and mixing and aeration in the step 3 is neutralized with the metal chloride waste liquid produced by producing titanium pigment, and the PH is adjusted to be neutral;
step 5: discharging the mixture neutralized in the step 4 into a thickener for sedimentation and concentration;
step 6: and (3) carrying out filter pressing on the settled materials by using a filter press, collecting filtrate, then, entering a mechanical distillation recompression technical system, and transporting filter residues to a residue warehouse for storage.
Preferably, the electric mudstone in the step 1 is pulped in a lime milk preparation tank, and the lime milk position is controlled below 70% of the storage volume of the lime milk preparation tank.
Preferably, the alkaline waste liquid in the step 2 is input into a lime milk preparation tank to be mixed with lime milk, and the single input does not exceed 20% of the total liquid level of the lime milk preparation tank; and the input flow is controlled to be 0.1m 3 /min。
Preferably, the aeration time in step 3 is half an hour.
The alkaline waste liquid component is sodium hypochlorite, and the alkaline waste liquid is input into a lime milk preparation tank to react with lime milk, and then the neutralization reaction is carried out on acid waste liquid (metal chloride waste liquid) generated by producing titanium pigment, so that ammonia nitrogen in the lime milk can be reduced, a part of acid waste water can be neutralized, and carbide mud consumption can be reduced. After the neutralization reaction, the pH of the liquid is reduced from 13 to 7; the invention aims at the comprehensive utilization of the alkaline waste liquid and sewage, the product produced after the treatment of the above 6 steps is ferrous hydroxide, the product is piled up in a slag field, and sodium chloride is evaporated into salt after entering a mechanical distillation recompression technical system. If the ammonia nitrogen content brought by lime milk is not reduced by adding sodium hypochlorite, the content of ammonia nitrogen in the evaporated condensed water is more, and the water body can be eutrophicated although the emission standard can be met.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, alkaline waste liquid produced by titanium chloride white is input into a titanium white lime milk preparation tank, ammonia nitrogen in the lime milk is discharged in a nitrogen form through aeration, and then mixed liquid is input into a neutralization tank to neutralize metal chloride waste water, so that the alkaline waste liquid is treated under the condition of no need of triple effect evaporation; the alkaline waste liquid is alkaline, so that the metal chloride waste liquid can be neutralized, the consumption of the carbide mud is reduced, and the cost is further reduced; and the alkaline waste liquid reacts with ammonia nitrogen in lime milk to generate nitrogen, so that the total ammonia nitrogen in the neutralized waste water is reduced, and the eutrophication of water is reduced.
Drawings
FIG. 1 is a schematic flow chart of the present invention;
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A preferred embodiment of the present invention will be described in detail with reference to fig. 1;
step 1: adding water into a lime milk preparation tank to pulp the carbide mud, wherein the lime milk liquid level in the lime milk preparation tank is controlled below 70% of the storage volume of the lime milk preparation tank, so that the follow-up alkaline solution can not be added;
step 2: inputting alkaline waste liquid generated in the production of titanium chloride into a lime milk preparation tank, and inputting the alkaline waste liquid into the lime milk preparation tank, wherein the single input does not exceed 20% of the total liquid level of the lime milk preparation tank; and the input flow is controlled to be 0.1m 3 /min；
Step 3: inputting compressed air into a lime milk preparation tank, and continuously stirring for aeration for half an hour to enable sodium hypochlorite to fully react with ammonia nitrogen in the carbide mud;
step 4: the lime milk after stirring and mixing in the step 3 is input into a neutralization tank to be neutralized with metal chloride, and the PH is adjusted to be neutral;
step 5: discharging the mixture neutralized in the step 4 into a thickener for sedimentation and concentration;
step 6: and (3) carrying out filter pressing on the settled materials by using a filter press, collecting filtrate, then, entering a mechanical distillation recompression technical system, and transporting filter residues to a residue warehouse for storage.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (3)

1. A sewage treatment method for producing titanium dioxide by a chlorination process is characterized by comprising the following steps:
step 1: adding water to slurry the carbide sludge to form lime milk;
step 2: mixing alkaline waste liquid generated in the production of titanium chloride white with lime milk;
step 3: aerating the mixture in the step 2 by compressed air to fully react the sodium hypochlorite with ammonia nitrogen in lime milk;
step 4: the mixture produced after stirring and mixing and aeration in the step 3 is neutralized with the metal chloride waste liquid produced by producing titanium pigment, and the PH is adjusted to be neutral;
step 5: discharging the mixture neutralized in the step 4 into a thickener for sedimentation and concentration;
step 6: the settled materials are subjected to filter pressing by a filter press, filtrate is collected and then enters a mechanical distillation recompression technical system, and filter residues are transported to a residue warehouse for storage;
the aeration time in step 3 was half an hour.
2. The method for treating sewage generated by producing titanium pigment by a chlorination process according to claim 1, wherein the electric mudstone in the step 1 is pulped in a lime milk preparation tank, and the lime milk position is controlled below 70% of the storage volume of the lime milk preparation tank.
3. The method for treating sewage generated by producing titanium pigment by a chlorination process according to claim 1, wherein the alkaline waste liquid in the step 2 is input into a lime milk preparation tank to be mixed with lime milk, and the single input is not more than 20% of the total liquid level of the lime milk preparation tank; and the input flow rate was controlled at 0.1m3/min.
CN202111254012.3A 2021-10-27 2021-10-27 Sewage treatment method for producing titanium dioxide by using chlorination process Active CN113912234B (en)

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CA2746480A1 (en) * 2008-12-12 2010-06-17 Uhde Gmbh Removal of ammonia nitrogen, ammonium nitrogen and urea nitrogen by oxidation with hypochlorite-containing solutions from exhaust air in plants for producing ammonia and urea
CN106311719A (en) * 2016-08-22 2017-01-11 四川龙蟒钛业股份有限公司 Recycling method for carbide slag

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CN203333413U (en) * 2013-06-21 2013-12-11 河南永银化工实业有限公司 System for comprehensively utilizing wastewater generated during production of polyvinyl chloride (PVC) production by calcium carbide method
CN106517621B (en) * 2015-09-09 2021-08-10 有研稀土新材料股份有限公司 Recycling process of ammonium chloride-containing wastewater
CN105417823A (en) * 2015-12-25 2016-03-23 周振喜 Method of recycling ammonia from low-concentration ammonium chloride waste water
CN105884082A (en) * 2016-05-26 2016-08-24 宜宾天原集团股份有限公司 Method for treating acid wastewater in titanium dioxide production process through chlorination method
CN106365292A (en) * 2016-08-30 2017-02-01 四川龙蟒钛业股份有限公司 Recycling method of carbide slag slurry supernate
CN106396184A (en) * 2016-11-17 2017-02-15 上海晶宇环境工程股份有限公司 Ammonia stripping process and device for high-ammonia-nitrogen wastewater
CN109095677A (en) * 2018-09-20 2018-12-28 攀钢集团钛业有限责任公司 Containing sodium hypochlorite waste water and sulfate process titanium dioxide acid waste water integrated conduct method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2746480A1 (en) * 2008-12-12 2010-06-17 Uhde Gmbh Removal of ammonia nitrogen, ammonium nitrogen and urea nitrogen by oxidation with hypochlorite-containing solutions from exhaust air in plants for producing ammonia and urea
CN106311719A (en) * 2016-08-22 2017-01-11 四川龙蟒钛业股份有限公司 Recycling method for carbide slag

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