CN108164046A - A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater - Google Patents

A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater Download PDF

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Publication number
CN108164046A
CN108164046A CN201810081977.9A CN201810081977A CN108164046A CN 108164046 A CN108164046 A CN 108164046A CN 201810081977 A CN201810081977 A CN 201810081977A CN 108164046 A CN108164046 A CN 108164046A
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China
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wastewater
desulfurization
desulfurization wastewater
magnesium
recycling
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CN201810081977.9A
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Inventor
马永鹏
母佰龙
张肖静
王腾飞
楚航
陈召
袁东丽
周月
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Zhengzhou University of Light Industry
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Zhengzhou University of Light Industry
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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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • 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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Fertilizers (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The present invention discloses a kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater, includes the following steps：（1）After the oxidized magnesium processes desulfurization of industrial smoke, desulfurization wastewater is obtained；Under stirring condition, desulfurization wastewater is mixed with ammonia nitrogen waste water, it is 3 ~ 6 to adjust its pH value, is stood, and generates ammonium sulfate magnesium precipitate, separation of solid and liquid；（2）Ammonium sulfate magnesium precipitate after separation is purified, obtains the raw material of slow release fertilizer.In the desulfurization wastewater that the present invention is formed using magnesium oxide method desulfurization high-salt wastewater is formed containing a large amount of magnesium sulfate, and contain a large amount of ammonium ion and sulfate ion in high ammonia-nitrogen wastewater, the two mixing generates ammonium sulfate magnesium precipitate, the ammonium ion and sulfate ion in the magnesium sulfate and high ammonia-nitrogen wastewater in desulfurization wastewater are effectively removed, subsequent processing, reduction expense cost conducive to waste water.

Description

A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater
Technical field
The invention belongs to Industrial Wastewater Treatment and application technology as the second resource fields, and in particular to a kind of to be handled with desulfurization wastewater The method of high-concentration ammonia nitrogenous wastewater and recycling.
Background technology
With the fast development of China's economy, non-ferrous metal metallurgy, chemical fertilizer and coal chemical industry also grow up therewith.Have Non-ferrous metal smelting process and other industry coal-boilers can all generate SO2Flue gas, coal-burned industrial boiler discharge SO every year2About 6,400,000 T accounts for about national SO2The 32% of discharge capacity, non-ferrous metal metallurgy discharge accounts for about 8%, in flue gas desulfurization course, can generate a large amount of Desulfurization wastewater.Meanwhile in industrial processes, the ammonia nitrogen waste water of high concentration is generated, ammonia-nitrogen content is about 1000- 160000 mg/L, the ammonia nitrogen kind compound content in waste water is high, can lead to body eutrophication and environmental pollution, but at waste water It is larger to manage difficulty.
At present, the method for handling ammonia nitrogen waste water mainly has：Bioanalysis, chemical method, blow-off method and catalytic oxidation.Bioanalysis More demanding to the growing environment of microorganism, reaction rate is relatively slow and the sludge acclimatization time is longer, the ammonia nitrogen waste water pair of high concentration The growth of microorganism is unfavorable, accordingly, it is difficult to Biochemical method high-concentration ammonia nitrogenous wastewater；Equipment that blow-off method uses is simple, behaviour Work is stablized, but the very high, high energy consumption to the temperature requirement of waste water, and is also easy to produce secondary pollution, and therefore, application is restricted；It urges Change oxidizing process and require excessively high to equipment control, application range is very narrow.
The method of desulfurizing industrial fume has very much, such as lime/lime stone-gypsum, sodium-hydroxide method, sodium sulfite Method, magnesium oxide method, peroxide passivation, ammonia process etc..The desulfurization wastewater that wherein magnesium oxide method desulfurization is formed contains a large amount of magnesium sulfate, shape Biochemical method is not easily passed through into high-salt wastewater, magnesium resource is caused to waste if direct emission.It is provided in view of magnesium in desulfurization wastewater The recycling of ammonium in source and high ammonia-nitrogen wastewater, the present invention are that one kind can using desulfurization wastewater processing ammonia nitrogen waste water and recycling Capable technology.
Invention content
Present invention aims at provide a kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater.
Based on above-mentioned purpose, the present invention takes following technical scheme：
A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater, includes the following steps：
（1）After the oxidized magnesium processes desulfurization of industrial smoke, desulfurization wastewater is obtained；Under stirring condition, by desulfurization wastewater and ammonia nitrogen waste water Mixing, it is 3 ~ 6 to adjust its pH value, is stood, and generates ammonium sulfate magnesium precipitate, separation of solid and liquid；
（2）By the ammonium sulfate magnesium after separation（(NH4)2Mg(SO4)2·6H2O）Deposition and purification obtains the raw material of slow release fertilizer.
Main component is magnesium sulfate in the desulfurization wastewater, in ammonia nitrogen waste water main component include ammonium ion and sulfate radical from Son, NH in composite waste4 +、Mg2+、SO4 2-Molar concentration rate be (2~6) ︰（2~4）︰ 1.
Step 1）Separation of solid and liquid is filtering interception, gravitational settling or centrifugation.
Step 2）Using ethyl alcohol cleaning, centrifugation, ultra-pure water cleaning, centrifugation repeat to use ammonium sulfate magnesium precipitate after separation Ethyl alcohol, centrifuges 3-5 times ultra-pure water cleaning.
Step 1）Speed of agitator is 400-800 r/min, mixing time 1-3h；Time of repose is 20-40min.
The reaction process of magnesium oxide method desulfurization and desulfurization wastewater and ammonia nitrogen waste water is as follows：
MgO+H2O → Mg (OH)2 (1)
Mg (OH)2+SO2 → MgSO3+ H2O (2)
2MgSO3+O2 → 2MgSO4 (3)
MgSO4+(NH4)2SO4+6H2O → (NH4)2Mg(SO4)2·6H2O↓ (4)
Compared with prior art, the invention has the advantages that：
1）High-salt wastewater is formed containing a large amount of magnesium sulfate in the desulfurization wastewater that the present invention is formed using magnesium oxide method desulfurization, and it is high Ammonium sulfate magnesium precipitate is generated, is effectively removed containing a large amount of ammonium ion and sulfate ion, the two mixing in ammonia nitrogen waste water The ammonium ion and sulfate ion in magnesium sulfate and high ammonia-nitrogen wastewater in desulfurization wastewater, subsequent processing, reduction conducive to waste water Expense cost；
2）The treatment of wastes with processes of wastes against one another, and magnesium, nitrogen, Sulphur ressource are recycled, as the raw material of slow-release fertilizer, improve economic well-being of workers and staff.
Description of the drawings
Fig. 1 is the XRD diagram of sediment of the invention, magnesium sulfate, ammonium sulfate and ammonium sulfate magnesium standard diagram.
Specific embodiment
Embodiment 1
A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater, includes the following steps：
（1）By industrial smoke（The coal-burning boiler used in process of production from a certain chemical fertilizer factory, to contain SO2Exhaust gas）It is oxidized After magnesium processes desulfurization, desulfurization wastewater is obtained, main component is magnesium sulfate in the desulfurization wastewater, and magnesium sulfate concentration is 1200 mg/L；Nitrogen Ammonia nitrogen waste water is generated in fertile production process, ammonia nitrogen concentration is 850 mg/L in ammonia nitrogen waste water, and sulfate concentration is 1800 mg/L, In speed of agitator under the conditions of 450 r/min, desulfurization wastewater is mixed with ammonia nitrogen waste water, NH in composite waste is controlled4 +、Mg2+、 SO4 2-Molar concentration rate be NH4 +︰ Mg2+︰ SO4 2-1 ︰ 3.1 of=5.2 ︰ stir 2h, and the pH value that composite waste is adjusted with sulfuric acid is 4.8,30min is stood, generates ammonium sulfate magnesium precipitate, separation of solid and liquid（Gravity settling separation）, ammonia nitrogen concentration in the waste water after separation 50 mg/L or so are down to, the concentration of magnesium sulfate is down to 100 mg/L or so, into subsequent treatment process；
（2）By the ammonium sulfate magnesium after separation（(NH4)2Mg(SO4)2·6H2O）Precipitation is cleaned using ethyl alcohol, centrifugation, and ultra-pure water is clear It washes, centrifuge, repeat using ethyl alcohol, ultra-pure water cleaning, centrifuge 5 times, obtain the raw material of slow release fertilizer.
After measured, step 1）In the mixed recyclable 2.9 kg (NH of waste water per ton4)2Mg(SO4)2·6H2O is precipitated.
Embodiment 2
A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater, includes the following steps：
（1）By industrial smoke（From Henan Lead-zinc Smelting Enterprises, in art production process, the smelting of nonferrous metallic ores Generate a large amount of middle low concentration SO2Exhaust gas）Oxidized magnesium processes desulfurization（Wet-type magnesium method desulfurization）Afterwards, desulfurization wastewater, the desulfurization are obtained Main component is magnesium sulfate in waste water, and magnesium sulfate concentration is 1800 mg/L；It is produced in its mating ammonium sulfate fertilizer factory production process Raw ammonia nitrogen waste water, main component includes ammonium ion and sulfate ion in ammonia nitrogen waste water, and ammonia nitrogen concentration is 980 mg/L, sulfate radical A concentration of 2620 mg/L, in speed of agitator under the conditions of 520 r/min, desulfurization wastewater is mixed with ammonia nitrogen waste water, control is mixed Close NH in waste water4 +、Mg2+、SO4 2-Molar concentration rate be NH4 +︰ Mg2+︰ SO4 2-1 ︰ 2.7 of=4 ︰ stir 2h, its pH are adjusted with sulfuric acid It is 5.5 to be worth, and stands 30min, generates ammonium sulfate magnesium precipitate, is centrifuged, and ammonia nitrogen concentration is down to 50 mg/L in the waste water after separation Left and right, the concentration of magnesium sulfate is down to 100 mg/L or so, into subsequent treatment process；
（2）By the ammonium sulfate magnesium after separation（(NH4)2Mg(SO4)2·6H2O）Precipitation is cleaned using ethyl alcohol, centrifugation, and ultra-pure water is clear It washes, centrifuge, repeat using ethyl alcohol, ultra-pure water cleaning, centrifuge 3 times, obtain the raw material of slow release fertilizer.
After measured, step 1）In the mixed recyclable 4.54 kg (NH of waste water per ton4)2Mg(SO4)2·6H2O is precipitated.
By (NH made from embodiment4)2Mg(SO4)2·6H2O precipitations carry out X-ray diffraction, and collection of illustrative plates is as shown in Figure 1.
From fig. 1, it can be seen that the sediment has good crystallinity, MgSO4Diffraction maximum, also have in sediment corresponding Diffraction maximum, (NH4)2SO4Diffraction maximum have corresponding diffraction maximum in precipitation.The diffraction maximum of sediment and (NH4)2Mg(SO4)2· 6H2The standard PDF cards of O compare, and find the diffraction maximum and (NH of sediment4)2Mg(SO4)2·6H2The standard PDF cards of O Diffraction maximum is very much like, thus proves, which is (NH4)2Mg(SO4)2·6H2O。

Claims (5)

  1. A kind of 1. method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater, which is characterized in that include the following steps：
    （1）After the oxidized magnesium processes desulfurization of industrial smoke, desulfurization wastewater is obtained；Under stirring condition, by desulfurization wastewater and ammonia nitrogen waste water Mixing, it is 3 ~ 6 to adjust its pH value, is stood, and generates ammonium sulfate magnesium precipitate, separation of solid and liquid；
    （2）Ammonium sulfate magnesium precipitate after separation is purified, obtains the raw material of slow release fertilizer.
  2. 2. the method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater according to claims 1, feature It is, main component is magnesium sulfate in the desulfurization wastewater, and main component includes ammonium ion and sulfate ion in ammonia nitrogen waste water, NH in composite waste4 +、SO4 2-、Mg2+Molar concentration rate be (2~6) ︰（2~4）︰ 1.
  3. 3. the method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater according to claims 2, feature It is, step 1）Separation of solid and liquid is filtering interception, gravitational settling or centrifugation.
  4. 4. the method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater according to claims 3, feature It is, step 2）Using ethyl alcohol cleaning, centrifugation, ultra-pure water cleaning, centrifugation are repeated using second ammonium sulfate magnesium precipitate after separation Alcohol, centrifuges 3-5 times ultra-pure water cleaning.
  5. 5. the method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater according to claims 4, feature It is, step 1）Speed of agitator is 400-800 r/min, mixing time 1-3h；Time of repose is 20-40min.
CN201810081977.9A 2018-01-17 2018-01-29 A kind of method that high-concentration ammonia nitrogenous wastewater and recycling are handled with desulfurization wastewater Pending CN108164046A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174174A (en) * 2020-09-18 2021-01-05 东江环保股份有限公司 Method for preparing magnesium ammonium sulfate hexahydrate by recycling copper-containing electroplating wastewater
CN114506974A (en) * 2022-02-10 2022-05-17 内蒙古科技大学包头师范学院 Chemical and biological method for synchronous resource recovery treatment of three kinds of rare earth metallurgical wastewater

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1554595A (en) * 2003-12-30 2004-12-15 尹德文 Method for treating magnesium sulfate mather slution after producing boric acid by sulfuric acid method
EP2657319A1 (en) * 2012-04-27 2013-10-30 K+S KALI GmbH Composition based on magnesium sulphate and diammonium hydrogen phosphate
CN104803400A (en) * 2014-01-24 2015-07-29 中国科学院过程工程研究所 Ammonium magnesium sulfate preparation method
CN105040038A (en) * 2015-07-08 2015-11-11 长沙矿冶研究院有限责任公司 Method for carrying out demagging on electrolytic manganese anolyte with ammonium sulfate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1554595A (en) * 2003-12-30 2004-12-15 尹德文 Method for treating magnesium sulfate mather slution after producing boric acid by sulfuric acid method
EP2657319A1 (en) * 2012-04-27 2013-10-30 K+S KALI GmbH Composition based on magnesium sulphate and diammonium hydrogen phosphate
CN104803400A (en) * 2014-01-24 2015-07-29 中国科学院过程工程研究所 Ammonium magnesium sulfate preparation method
CN105040038A (en) * 2015-07-08 2015-11-11 长沙矿冶研究院有限责任公司 Method for carrying out demagging on electrolytic manganese anolyte with ammonium sulfate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
吕天宝: "《工业脱硫及综合利用技术》", 30 April 2011 *
郭如新: ""硫酸盐型硫肥及其在农业中的应用"", 《硫磷设计与粉体工程》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174174A (en) * 2020-09-18 2021-01-05 东江环保股份有限公司 Method for preparing magnesium ammonium sulfate hexahydrate by recycling copper-containing electroplating wastewater
CN114506974A (en) * 2022-02-10 2022-05-17 内蒙古科技大学包头师范学院 Chemical and biological method for synchronous resource recovery treatment of three kinds of rare earth metallurgical wastewater

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