WO2023165020A1 - 一种氨氮废水脱氨处理的方法 - Google Patents

一种氨氮废水脱氨处理的方法 Download PDF

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WO2023165020A1
WO2023165020A1 PCT/CN2022/092512 CN2022092512W WO2023165020A1 WO 2023165020 A1 WO2023165020 A1 WO 2023165020A1 CN 2022092512 W CN2022092512 W CN 2022092512W WO 2023165020 A1 WO2023165020 A1 WO 2023165020A1
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ammonia
ammonia nitrogen
nitrogen wastewater
wastewater
stripping
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PCT/CN2022/092512
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English (en)
French (fr)
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陈琪
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无锡中天固废处置有限公司
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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
    • 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
    • C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/448—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by pervaporation
    • 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
    • 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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Definitions

  • the embodiment of the present application relates to the technical field of wastewater treatment, for example, a method for deammonization treatment of ammonia nitrogen wastewater.
  • ammonia nitrogen pollution will cause great harm to human health and the ecological environment.
  • Ammonia nitrogen is one of the main oxygen-consuming pollutants in water bodies. If it is directly discharged into water bodies, it will easily cause eutrophication of water bodies.
  • Ammonia nitrogen wastewater is produced in a large amount, mainly including industrial wastewater and domestic sewage. The former comes from petrochemical, metallurgy, pharmaceutical, chemical fertilizer, electronics and other industries.
  • ammonia nitrogen wastewater also includes secondary effluent from waste treatment plants, etc., including Ammonia nitrogen wastewater needs to be treated with ammonia nitrogen removal technology before it can be discharged.
  • common ammonia nitrogen removal methods include biological method, air stripping and stripping method, chemical precipitation method, breakpoint chlorine addition method and supported gas film method, etc.
  • Biological denitrification method is the most commonly used method. It mainly uses microorganisms to convert ammonia nitrogen in water into non-toxic and harmless nitrogen under the action of biochemical treatment such as anaerobic, anoxic or aerobic. This method has relatively high requirements for wastewater quality.
  • ammonia stripping and stripping process is simple, and the treatment effect is stable, but the energy consumption is high, the cost is high, and it is easy to cause secondary pollution , requires frequent disassembly and cleaning; chemical precipitation and breakpoint chlorination can effectively remove ammonia nitrogen in wastewater, but will introduce new compounds, which may cause secondary pollution and affect the reusability of wastewater; supported air film method Although the concentration of ammonia nitrogen can be sufficiently reduced, water seepage is usually serious, and it is difficult to obtain desired by-products.
  • CN 101318752A discloses a method and device for recycling ammonia nitrogen wastewater, the method comprising: adjusting the pH value of ammonia nitrogen wastewater in an automatic dosing device, preheating in a preheating device; uniformly distributing water through a spraying device in the removal section and collecting it in the In the liquid storage area at the bottom, after the ammonia is blown off by forced air blast, the wastewater is repeatedly removed from the ammonia in the circulating spray system, and then discharged from the outlet weir after purification; the ammonia-containing waste gas is filtered by the demisting device and then sprayed in several stages to absorb it into ammonia water The crude product is recovered, and the purge gas is evacuated from the top. In this method, the ammonia nitrogen wastewater is sprayed and then blown off by blasting, and the waste gas is sprayed and absorbed after passing through the demisting device. Limited, and there are fewer types of wastewater suitable for treatment.
  • CN 108706672A discloses a method for recycling ammonia nitrogen wastewater, which includes the following steps: adjusting the pH of ammonia nitrogen wastewater to 10-12, degassing with a deamination membrane, and then absorbing it through an acid solution to obtain deamination wastewater and ammonia salt solution; Air is passed into the ammonia salt solution for blowing off, and the blown off raffinate I and ammonia-containing mixed gas I are obtained; the absorption liquid is used to go through the shell to absorb the ammonia-containing mixed gas I, and ammonia water is obtained; air is passed into the ammonia water for blowing Take off to obtain stripping raffinate II and ammonia-containing mixed gas II; the ammonia-containing mixed gas II is absorbed by the ammonia water obtained in the previous step to obtain high-quality ammonia water.
  • This method only adopts deamination membrane degassing and then absorption for the treatment of ammonia nitrogen wastewater, and the subsequent treatment is the treatment of the ammonia salt solution obtained after the absorption of ammonia gas, which is equivalent to only one deamination treatment of the initial waste liquid, and there is no Combination process deamination of ammonia nitrogen wastewater, the removal rate of ammonia nitrogen is low, and is greatly affected by the type of wastewater.
  • An embodiment of the present application provides a method for deamination treatment of ammonia nitrogen wastewater.
  • the method adopts a combined process for deamination treatment.
  • the combined process adopts air stripping, stripping stripping and osmotic deamination in sequence.
  • the method enables the ammonia nitrogen in the waste water to adopt a suitable treatment process at different concentrations to achieve a higher removal rate of ammonia nitrogen.
  • the overall cost of the method is low, the treatment capacity is large, and secondary pollution will not be caused.
  • An embodiment of the present application provides a method for deammonization treatment of ammonia nitrogen wastewater, the method comprising the following steps:
  • step (3) The secondary ammonia-nitrogen wastewater obtained in step (2) is subjected to osmotic deamination to obtain treated ammonia-nitrogen wastewater.
  • the combination of the above operations and the selection of the sequence are all selected within the range of ammonia nitrogen concentration suitable for treatment, and
  • the operation of each step is relatively simple, the cost is low, the removal rate of ammonia nitrogen is high, and the remaining components can be recycled; the method has a large treatment rate and treatment capacity for wastewater, and is suitable for treating various types of ammonia nitrogen-containing wastewater, and will not cause secondary pollution.
  • the source of the ammonia-nitrogen wastewater to be treated in step (1) includes any one or a combination of at least two of landfill leachate, ammonia-containing waste gas treatment absorption liquid or ammonium-containing waste liquid produced by smelting, Typical but non-limiting examples of the combination include: the combination of landfill leachate and ammonia-containing waste gas treatment absorption liquid, the combination of ammonia-containing waste gas treatment absorption liquid and ammonium-containing waste liquid produced by smelting, landfill leachate, ammonia-containing waste gas treatment absorption The combination of liquid and ammonium-containing waste liquid produced by smelting, etc.
  • the ammonia nitrogen content in the ammonia nitrogen wastewater to be treated in step (1) is 10-100g/L, such as 10g/L, 30g/L, 50g/L, 60g/L, 80g/L or 100g/L, etc., but It is not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the composition of the ammonia nitrogen wastewater to be treated in step (1) includes any one or a combination of at least two of ammonium sulfate, ammonium carbonate or ammonium chloride, and the typical but non-limiting examples of the combination are: ammonium sulfate and Combination of ammonium carbonate, combination of ammonium carbonate and ammonium chloride, combination of ammonium sulfate, ammonium carbonate and ammonium chloride, etc.
  • the adjustment of pH in step (1) is to adjust the pH value of ammonia nitrogen wastewater to 10-14, such as 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5 or 14, etc., but It is not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the purpose of adjusting the pH of ammonia nitrogen wastewater before treatment is to make ammonia nitrogen mainly exist in the form of NH 3 , which facilitates the subsequent removal of NH 3 .
  • the air stripping in step (1) is air circulation stripping.
  • the air stripping temperature in step (1) is 20-50°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, etc., but not limited to the listed ones Numerical values, other unlisted numerical values within this numerical range are also applicable.
  • the time for blowing off the air in step (1) is 0.5-2h, such as 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h or 2h, etc., but not limited to the listed values, the Other unrecited values within the range of values also apply.
  • the ammonia blown out of the air in step (1) is absorbed with water, and recovered to obtain aqueous ammonia.
  • the ammonia nitrogen content of the primary ammonia nitrogen wastewater in step (1) is 1-5g/L, such as 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5g/L, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
  • step (2) the stripping and stripping described in step (2) is carried out by steam stripping.
  • the stripping temperature in step (2) is 85°C to 105°C, such as 85°C, 90°C, 95°C, 100°C or 105°C, etc., but not limited to the listed values, the value range Other values not listed in the same applies.
  • the stripping time in step (2) is 0.1-0.5h, such as 0.1h, 0.2h, 0.25h, 0.33h, 0.4h, 0.45h or 0.5h, etc., but not limited to the listed
  • the numerical value of , other unlisted numerical values in this numerical range are also applicable.
  • the temperature of the steam is relatively high during stripping and stripping. Since the contact time with the waste water is not long, a small amount of steam cools down and turns into a liquid phase, and most of the steam is still taken out in the form of a gas phase.
  • the heat exchange of the air in the step (1) increases the temperature of the air, thereby increasing the amount of ammonia removed when the air is blown off.
  • the steam and the ammonia carried out after the stripping described in step (2) are first exchanged with the air used for the stripping in step (1), and then absorbed with water.
  • the ammonia nitrogen content of the secondary ammonia nitrogen wastewater in step (2) is 200-800ppm, such as 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm or 800ppm, etc., but not limited to the listed values, within the range of values Other values not listed also apply.
  • the pervasive deamination in step (3) is treated with a pervaporation membrane.
  • the permeation deamination temperature in step (3) is 20-40°C, such as 20°C, 25°C, 30°C, 35°C or 40°C, etc., but it is not limited to the listed values. Other values not listed also apply.
  • the pressure difference on both sides of the pervaporation membrane during the pervaporation deamination is 0.1-0.5MPa, such as 0.1MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa or 0.5MPa, etc., but not limited to For the listed values, other unlisted values within the range of values are also applicable.
  • the permeation of ammonia is driven by the gas partial pressure difference on both sides of the pervaporation membrane.
  • the material of the pervaporation membrane includes any one of ceramics, polyvinyl chloride (PVC) or polyvinyl alcohol (PVA), and the type of ceramics includes aluminosilicate, boroaluminate salt etc.
  • the ammonia molecules pass through the pervaporation membrane and enter the other side, are absorbed by the acid liquid, and maintain the pressure difference on both sides of the pervaporation membrane, and the liquid molecules do not pass through the pervaporation membrane to ensure the pervaporation
  • the vaporization process proceeds normally.
  • the ammonia nitrogen content in the ammonia nitrogen wastewater after the treatment in step (3) is reduced to below 15ppm, such as 15ppm, 12ppm, 10ppm, 8ppm, 6ppm, 4ppm or 2ppm, etc., but not limited to the listed values , other unlisted values within this value range are also applicable.
  • the composition of the treated ammonia nitrogen wastewater in step (3) includes sodium sulfate and/or sodium chloride.
  • the treated solution basically does not contain ammonia or ammonium ions, and the cations are mainly sodium ions or potassium ions.
  • the method includes the following steps:
  • (1) adjust the pH of the ammonia nitrogen wastewater to be treated, the ammonia nitrogen content in the ammonia nitrogen wastewater to be treated is 10 ⁇ 100g/L
  • the composition of the ammonia nitrogen wastewater includes any one or at least two of ammonium sulfate, ammonium carbonate or ammonium chloride
  • the ammonia that the air is stripped out is absorbed by water, and reclaims to obtain ammoniacal liquor;
  • step (2) The primary ammonia nitrogen waste water obtained in step (1) is stripped and stripped, and the stripped strip is stripped with steam, the temperature of the stripped stripped is 85 ⁇ 105°C, and the time is 0.1 ⁇ 0.5h, obtain secondary ammonia-nitrogen waste water, the ammonia nitrogen content of described secondary ammonia-nitrogen waste water is 200 ⁇ 800ppm;
  • the steam after described stripping blow-off and the ammonia that take out are first exchanged heat with the air used for step (1) blow-off, reabsorbed with water;
  • step (3) The secondary ammonia-nitrogen waste water obtained in step (2) is subjected to osmotic deamination, and the pervaporation membrane is used for processing the permeation deamination, and the temperature of the permeation deamination is 20 ⁇ 40° C.
  • the pressure difference is 0.1-0.5 MPa, and the material of the pervaporation membrane includes any one of ceramics, polyvinyl chloride or polyvinyl alcohol.
  • the ammonia molecules pass through the pervaporation membrane and enter the other side , is absorbed by the acid solution to maintain the pressure difference on both sides of the pervaporation membrane, and the rest is treated ammonia nitrogen wastewater, and the ammonia nitrogen content in the treated ammonia nitrogen wastewater is reduced to below 15ppm.
  • the method described in the embodiment of the application adopts a combined process to carry out deammonification treatment according to the composition of the ammonia nitrogen wastewater, and the combined process adopts the methods of air stripping, stripping stripping and osmotic deamination successively, so that the ammonia nitrogen in the waste water can be Adopt appropriate treatment process at different concentrations to achieve higher ammonia nitrogen removal rate, which can reach more than 99.9%;
  • the method described in the embodiment of the present application is simple in operation and low in cost, and is suitable for treating various types of ammonia-nitrogen-containing wastewater with a large treatment capacity and will not cause secondary pollution.
  • Fig. 1 is a process flow diagram of the method for ammonia nitrogen wastewater deammonification treatment provided in Example 1 of the present application.
  • ammonia molecules pass through the pervaporation membrane and enter the other side to be absorbed by sulfuric acid, and the rest is treated ammonia nitrogen wastewater, the ammonia nitrogen content in the treated ammonia nitrogen wastewater is reduced to 5ppm.
  • the deamination rate of ammonia nitrogen wastewater is high, which can reach 99.95%; the cost of the method is low, and there is no secondary pollution.
  • the present embodiment provides a method for deammonification treatment of ammonia nitrogen wastewater, the method comprising the following steps:
  • the source of the ammonia-nitrogen wastewater to be treated is the ammonium-containing waste liquid produced by smelting
  • the ammonia-nitrogen content in the ammonia-nitrogen wastewater is 100g/L
  • the composition of the ammonia-nitrogen wastewater includes ammonium sulfate and ammonium chloride
  • Adjust the pH to 14 and then carry out air stripping.
  • the temperature of the air stripping is 20° C. and the time is 2 hours to obtain primary ammonia nitrogen wastewater.
  • the ammonia nitrogen content of the primary ammonia nitrogen wastewater is 5 g/L; the air stripping out
  • the ammonia water is absorbed, reclaims and obtains ammonia water;
  • step (2) The primary ammonia nitrogen wastewater obtained in step (1) is stripped and stripped, the stripped stripped is stripped with steam, the temperature of the stripped stripped is 85 ° C, and the time is 0.5h, to obtain Secondary ammonia-nitrogen wastewater, the ammonia nitrogen content of the secondary ammonia-nitrogen wastewater is 600ppm; the steam after the stripping stripping and the ammonia carried out are first exchanged with the air used for stripping in step (1), and then absorbed by water;
  • step (3) The secondary ammonia-nitrogen waste water obtained in step (2) is subjected to osmotic deamination, and the pervaporation membrane is used for processing the permeation deamination, and the temperature of the permeation deamination is 20° C.
  • the material of the pervaporation membrane is aluminosilicate ceramics.
  • the deamination rate of ammonia nitrogen wastewater is high, which can reach 99.98%.
  • the method has low cost and no secondary pollution.
  • the present embodiment provides a method for deammonification treatment of ammonia nitrogen wastewater, the method comprising the following steps:
  • step (2) The primary ammonia nitrogen waste water obtained in step (1) is stripped and stripped, the stripped stripped is stripped with steam, the temperature of the stripped stripped is 100°C, and the time is 0.2h, to obtain Secondary ammonia-nitrogen wastewater, the ammonia nitrogen content of the secondary ammonia-nitrogen wastewater is 300ppm; the steam after the stripping stripping and the ammonia carried out are first exchanged with the air used for stripping off in step (1), and then absorbed by water;
  • step (3) The secondary ammonia nitrogen wastewater obtained in step (2) is subjected to osmotic deamination, and the pervaporation membrane is used for processing the permeation deamination, and the temperature of the permeation deamination is 25° C., and the pressure difference on both sides of the pervaporation membrane is The material of the pervaporation membrane is polyvinyl alcohol. During the pervaporation deamination, ammonia molecules pass through the pervaporation membrane and enter the other side to be absorbed by hydrochloric acid. The remaining is ammonia nitrogen wastewater after treatment. The ammonia nitrogen content in the post-ammonia nitrogen wastewater is reduced to 10ppm.
  • the deamination rate of ammonia nitrogen wastewater is high, which can reach 99.96%.
  • the method has low cost and no secondary pollution.
  • the present embodiment provides a method for deammonification treatment of ammonia nitrogen wastewater, the method comprising the following steps:
  • the source of the ammonia-nitrogen wastewater to be treated is the ammonia-containing waste gas treatment absorption liquid
  • the ammonia nitrogen content in the ammonia-nitrogen wastewater is 75g/L
  • the composition of the ammonia-nitrogen wastewater includes ammonium chloride, adjust the pH to 11 , and then carry out air blow-off, the temperature of described air blow-off is 40 °C, and the time is 1.25h, obtains primary ammonia nitrogen waste water, and the ammonia nitrogen content of described primary ammonia nitrogen waste water is 3.6g/L
  • the ammonia nitrogen that described air blow off comes out Absorbed with water, recovered to obtain ammonia water;
  • step (2) The primary ammonia nitrogen waste water obtained in step (1) is stripped and stripped, the stripped stripped is stripped with steam, the temperature of the stripped stripped is 90°C, and the time is 0.4h, to obtain Secondary ammonia-nitrogen wastewater, the ammonia-nitrogen content of the secondary ammonia-nitrogen wastewater is 500ppm; the steam after the stripping stripping and the ammonia carried out first exchange heat with the air used for stripping off in step (1), and then absorb it with water;
  • step (3) The secondary ammonia nitrogen wastewater obtained in step (2) is subjected to osmotic deamination, and the osmotic deamination is processed by a pervaporation membrane, and the temperature of the osmotic deamination is 35° C. is 0.4MPa, and the material of the pervaporation membrane is polyvinyl chloride.
  • the pervaporation deamination ammonia molecules pass through the pervaporation membrane and enter the other side to be absorbed by hydrochloric acid, and the rest is ammonia nitrogen wastewater after treatment.
  • the ammonia nitrogen content in the post-ammonia nitrogen wastewater was reduced to 9ppm.
  • the deamination rate of ammonia nitrogen wastewater is high, which can reach 99.99%.
  • the method has low cost and no secondary pollution.
  • the method described in the application adopts a combined process for deamination treatment according to the composition of the ammonia nitrogen wastewater, and the combined process adopts the methods of air stripping, stripping stripping and osmotic deamination successively, so that the waste water
  • the ammonia nitrogen can adopt suitable treatment process at different concentrations to achieve a higher removal rate of ammonia nitrogen, which can reach more than 99.9%; the method is simple to operate, low in cost, suitable for treating various types of ammonia nitrogen-containing wastewater, and has a large processing capacity , will not cause secondary pollution.
  • the present application uses the above-mentioned embodiments to illustrate the detailed devices and methods of the present application, but the present application is not limited to the above-mentioned detailed devices and methods, that is, it does not mean that the present application must rely on the above-mentioned detailed devices and methods to be implemented.
  • Those skilled in the art should understand that any improvement to the application, equivalent replacement of the device of the application, addition of auxiliary devices, selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.

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Abstract

一种氨氮废水脱氨处理的方法，包括以下步骤：将待处理氨氮废水调节pH后进行空气吹脱，得到一次氨氮废水；将一次氨氮废水进行汽提吹脱，得到二次氨氮废水；将二次氨氮废水进行渗透脱氨，得到处理后氨氮废水。根据氨氮废水的组成采用组合工艺进行脱氨处理，使得废水中的氨氮能够在不同浓度时采用合适的处理工艺，以实现更高的氨氮去除率。

Description

一种氨氮废水脱氨处理的方法 技术领域
本申请实施例涉及废水处理技术领域，例如一种氨氮废水脱氨处理的方法。
背景技术
作为常见的水体和大气污染，氨氮污染对人类健康和生态环境都会产生极大的危害，氨氮是水体中的主要耗氧污染物之一，若直接排入水体，容易引起水体的富营养化。氨氮废水产生量较大，主要包括工业废水及生活污水，前者来自于石油化工、冶金、制药、化肥、电子等行业，除此之外，氨氮废水还包括垃圾处理厂的次级出水等，含氨氮废水需要采用氨氮脱除技术进行处理后才能排放。
目前，常见的氨氮脱除方法有生物法、吹脱及汽提法、化学沉淀法、折点加氯法和支撑气膜法等。生物脱氮法是其中最常用的方法，主要是利用微生物在厌氧、缺氧或好氧等生化处理作用下，使水中氨氮物质转化为无毒无害的氮气，该方法对废水水质要求较高，不适合低有机物、高浓度、高盐分、难降解的工业废水的脱氮；氨吹脱、汽提工艺流程简单、处理效果稳定，但能耗大、成本较高，容易导致二次污染，需要经常拆卸和清洗；化学沉淀法和折点加氯法可有效去除废水中的氨氮，但会引入新的化合物，有可能造成二次污染，影响废水的可回用性；支撑气膜法虽然能够将氨氮浓度充分降低，但通常水的渗透现象严重，难得到期待的副产品。
CN 101318752A公开了一种氨氮废水回用处理方法及装置，该方法包括：氨氮废水在自动加药装置调节pH值，在预热装置预热；经脱除工段喷淋装置均匀布水并汇集于底部储液区，采用强制鼓风将氨吹脱后，废水在循环喷淋系统重复脱除氨，净化后由出水堰排出；含氨废气经除雾装置过滤后进行若干级喷淋吸收成氨水粗品回收，净化气体从顶部排空。该方法将氨氮废水喷淋后鼓风吹脱，废气经除雾装置后喷淋吸收，该方法主要是采用吹脱及喷淋操作，未采用多种工艺组合的方式，对氨氮的脱除率有限，适合处理的废水种类较少。
CN 108706672A公开了一种氨氮废水的资源化处理方法，包括以下步骤：将氨氮废水的pH调节至10～12，采用脱氨膜脱气后通过酸液吸收，得到脱氨废 水和氨盐溶液；向氨盐溶液通入空气进行吹脱，得到吹脱残液I和含氨混合气I；采用吸收液走壳程对含氨混合气I进行吸收，得到氨水；向该氨水通入空气进行吹脱，得到吹脱残液II和含氨混合气II；通过上一步得到的氨水对含氨混合气II进行吸收，得到高质量浓度的氨水。该方法针对氨氮废水的处理只采用脱氨膜脱气后吸收，后续的处理均是对氨气吸收后所得氨盐溶液的处理，相当于对初始废液只进行了一次脱氨处理，并没有对氨氮废水进行组合工艺脱氨，氨氮去除率较低，且受废水种类影响较大。
综上所述，对于氨氮废水的处理，还需要根据废水的组成及氨氮含量，选择合适的组合工艺及其顺序，使之适合处理相应浓度下的废水，总体处理成本较低，氨氮脱除率高。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请一实施例提供一种氨氮废水脱氨处理的方法，所述方法根据氨氮废水的组成采用组合工艺进行脱氨处理，所述组合工艺依次采用空气吹脱、汽提吹脱和渗透脱氨的方法，使得废水中的氨氮能够在不同浓度时采用合适的处理工艺，以达到更高的氨氮去除率，同时所述方法的整体成本较低，处理量大，不会造成二次污染。
本申请一实施例提供了一种氨氮废水脱氨处理的方法，所述方法包括以下步骤：
(1)将待处理氨氮废水调节pH后进行空气吹脱，得到一次氨氮废水；
(2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，得到二次氨氮废水；
(3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，得到处理后氨氮废水。
本申请中，对于氨氮废水的处理，废水中氨氮浓度较高时，单一的处理方法往往难以充分脱除氨氮，因而通常需要采用组合工艺，本申请中根据氨氮废水的组成及浓度，选择而合适的组合工艺，首先将废水调节至适合氨气脱除的pH值，在氨氮含量较高时先采用空气吹脱的方式，操作简便，成本较低，去除大量的氨氮，然后采用汽提吹脱，利用蒸汽的温度等特性将废水中氨进一步带 出，最终再采用渗透汽化的方式脱氨，上述操作的组合及其顺序的选择，均是在其适宜处理的氨氮浓度范围内选择的，且各步操作均较为简单，成本较低，氨氮的脱除率高，剩余组分能够回收利用；所述方法对废水的处理速率及处理量大，适合处理多种类的含氨氮废水，且不会造成二次污染。
以下作为本申请优选的技术方案，但不作为本申请提供的技术方案的限制，通过以下技术方案，可以更好地达到和实现本申请的技术目的和有益效果。
作为本申请优选的技术方案，步骤(1)所述待处理氨氮废水的来源包括垃圾渗滤液、含氨废气处理吸收液或冶炼产生的含铵废液中任意一种或至少两种的组合，所述组合典型但非限制性实例有：垃圾渗滤液和含氨废气处理吸收液的组合，含氨废气处理吸收液和冶炼产生的含铵废液的组合，垃圾渗滤液、含氨废气处理吸收液和冶炼产生的含铵废液的组合等。
优选地，步骤(1)所述待处理氨氮废水中氨氮含量为10～100g/L，例如10g/L、30g/L、50g/L、60g/L、80g/L或100g/L等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述待处理氨氮废水的组成包括硫酸铵、碳酸铵或氯化铵中任意一种或至少两种的组合，所述组合典型但非限制性实例有：硫酸铵和碳酸铵的组合，碳酸铵和氯化铵的组合，硫酸铵、碳酸铵和氯化铵的组合等。
作为本申请优选的技术方案，步骤(1)所述调节pH为将氨氮废水的pH值调节至10～14，例如10、10.5、11、11.5、12、12.5、13、13.5或14等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请中，氨氮废水在处理前调节pH的目的在于使得氨氮主要以NH 3的形式存在，便于后续NH 3的脱除。
优选地，步骤(1)所述空气吹脱为采用空气循环吹脱。
优选地，步骤(1)所述空气吹脱的温度为20～50℃，例如20℃、25℃、30℃、35℃、40℃、45℃或50℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(1)所述空气吹脱的时间为0.5～2h，例如0.5h、0.8h、1h、1.2h、1.5h、1.8h或2h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，步骤(1)所述空气吹脱出来的氨用水吸收， 回收得到氨水。
优选地，步骤(1)所述一次氨氮废水的氨氮含量为1～5g/L，例如1g/L、1.5g/L、2g/L、2.5g/L、3g/L、3.5g/L、4g/L、4.5g/L或5g/L等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，步骤(2)所述汽提吹脱为采用蒸汽进行吹脱。
优选地，步骤(2)所述汽提吹脱的温度为85～105℃，例如85℃、90℃、95℃、100℃或105℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(2)所述汽提吹脱的时间为0.1～0.5h，例如0.1h、0.2h、0.25h、0.33h、0.4h、0.45h或0.5h等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请中，汽提吹脱时蒸汽温度较高，由于与废水接触时间不长，少量蒸汽降温变为液相，大部分仍是以气相形式将氨带出，在采用水吸收氨之前先与步骤(1)中的空气换热，提高空气的温度，从而能够提高空气吹脱时氨的去除量。
作为本申请优选的技术方案，步骤(2)所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收。
优选地，步骤(2)所述二次氨氮废水的氨氮含量为200～800ppm，例如200ppm、300ppm、400ppm、500ppm、600ppm、700ppm或800ppm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，步骤(3)所述渗透脱氨采用渗透汽化膜进行处理。
优选地，步骤(3)所述渗透脱氨的温度为20～40℃，例如20℃、25℃、30℃、35℃或40℃等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，所述渗透脱氨时渗透汽化膜两侧的压差为0.1～0.5MPa，例如0.1MPa、0.2MPa、0.25MPa、0.3MPa、0.35MPa、0.4MPa或0.5MPa等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
本申请中，所述渗透脱氨过程中，氨气的渗透是以渗透汽化膜两侧的气体分压差作为推动力。
作为本申请优选的技术方案，所述渗透汽化膜的材质包括陶瓷、聚氯乙烯(PVC)或聚乙烯醇(PVA)中任意一种，所述陶瓷的种类包括硅铝酸盐、硼铝酸盐等。
优选地，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧，被酸液吸收，维持渗透汽化膜两侧的压差，液体分子不透过渗透汽化膜，以保证渗透汽化过程正常进行。
作为本申请优选的技术方案，步骤(3)所述处理后氨氮废水中氨氮含量降至15ppm以下，例如15ppm、12ppm、10ppm、8ppm、6ppm、4ppm或2ppm等，但并不仅限于所列举的数值，该数值范围内其他未列举的数值同样适用。
优选地，步骤(3)所述处理后氨氮废水的组成包括硫酸钠和/或氯化钠。
本申请中，所述氨氮废水脱氨后，根据pH调节时所用碱的种类，处理后溶液基本不含氨或铵根离子，阳离子以钠离子或钾离子为主。
作为本申请优选的技术方案，所述方法包括以下步骤：
(1)将待处理氨氮废水调节pH，所述待处理氨氮废水中氨氮含量为10～100g/L，氨氮废水的组成包括硫酸铵、碳酸铵或氯化铵中任意一种或至少两种的组合，调节pH至10～14，然后进行空气吹脱，所述空气吹脱的温度为20～50℃，时间为0.5～2h，得到一次氨氮废水，所述一次氨氮废水的氨氮含量为1～5g/L；所述空气吹脱出来的氨用水吸收，回收得到氨水；
(2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，所述汽提吹脱为采用蒸汽进行吹脱，所述汽提吹脱的温度为85～105℃，时间为0.1～0.5h，得到二次氨氮废水，所述二次氨氮废水的氨氮含量为200～800ppm；所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
(3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，所述渗透脱氨采用渗透汽化膜进行处理，所述渗透脱氨的温度为20～40℃，渗透汽化膜两侧的压差为0.1～0.5MPa，所述渗透汽化膜的材质包括陶瓷、聚氯乙烯或聚乙烯醇中任意一种，所述渗透脱氨时，氨气分子氨穿过渗透汽化膜进入另一侧，被酸液吸收，维持渗透汽化膜两侧的压差，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至15ppm以下。
与相关技术相比，本申请实施例具有以下有益效果：
(1)本申请实施例所述方法根据氨氮废水的组成采用组合工艺进行脱氨处 理，所述组合工艺依次采用空气吹脱、汽提吹脱和渗透脱氨的方法，使得废水中的氨氮能够在不同浓度时采用合适的处理工艺，以实现更高的氨氮去除率，可以达到99.9％以上；
(2)本申请实施例所述方法操作简单，成本较低，适合处理多种类的含氨氮废水，处理量大，不会造成二次污染。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是本申请实施例1提供的氨氮废水脱氨处理的方法的工艺流程图。
具体实施方式
渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧被硫酸吸收，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至5ppm。
本申请中，经过上述组合脱氨处理工艺，氨氮废水的脱氨率较高，可以达到99.95％；所述方法成本较低，无二次污染。
实施例3：
本实施例提供了一种氨氮废水脱氨处理的方法，所述方法包括以下步骤：
(1)将待处理氨氮废水调节pH，所述待处理氨氮废水的来源为冶炼产生的含铵废液，氨氮废水中氨氮含量为100g/L，氨氮废水的组成包括硫酸铵和氯化铵，调节pH至14，然后进行空气吹脱，所述空气吹脱的温度为20℃，时间为2h，得到一次氨氮废水，所述一次氨氮废水的氨氮含量为5g/L；所述空气吹脱出来的氨用水吸收，回收得到氨水；
(2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，所述汽提吹脱为采用蒸汽进行吹脱，所述汽提吹脱的温度为85℃，时间为0.5h，得到二次氨氮废水，所述二次氨氮废水的氨氮含量为600ppm；所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
(3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，所述渗透脱氨采用 渗透汽化膜进行处理，所述渗透脱氨的温度为20℃，渗透汽化膜两侧的压差为0.5MPa，所述渗透汽化膜的材质为硅铝酸盐陶瓷，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧被硫酸吸收，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至15ppm。
本申请中，经过上述组合脱氨处理工艺，氨氮废水的脱氨率较高，可以达到99.98％；所述方法成本较低，无二次污染。
实施例4：
本实施例提供了一种氨氮废水脱氨处理的方法，所述方法包括以下步骤：
(1)将待处理氨氮废水调节pH，所述待处理氨氮废水的来源为垃圾渗滤液，氨氮废水中氨氮含量为30g/L，氨氮废水的组成包括碳酸铵，调节pH至13，然后进行空气吹脱，所述空气吹脱的温度为25℃，时间为1.5h，得到一次氨氮废水，所述一次氨氮废水的氨氮含量为1.8g/L；所述空气吹脱出来的氨用水吸收，回收得到氨水；
(2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，所述汽提吹脱为采用蒸汽进行吹脱，所述汽提吹脱的温度为100℃，时间为0.2h，得到二次氨氮废水，所述二次氨氮废水的氨氮含量为300ppm；所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
(3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，所述渗透脱氨采用渗透汽化膜进行处理，所述渗透脱氨的温度为25℃，渗透汽化膜两侧的压差为0.2MPa，所述渗透汽化膜的材质为聚乙烯醇，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧被盐酸吸收，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至10ppm。
本申请中，经过上述组合脱氨处理工艺，氨氮废水的脱氨率较高，可以达到99.96％；所述方法成本较低，无二次污染。
实施例5：
本实施例提供了一种氨氮废水脱氨处理的方法，所述方法包括以下步骤：
(1)将待处理氨氮废水调节pH，所述待处理氨氮废水的来源为含氨废气处理吸收液，氨氮废水中氨氮含量为75g/L，氨氮废水的组成包括氯化铵，调节 pH至11，然后进行空气吹脱，所述空气吹脱的温度为40℃，时间为1.25h，得到一次氨氮废水，所述一次氨氮废水的氨氮含量为3.6g/L；所述空气吹脱出来的氨用水吸收，回收得到氨水；
(2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，所述汽提吹脱为采用蒸汽进行吹脱，所述汽提吹脱的温度为90℃，时间为0.4h，得到二次氨氮废水，所述二次氨氮废水的氨氮含量为500ppm；所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
(3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，所述渗透脱氨采用渗透汽化膜进行处理，所述渗透脱氨的温度为35℃，渗透汽化膜两侧的压差为0.4MPa，所述渗透汽化膜的材质为聚氯乙烯，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧被盐酸吸收，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至9ppm。
本申请中，经过上述组合脱氨处理工艺，氨氮废水的脱氨率较高，可以达到99.99％；所述方法成本较低，无二次污染。
综合上述实施例可以看出，本申请所述方法根据氨氮废水的组成采用组合工艺进行脱氨处理，所述组合工艺依次采用空气吹脱、汽提吹脱和渗透脱氨的方法，使得废水中的氨氮能够在不同浓度时采用合适的处理工艺，以实现更高的氨氮去除率，可以达到99.9％以上；所述方法操作简单，成本较低，适合处理多种类的含氨氮废水，处理量大，不会造成二次污染。
本申请通过上述实施例来说明本申请的详细装置与方法，但本申请并不局限于上述详细装置与方法，即不意味着本申请必须依赖上述详细装置与方法才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请装置的等效替换及辅助装置的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (12)

  1. 一种氨氮废水脱氨处理的方法，其包括以下步骤：
    (1)将待处理氨氮废水调节pH后进行空气吹脱，得到一次氨氮废水；
    (2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，得到二次氨氮废水；
    (3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，得到处理后氨氮废水。
  2. 根据权利要求1所述的方法，其中，步骤(1)所述待处理氨氮废水的来源包括垃圾渗滤液、含氨废气处理吸收液或冶炼产生的含铵废液中任意一种或至少两种的组合。
  3. 根据权利要求1所述的方法，其中，步骤(1)所述待处理氨氮废水中氨氮含量为10～100g/L。
  4. 根据权利要求1所述的方法，其中，步骤(1)所述待处理氨氮废水的组成包括硫酸铵、碳酸铵或氯化铵中任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的方法，其中，步骤(1)所述调节pH为将氨氮废水的pH值调节至10～14；
    优选地，步骤(1)所述空气吹脱为采用空气循环吹脱；
    优选地，步骤(1)所述空气吹脱的温度为20～50℃；
    优选地，步骤(1)所述空气吹脱的时间为0.5～2h。
  6. 根据权利要求1-5任一项所述的方法，其中，步骤(1)所述空气吹脱出来的氨用水吸收，回收得到氨水；
    优选地，步骤(1)所述一次氨氮废水的氨氮含量为1～5g/L。
  7. 根据权利要求1-6任一项所述的方法，其中，步骤(2)所述汽提吹脱为采用蒸汽进行吹脱；
    优选地，步骤(2)所述汽提吹脱的温度为85～105℃；
    优选地，步骤(2)所述汽提吹脱的时间为0.1～0.5h。
  8. 根据权利要求1-7任一项所述的方法，其中，步骤(2)所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
    优选地，步骤(2)所述二次氨氮废水的氨氮含量为200～800ppm。
  9. 根据权利要求1-8任一项所述的方法，其中，步骤(3)所述渗透脱氨采用渗透汽化膜进行处理；
    优选地，步骤(3)所述渗透脱氨的温度为20～40℃；
    优选地，所述渗透脱氨时渗透汽化膜两侧的压差为0.1～0.5MPa。
  10. 根据权利要求9所述的方法，其中，所述渗透汽化膜的材质包括陶瓷、聚氯乙烯或聚乙烯醇中任意一种；
    优选地，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧，被酸液吸收，维持渗透汽化膜两侧的压差。
  11. 根据权利要求1-10任一项所述的方法，其中，步骤(3)所述处理后氨氮废水中氨氮含量降至15ppm以下；
    优选地，步骤(3)所述处理后氨氮废水的组成包括硫酸钠和/或氯化钠。
  12. 根据权利要求1-11任一项所述的方法，其包括以下步骤：
    (1)将待处理氨氮废水调节pH，所述待处理氨氮废水中氨氮含量为10～100g/L，氨氮废水的组成包括硫酸铵、碳酸铵或氯化铵中任意一种或至少两种的组合，调节pH至10～14，然后进行空气吹脱，所述空气吹脱的温度为20～50℃，时间为0.5～2h，得到一次氨氮废水，所述一次氨氮废水的氨氮含量为1～5g/L；所述空气吹脱出来的氨用水吸收，回收得到氨水；
    (2)将步骤(1)得到的一次氨氮废水进行汽提吹脱，所述汽提吹脱为采用蒸汽进行吹脱，所述汽提吹脱的温度为85～105℃，时间为0.1～0.5h，得到二次氨氮废水，所述二次氨氮废水的氨氮含量为200～800ppm；所述汽提吹脱后的蒸汽和带出的氨先与步骤(1)吹脱所用空气换热，再用水吸收；
    (3)将步骤(2)得到的二次氨氮废水进行渗透脱氨，所述渗透脱氨采用渗透汽化膜进行处理，所述渗透脱氨的温度为20～40℃，渗透汽化膜两侧的压差为0.1～0.5MPa，所述渗透汽化膜的材质包括陶瓷、聚氯乙烯或聚乙烯醇中任意一种，所述渗透脱氨时，氨气分子穿过渗透汽化膜进入另一侧被酸液吸收，维持渗透汽化膜两侧的压差，剩余的为处理后氨氮废水，所述处理后氨氮废水中氨氮含量降至15ppm以下。
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