WO2022227418A1 - 金属盐协同栲胶脱除污泥臭味的方法、脱臭污泥及其应用 - Google Patents

金属盐协同栲胶脱除污泥臭味的方法、脱臭污泥及其应用 Download PDF

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WO2022227418A1
WO2022227418A1 PCT/CN2021/123978 CN2021123978W WO2022227418A1 WO 2022227418 A1 WO2022227418 A1 WO 2022227418A1 CN 2021123978 W CN2021123978 W CN 2021123978W WO 2022227418 A1 WO2022227418 A1 WO 2022227418A1
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sludge
tannin extract
deodorized
parts
metal salt
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PCT/CN2021/123978
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English (en)
French (fr)
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刘明华
林剑涛
姜疏雨
杨宇川
周郁欣
刘以凡
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福州大学
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Priority to US18/287,034 priority Critical patent/US11952298B2/en
Publication of WO2022227418A1 publication Critical patent/WO2022227418A1/zh

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/148Combined use of inorganic and organic substances, being added in the same treatment step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/147Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/02Odour removal or prevention of malodour
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the invention belongs to the technical field of sludge treatment, and more particularly relates to a method for deodorizing sludge with metal salts and tannin extract, deodorizing sludge and applications thereof.
  • Sludge is an inevitable product of sewage treatment plants in the process of treating domestic and industrial wastewater. It is characterized by a large amount of production and complex components. It contains a large number of pathogenic microorganisms, heavy metals and organic matter, and is easily corrupted and smelly. Sludge that has not been properly and safely treated is likely to cause harm to soil, water sources and even human bodies through the food chain after re-entering the environment. Moreover, proper and reasonable treatment and utilization of sludge can make it "turn waste into treasure", resulting in a huge amount of waste. Ecological, economic and social benefits.
  • the use of concentration, digestion, dehydration, drying and other treatment methods can reduce the moisture in the sludge, significantly reduce the volume, facilitate storage and transportation, and thus facilitate the realization of further resources such as incineration, composting, building materials, and pyrolysis oil. utilization process.
  • the sludge will release a variety of toxic and harmful gases (such as ammonia, hydrogen sulfide, methyl mercaptan, methyl sulfide, carbon disulfide, dioxin, etc.) during the above-mentioned treatment and disposal, resulting in a large number of irritating and unpleasant odors. , seriously affecting the surrounding living environment and life and health.
  • the existing sludge deodorization methods include physical method, biological method and chemical method.
  • 1Physical method refers to a method of masking, transferring or diluting the odor in the sludge by physical means without changing the nature of the sludge.
  • Common physical deodorization methods include activated carbon adsorption, liquid adsorption, etc.
  • Activated carbon has developed pore structure, high specific surface area and abundant surface active groups, which can realize the specific adsorption of malodorous substances. This method has high deodorization efficiency and simple maintenance.
  • due to the high cost of activated carbon materials limited adsorption capacity and inability to solve the problem from the root cause, it is generally suitable for post-treatment of deodorized gas.
  • the biological method uses specific microorganisms to capture the odorous substances in the sludge and digest and decompose them.
  • the biological method has a wide range of applications. In addition to removing common H 2 S and NH 3 , it also has a certain effect on odors such as mercaptans and sulfides, and does not produce secondary pollution. However, there are disadvantages such as relatively high operation and maintenance costs, and the survival of microorganisms is easily affected by the environment.
  • the main principle of the chemical method is that the odorous substances in the sludge can react with certain chemical substances, thereby changing the chemical properties of the odor to achieve the purpose of deodorization.
  • the commonly used chemical deodorization methods in practical applications mainly include: chemical oxidation method, chemical absorption method and combustion method.
  • the chemical deodorization process is highly targeted and has a good deodorization effect for high-concentration odor environments.
  • the removal of odor from sludge by chemical methods also has certain limitations.
  • the addition of chlorine-containing oxidants in the sludge deodorization process may increase the content of chlorine in the sludge, which may easily lead to the production of a large amount of highly toxic dioxins in the sludge incineration, building materials burning and other resource utilization processes. .
  • ozone as an oxidant can remove the hydrogen sulfide gas released from the sludge by means of an extremely fast reaction speed, but the properties of ozone are unstable, corrode equipment and pipeline materials, and the preparation cost is high, which limits the wide application of this technology .
  • Tannin extract also known as plant tannin
  • plant tannin is a kind of secondary metabolite with polyphenol structure that widely exists in plants, mainly in the bark, roots, leaves and fruits of plants.
  • the reserves of tannin extract in nature are very rich, and it is the fourth largest forest by-product after cellulose, lignin and hemicellulose.
  • Chinese invention patent application CN202010775794.4 discloses a method for dewatering and conditioning sludge based on a protein denaturant.
  • Chinese invention patent application CN202010529402.6 discloses a method for enhancing the dehydration performance of activated sludge by cationic starch grafted and condensed tannins.
  • the branch-condensed tannin suspension is cooled to room temperature and then added to the activated sludge, and the reaction is carried out in a mixer. After the reaction is complete, an activated sludge with enhanced dehydration performance is obtained.
  • the above invention patents only focus on the role of tannin extract in improving sludge dewatering performance, but do not realize that tannin extract with polyphenolic hydroxyl structure can inhibit the formation of malodorous substances in sludge, and has certain potential for realizing sludge deodorization. .
  • the sludge treated by the technical method of the above-mentioned invention patent application will still produce odors such as ammonia, hydrogen sulfide, methyl mercaptan, methyl sulfide, carbon disulfide and other odors during subsequent incineration, pyrolysis or carbonization and other resource utilization processes
  • odors such as ammonia, hydrogen sulfide, methyl mercaptan, methyl sulfide, carbon disulfide and other odors during subsequent incineration, pyrolysis or carbonization and other resource utilization processes
  • the problem of toxic and harmful substances such as odor gas and dioxin needs to be properly solved.
  • the inventor provides a method for removing the odor of sludge with metal salts in conjunction with tannin extract, comprising the following steps:
  • the pH value of the sludge deodorization reaction system is controlled to be 6.2 to 7.5, and the stirring is continued at a speed of 15 r/min to 120 r/min for 1 h to 3 h, and then allowed to stand for 12 h to 48 h.
  • the inventor provides a deodorized sludge, which is obtained by using the method described in the first aspect of the present invention.
  • the inventor provides an application of deodorized sludge, wherein the deodorized sludge is the deodorized sludge described in the second aspect of the present invention.
  • the method for removing the odor of sludge with metal salts and tannin extract innovatively utilizes the characteristic that tannin extract is rich in phenolic hydroxyl groups provided by the present invention, so that tannin extract is used as a kind of polybasic ligand to undergo complex reaction with metal ions , form a stable five-membered ring chelate, and at the same time continue to complex with sludge extracellular polymers (mainly composed of proteins and polysaccharides), and form cross-links between protein peptide chains through hydrophobic bonds and hydrogen bonds.
  • the method for removing the odor of sludge with metal salt and tannin extract provided by the present invention satisfies the principle of sludge reduction. Since sludge extracellular polymers commonly exist inside and on the surface of sludge flocs, they are an important factor affecting the performance of sludge filtration and dewatering. Tannin extract is easily complexed with extracellular polymers, reducing the surface hydrophilicity of protein molecules, so that the sludge flocs become loose, the bound water of the sludge is released, and the dewatering and drying performance of the sludge is improved.
  • the method for removing the odor of sludge with metal salt and tannin extract provided by the present invention satisfies the principle of resource utilization of sludge.
  • the tannin extract adopted in the present invention has various advantages such as wide source, low cost, green environmental protection and the like. Using tannin extract to deodorize sludge can avoid the generation of secondary pollution, is safe and reliable, and also provides a new technical path for the resource utilization of tannin extract.
  • the entire sludge deodorization process of the present invention is simple and feasible, flexible in operation, does not require complex and harsh reaction conditions and expensive equipment, and has low operating costs, and the obtained deodorized sludge can be used in applications including but not limited to incineration, Supporting pretreatment technology for resource utilization such as pyrolysis or carbonization.
  • the inventor provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following steps:
  • the pH value of the sludge deodorization reaction system is controlled to be 6.2 to 7.5, and the stirring is continued at a speed of 15 r/min to 120 r/min for 1 h to 3 h, and then allowed to stand for 12 h to 48 h.
  • the tannin extract in the present invention is a natural plant extract, which has wide sources, low cost and environmental protection.
  • the invention innovatively utilizes the characteristic that tannin extract is rich in phenolic hydroxyl structure, and can be used as a multi-base ligand to undergo complex reaction with metal ions to form a stable five-membered ring chelate, and at the same time continue to interact with extracellular sludge.
  • Polymers (mainly composed of proteins and polysaccharides) undergo complexation to form cross-links between protein peptide chains through hydrophobic bonds and hydrogen bonds, reducing the bioavailability of proteins and other macromolecules in sludge, and effectively inhibiting sulfidation
  • the production of hydrogen, methyl mercaptan, methyl sulfide, carbon disulfide, dimethyl disulfide and other low-volatile sulfides with low odor thresholds can significantly remove the odor generated during the two processes of sludge standing and combustion.
  • the metal salt treatment solution is 0.5% to 2.5% of one or more mixtures of ferrous sulfate, ferric sulfate, aluminum sulfate, ferric nitrate and ferrous ammonium sulfate % aqueous solution.
  • the vegetable tannin contained in the tannin extract reacts with ferrous ions to form ferrous tannins or iron tannins complexes, wherein ferrous tannins are unstable and are easily oxidized in the air to generate The complex of iron tannin is blue-black.
  • the metal salt treatment solution of the present invention is a sulfate or nitrate solution of ferrous ion, aluminum ion or iron ion, preferably a sulfate or nitrate solution of ferrous ion or iron ion.
  • the tannin extract treatment solution is one or more selected from the group consisting of bayberry tannin extract, larch extract, rubber bowl extract, Quercus extract and Vitex bark extract. 5% to 50% aqueous solution of the mixture.
  • Myrica tannin extract, larch tannin extract, rubber bowl extract extract, quince extract and wattle bark extract are extracted from bark, wood, husk and other plant raw materials with more tannins, and are made by concentrating The product is brownish yellow to tan in appearance, divided into powder and block.
  • the pH adjusting agent is a 2% to 8% aqueous solution of one or more mixtures of acetic acid, sulfamic acid, sulfuric acid, formic acid and oxalic acid.
  • the reaction temperature of the sludge deodorization reaction system is controlled to be 25°C to 80°C.
  • the increase of temperature helps the dispersion and penetration of tannins in tannin extract, and also promotes the combination of tannins and extracellular polymers in sludge.
  • the reaction temperature of the sludge deodorization reaction system of the present invention is controlled to be 25°C to 80°C.
  • 9320 to 9910 parts of the sludge to be deodorized and 20 to 100 parts of the metal salt treatment solution are uniformly mixed for 1 h to 3 h at a speed of 15 r/min to 120 r/min.
  • the sludge to be deodorized includes domestic sewage sludge, industrial wastewater sludge, drainage pipe sludge and/or water body bottom sludge.
  • the sludge to be deodorized includes untreated primary sludge, secondary sludge, untreated primary sludge and secondary sludge mixed with primary sludge , One or more of digested sludge that has undergone aerobic digestion or anaerobic digestion, and dewatered and dried sludge.
  • a deodorized sludge, the deodorized sludge is obtained by the method described in the first aspect of the present invention.
  • the content of hydrogen sulfide, methyl mercaptan, methyl sulfide, carbon disulfide, dimethyl disulfide and other low-volatile sulfides with low odor thresholds in the deodorized sludge obtained by the method of the first aspect of the present invention is greatly reduced, Since the bound water of the sludge is released, the dewatering and drying performance of the deodorized sludge is improved.
  • deodorized sludge is the deodorized sludge described in the second aspect of the present invention.
  • the deodorized sludge described in the second aspect of the present invention also contains a large amount of organic matter.
  • the deodorized sludge can be applied to forms including but not limited to incineration, pyrolysis or carbonization. resource utilization.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 2.5%
  • the tannin extract treatment solution is an aqueous solution of bayberry tannin extract with a mass percentage of 50%
  • the pH adjuster is a mass percentage of For 8% aqueous acetic acid.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of aluminum sulfate with a mass percentage of 0.5%
  • the tannin extract treatment solution is an aqueous solution of myrica tannin extract with a mass percentage of 5%
  • the pH adjuster is a mass percentage of 2% oxalic acid in water.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 2.5%
  • the tannin extract treatment solution is an aqueous solution of bayberry tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass percentage of It is a 2% aqueous solution of sulfamic acid.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 1.25%
  • the tannin extract treatment solution is an aqueous solution of bayberry tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass percentage of It is a 2% aqueous solution of sulfamic acid.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferric nitrate with a mass percentage of 2.5%
  • the tannin extract treatment solution is an aqueous solution of Myrica tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass percentage of It is a 2% aqueous solution of sulfuric acid.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous ammonium sulfate with a mass percentage of 1.25%
  • the tannin extract treatment solution is an aqueous solution of bayberry tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass Percentage is 2% formic acid in water.
  • the present embodiment provides a kind of method that metal salt cooperates with tannin extract to remove the odor of sludge, and it comprises the following concrete steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 1.25%
  • the tannin extract treatment solution is an aqueous solution of larch tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass Percentage is 2% sulfamic acid in water.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferric sulfate with a mass percentage of 1.25%
  • the tannin extract treatment solution is an aqueous solution of tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass percentage of Percentage is 4% acetic acid in water.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 0.5%
  • the tannin extract treatment solution is an aqueous solution of quebracho tannin extract with a mass percentage of 20%
  • the pH adjuster is a mass percentage of The percentage is 2% oxalic acid in water.
  • the present embodiment provides a method for removing the odor of sludge with metal salts and tannin extract, comprising the following specific steps:
  • the metal salt treatment solution is an aqueous solution of ferrous sulfate with a mass percentage of 1.25%
  • the tannin extract treatment solution is an aqueous solution of larch tannin extract with a mass percentage of 10%
  • the pH adjuster is a mass Percentage is 2% acetic acid in water.
  • the metal salt treatment solution is an aqueous ferrous sulfate solution with a mass percentage of 1.25%
  • the pH adjuster is an acetic acid aqueous solution with a mass percentage of 2%.
  • the stirring device First, put 9880 parts of the sludge to be deodorized from the water body sediment into the stirring device, control the reaction temperature to 40°C, turn on the stirrer and stir at a speed of 90r/min for 1h to make it evenly mixed. Then 100 parts of tannin extract treatment solution and 20 parts of pH adjuster were mixed and added into the stirring device, and the pH was controlled to 7.5 and stirred at a speed of 90 r/min for 2 h.
  • the tannin extract treatment solution is an aqueous solution of larch tannin extract with a mass percentage of 10%
  • the pH adjuster is an acetic acid aqueous solution with a mass percentage of 2%.
  • the deodorized sludge obtained by the methods of sludge deodorization in Examples 1 to 10 and Comparative Examples 1 and 2 was detected and analyzed for deodorization data, and ammonia gas (including under two states of standing and burning) was obtained by using a gas detector.
  • ammonia gas including under two states of standing and burning
  • the gas indicators of ammonia gas) and hydrogen sulfide are listed in Table 2 and Table 3.
  • Example 7 Metal salts (Comparative Example 1) or tannin extract (Comparative Example 2) were used. Among them, the treatment method of Example 7 has the best effect on sludge deodorization. It can remove 84.06% of ammonia and more than 83.33% of hydrogen sulfide under static conditions, and can remove 78.01% of ammonia and 76.09% of ammonia under combustion conditions. % hydrogen sulfide.
  • the effect of using larch tannin extract for sludge deodorization is better than that of other tannin extracts, and the effect of using ferrous sulfate for sludge deodorization is better than that of other metal salts.

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Abstract

本发明属于污泥处理技术领域,更具体地涉及一种金属盐协同栲胶脱除污泥臭味的方法、脱臭污泥及其应用。本发明提供了一种处理效率高、环境友好、投资成本低且满足后续焚烧、热解或炭化等资源化利用的无害化要求的污泥除臭技术。利用栲胶中含有丰富的酚羟基的特性,将其作为一种多基配体与金属离子发生络合反应,降低蛋白质和其他大分子的生物利用度,有效抑制低挥发性硫化物的产生,显著脱除污泥静置和燃烧两种过程中产生的恶臭。本发明整个除臭工艺流程简单可行、操作灵活、无需复杂苛刻的反应条件和昂贵的仪器设备,运行成本低,且能够作为污泥焚烧、热解或炭化等资源化利用的配套前处理技术。

Description

金属盐协同栲胶脱除污泥臭味的方法、脱臭污泥及其应用 技术领域
本发明属于污泥处理技术领域,更具体地涉及一种金属盐协同栲胶脱除污泥臭味的方法、脱臭污泥及其应用。
背景技术
污泥是污水处理厂在处理生活和工业废水过程中的必然产物,其特征是产生量大且成分复杂,含有大量的病原微生物、重金属和有机物,容易腐化发臭。未经妥善安全处理的污泥在重新进入环境后容易对土壤、水源甚至通过食物链对人体造成危害,况且对污泥进行适当合理的处理利用,可以使其“变废为宝”,产生巨大的生态、经济和社会效益。目前,利用浓缩、消化、脱水、干燥等处理方法可以减少污泥中的水分,显著减小体积,便于贮存和运输,从而有利于实现进一步的焚烧、堆肥、制建材、热解制油等资源化利用过程。然而,污泥在上述处理处置过程中会释放出多种有毒有害气体(如氨气、硫化氢、甲硫醇、甲硫醚、二硫化碳、二噁英等),产生大量刺激难闻的恶臭气味,严重影响周边生活环境和生命健康。并且,随着城镇化的快速发展,人们的公众环境意识不断增强,污泥恶臭已引起越来越多的关注。因此,污泥恶臭的有效控制已经成为污泥资源化利用中面临的重大现实问题。
现有的污泥脱臭方法包括物理法、生物法和化学法。①物理法是指不改变污泥本质的情况下,通过物理手段将污泥中的臭味遮蔽、转移或者稀释的一种方法。常见的物理脱臭方法包括活性炭吸附法、液体吸附法等。活性炭具有发达的孔隙结构、高比表面积和丰富的表面活性基团,能够实现对恶臭物质的特异性吸附。该方法脱臭效率高、维护简单,但由于活性炭材料成本较高、吸附容量有限且不能从根源上解决问题,一般适用于脱臭气体的后处理。②生物法是利用特定的微生物捕获污泥中的恶臭物质,并进行消化分解。 生物法应用范围较广,除了能够去除常见的H 2S和NH 3外,对硫醇、硫醚等臭气也有一定的效果,且不产生二次污染。然而存在运行维护费用相对较高、微生物的生存易受环境影响的缺陷。③化学法主要原理是污泥中恶臭物质能与某些化学物质产生反应,从而改变臭气的化学性质以达到除臭的目的。目前,实际应用中常用的化学除臭方法主要包括:化学氧化法、化学吸收法和燃烧法等。化学脱臭工艺具有较强针对性,对于高浓度臭气环境具有良好的脱臭效果。然而,通过化学法去除污泥中的臭味也存在一定的局限性。例如,在污泥除臭过程中投加含氯氧化剂可能会增加污泥中氯元素的含量,容易致使污泥在焚烧、建材烧制等资源化利用过程中产生大量具有强毒性的二噁英。另外,采用臭氧作为氧化剂可以凭借极快的反应速度去除污泥中释放的硫化氢气体,但臭氧性质不稳定,会腐蚀设备及管道材料,且制备成本较高,从而限制了该技术的广泛应用。
近年来,来源广泛、成本低廉、可生物降解、无二次污染的天然高分子材料受到广泛应用。栲胶又称植物单宁,是一类广泛存在于植物体内的具有多元酚结构的次生代谢物,主要存在于植物的皮、根、叶、果中。自然界中栲胶的储量非常丰富,是仅次于纤维素、木质素、半纤维素的第四大林副产品。目前,已有研究致力于将栲胶引入污泥的处理处置和资源化利用过程中。例如,中国发明专利申请CN202010775794.4公开了一种基于蛋白质变性剂的污泥脱水调理方法,通过向待调理污泥中加入以栲胶为主要成分的蛋白质变性剂,并施以磁力搅拌,以充分进行蛋白质变性反应,在反应过程中通过蛋白质络合变性作用削减胞外蛋白质的表面亲水性能,之后加入蛋白质乳化凝聚剂并快速搅拌,以进一步辅助促进污泥中持水性胞外蛋白质的凝结聚集,降低蛋白质的分散持水性能,进而大幅削减污泥絮体的整体持水能力,提高污泥脱水性能。中国发明专利申请CN202010529402.6公开了一种阳离子淀粉接枝缩合单宁强化活性污泥脱水性能的方法,通过将阳离子淀粉接枝缩合单宁加入到蒸馏水中,糊化至均匀,获得阳离子淀粉接枝缩合单宁悬浮液,冷 却至室温后再加入活性污泥中,并在搅拌机中进行反应,反应完全后获得脱水性能被强化的活性污泥。
上述发明专利仅仅关注到栲胶在提升污泥脱水性能方面的作用,并没有认识到具备多酚羟基结构的栲胶能够抑制污泥中恶臭物质的形成,对于实现污泥的脱臭具有一定的潜力。另一方面,上述发明专利申请的技术方法处理后的污泥在后续焚烧、热解或炭化等资源化利用过程中仍然会出现氨气、硫化氢、甲硫醇、甲硫醚、二硫化碳等臭味气体以及二噁英等有毒有害物质的问题有待妥善解决。
综上所述,开发一种处理效率高、环境友好、投资成本低且满足后续焚烧、热解或炭化等资源化利用的无害化要求的污泥除臭技术具有十分重要的意义。
发明内容
鉴于背景技术存在的上述技术问题,需要提供一种金属盐协同栲胶脱除污泥臭味的方法,所述方法需满足污泥后续焚烧、热解或炭化等资源化利用要求,并且适用于多种来源和类型的污泥。所述方法通过金属盐与栲胶的协同效应和络合作用实现对污泥的改性,能够从源头抑制恶臭物质的产生与发散,并且改性后的污泥能够进一步实现焚烧、热解或炭化等处置方法的无害化和资源化利用。
为实现上述目的,在本发明的第一方面,发明人提供了一种金属盐协同栲胶脱除污泥臭味的方法,包括以下步骤:
以重量份计,将9320份~9910份待除臭污泥与20份~100份金属盐处理溶液混合均匀,加入50份~500份栲胶处理溶液与20份~80份pH调节剂的混合物,得到污泥除臭反应体系,
控制所述污泥除臭反应体系的pH值为6.2~7.5继续以15r/min~120r/min的速度搅拌1h~3h,静置12h~48h。
在本发明的第二方面,发明人提供了一种脱臭污泥,所述脱臭污泥采用在本发明的第一方面所述方法处理得到。
在本发明的第三方面,发明人提供了一种脱臭污泥的应用,所述脱臭污泥为在本发明的第二方面所述的脱臭污泥。
区别于现有技术,上述技术方案至少具有以下有益效果:
1、本发明提供的金属盐协同栲胶脱除污泥臭味的方法创新地利用栲胶中含有丰富的酚羟基的特性,使栲胶作为一种多基配体与金属离子发生络合反应,形成稳定的五元环螯合物,同时继续与污泥胞外聚合物(主要为蛋白质和多糖等构成)发生络合作用,通过疏水键和氢键的方式在蛋白质肽链间形成交联,降低蛋白质和其他大分子的生物利用度,有效抑制硫化氢、甲硫醇、甲硫醚、二硫化碳、二甲二硫醚等具有低嗅阈值的低挥发性硫化物的产生,显著脱除污泥静置和燃烧两种过程中产生的恶臭,满足污泥的无害化原则。
2、本发明提供的金属盐协同栲胶脱除污泥臭味的方法,满足污泥的减量化原则。由于污泥胞外聚合物普遍存在于污泥絮体内部及表面,是影响污泥过滤脱水性能的重要因素。栲胶易与胞外聚合物络合,降低蛋白质分子的表面亲水性,使得污泥絮体变得松散,污泥的结合水得到释放,污泥的脱水干化性能有所提高。
3、本发明提供的金属盐协同栲胶脱除污泥臭味的方法,满足污泥的资源化原则。本发明所采用的栲胶作为一种天然的植物提取物,具备来源广泛、成本低廉、绿色环保等多种优点。利用栲胶对污泥进行脱臭,能够避免二次污染的产生、安全可靠,也为栲胶的资源化利用提供了一种新的技术路径。同时,本发明的整个污泥除臭工艺流程简单可行、操作灵活、无需复杂苛刻的反应条件和昂贵的仪器设备,运行成本低,且所得到的脱臭污泥可应用于包括但不限于焚烧、热解或炭化等资源化利用的配套前处理技术。
具体实施方式
下面详细说明本发明第一方面所述金属盐协同栲胶脱除污泥臭味的方法、第二方面所述的脱臭污泥和第三方面所述的脱臭污泥的应用。
首先说明本发明第一方面所述金属盐协同栲胶脱除污泥臭味的方法。
在本发明的第一方面,发明人提供了一种金属盐协同栲胶脱除污泥臭味的方法,包括以下步骤:
以重量份计,将9320份~9910份待除臭污泥与20份~100份金属盐处理溶液混合均匀,加入50份~500份栲胶处理溶液与20份~80份pH调节剂的混合物,得到污泥除臭反应体系,
控制所述污泥除臭反应体系的pH值为6.2~7.5继续以15r/min~120r/min的速度搅拌1h~3h,静置12h~48h。
本发明中的栲胶为天然的植物提取物,来源广泛、成本低廉、绿色环保。本发明创新地利用栲胶中含有丰富的酚羟基结构的特性,可以作为一种多基配体与金属离子发生络合反应,形成稳定的五元环螯合物,同时继续与污泥胞外聚合物(主要为蛋白质和多糖等构成)发生络合作用,通过疏水键和氢键的方式在蛋白质肽链间形成交联,降低污泥中蛋白质和其他大分子的生物利用度,有效抑制硫化氢、甲硫醇、甲硫醚、二硫化碳、二甲二硫醚等具有低嗅阈值的低挥发性硫化物的产生,显著脱除污泥静置和燃烧两种过程中产生的恶臭。
根据本发明优选的实施例,以质量百分比计,所述金属盐处理溶液为硫酸亚铁、硫酸铁、硫酸铝、硝酸铁和硫酸亚铁铵中的一种或几种混合物的0.5%~2.5%水溶液。在本发明中,栲胶所含的植物单宁与亚铁离子反应生成单宁酸亚铁或单宁酸铁络合物,其中,单宁酸亚铁不稳定,在空气中很容易氧化生成单宁酸铁的络合物而呈蓝黑色。因此,本发明所述金属盐处理溶液为亚铁离子、铝离子或铁离子的硫酸盐或硝酸盐溶液,优选亚铁离子或铁离子的硫酸盐或硝酸盐溶液。
根据本发明优选的实施例,以质量百分比计,所述栲胶处理溶液为杨梅栲胶、落叶松栲胶、橡椀栲胶、坚木栲胶和荆树皮栲胶中的一种或几种混合物的5%~50%水溶液。杨梅栲胶、落叶松栲胶、橡椀栲胶、坚木栲胶和荆树皮栲胶均为含单宁较多的树皮、木材、果壳等植物原料用水浸提,经过浓缩制成的产品,外观呈棕黄到棕褐色,分粉状和块状。
根据本发明优选的实施例,以质量百分比计,所述pH调节剂为乙酸、氨基磺酸、硫酸、甲酸和草酸中的一种或几种混合物的2%~8%水溶液。
根据本发明优选的实施例,控制所述污泥除臭反应体系的反应温度为25℃~80℃。温度的升高有助于栲胶中单宁的分散和渗透,也会促进单宁与污泥胞外聚合物的结合。但当温度过高时,单宁的氧化作用加快且污泥中蛋白质容易变性,丧失生物活性。因此,本发明所述污泥除臭反应体系的反应温度控制为25℃~80℃。
根据本发明优选的实施例,所述将9320份~9910份待除臭污泥与20份~100份金属盐处理溶液混合均匀为以15r/min~120r/min的速度搅拌1h~3h。
根据本发明优选的实施例,所述待除臭污泥包括生活污水污泥、工业废水污泥、排水管渠污泥和/或水体底泥。
根据本发明优选的实施例,所述待除臭污泥包括未经处理的初沉淀污泥、二沉剩余污泥、未经处理的初沉淀污泥和二沉剩余污泥混合的原污泥、经过好氧消化或厌氧消化的消化污泥、脱水干化污泥中的一种或几种。
其次说明本发明第二方面所述脱臭污泥。
一种脱臭污泥,所述脱臭污泥采用在本发明的第一方面所述方法处理得到。
采用本发明第一方面所述方法处理得到的脱臭污泥的硫化氢、甲硫醇、甲硫醚、二硫化碳、二甲二硫醚等具有低嗅阈值的低挥发性硫化物的含量大大降低,由于污泥的结合水被释放,因此该脱臭污泥的脱水干化性能得到提高。
最后说明本发明第三方面所述脱臭污泥的应用。
一种脱臭污泥的应用,所述脱臭污泥为在本发明的第二方面所述的脱臭污泥。
本发明第二方面所述的脱臭污泥还含有大量的有机质,在经过本发明第一方面所述方法充分脱臭之后,可以将脱臭污泥应用于包括但不限于焚烧、热解或炭化等形式的资源化利用中。
为详细说明技术方案的技术内容、构造特征、所实现目的及效果,以下结合具体实施例详予说明。应理解,这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例一
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9320份来源于生活污水的待除臭污泥放入搅拌装置内,控制反应温度为25℃,然后加入100份金属盐处理溶液,打开搅拌器以120r/min的速度搅拌1h,使其混合均匀。再将500份栲胶处理溶液与80份pH调节剂混合后加入搅拌装置内,控制pH为6.2并以120r/min的速度搅拌3h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为2.5%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为50%的杨梅栲胶水溶液,所述pH调节剂为质量百分数为8%的乙酸水溶液。
实施例二
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9910份来源于工业废水的待除臭污泥放入搅拌装置内,控制反应温度为60℃,然后加入20份金属盐处理溶液,打开搅拌器以15r/min的速度 搅拌1h,使其混合均匀。再将50份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以15r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为0.5%的硫酸铝水溶液,所述栲胶处理溶液为质量百分数为5%的杨梅栲胶水溶液,所述pH调节剂为质量百分数为2%的草酸水溶液。
实施例三
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9780份来源于城市污水处理厂的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入100份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为2.5%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为10%的杨梅栲胶水溶液,所述pH调节剂为质量百分数为2%的氨基磺酸水溶液。
实施例四
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9830份来源于生活污水的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为10%的杨 梅栲胶水溶液,所述pH调节剂为质量百分数为2%的氨基磺酸水溶液。
实施例五
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9830份来源于生活污水的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置18h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为2.5%的硝酸铁水溶液,所述栲胶处理溶液为质量百分数为10%的落杨梅栲胶水溶液,所述pH调节剂为质量百分数为2%的硫酸水溶液。
实施例六
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9830份来源于生活污水的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置18h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸亚铁铵水溶液,所述栲胶处理溶液为质量百分数为10%的杨梅栲胶水溶液,所述pH调节剂为质量百分数为2%的甲酸水溶液。
实施例七
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具 体步骤:
首先将9830份来源于生活污水的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为10%的落叶松栲胶水溶液,所述pH调节剂为质量百分数为2%的氨基磺酸水溶液。
实施例八
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9810份来源于排水管渠的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与40份pH调节剂混合后加入搅拌装置内,控制pH为6.6并以90r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸铁水溶液,所述栲胶处理溶液为质量百分数为10%的荆树皮栲胶水溶液,所述pH调节剂为质量百分数为4%的乙酸水溶液。
实施例九
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9760份来源于水体底泥的待除臭污泥放入搅拌装置内,控制反应温度为60℃,然后加入20份金属盐处理溶液,打开搅拌器以60r/min的速度搅拌1h,使其混合均匀。再将200份栲胶处理溶液与20份pH调节剂混合后 加入搅拌装置内,控制pH为7.5并以60r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为0.5%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为20%的坚木栲胶水溶液,所述pH调节剂为质量百分数为2%的草酸水溶液。
实施例十
本实施例提供一种金属盐协同栲胶脱除污泥臭味的方法,其包括如下具体步骤:
首先将9830份来源于水体底泥的待除臭污泥放入搅拌装置内,控制反应温度为80℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h,静置12h后即可有效脱除污泥中的臭味。在本实施例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸亚铁水溶液,所述栲胶处理溶液为质量百分数为10%的落叶松栲胶水溶液,所述pH调节剂为质量百分数为2%的乙酸水溶液。
对比例一
首先将9930份来源于水体底泥的待除臭污泥放入搅拌装置内,控制反应温度为40℃,然后加入50份金属盐处理溶液,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h。在本对比例中,所述金属盐处理溶液为质量百分数为1.25%的硫酸亚铁水溶液,所述pH调节剂为质量百分数为2%的乙酸水溶液。
对比例二
首先将9880份来源于水体底泥的待除臭污泥放入搅拌装置内,控制反应 温度为40℃,打开搅拌器以90r/min的速度搅拌1h,使其混合均匀。再将100份栲胶处理溶液与20份pH调节剂混合后加入搅拌装置内,控制pH为7.5并以90r/min的速度搅拌2h。在本对比例中,所述栲胶处理溶液为质量百分数为10%的落叶松栲胶水溶液,所述pH调节剂为质量百分数为2%的乙酸水溶液。
上述实施例一至实施例十、对比例一和二采用的脱除污泥臭味的方法涉及的工艺参数详见表一。
表一 本发明实施例一至实施例十工艺参数
Figure PCTCN2021123978-appb-000001
Figure PCTCN2021123978-appb-000002
Figure PCTCN2021123978-appb-000003
对实施例一到十、对比例一和二的污泥脱臭的方法得到的脱臭污泥进行除臭数据的检测与分析,利用气体检测仪得出氨气(包括静置和燃烧两种状态下的氨气指标)与硫化氢的气体指标为表二、表三所列。
表二 本发明实施例中污泥脱臭前后氨气检测指标
Figure PCTCN2021123978-appb-000004
表三 本发明实施例污泥脱臭前后硫化氢检测指标
Figure PCTCN2021123978-appb-000005
对上述实施例和对比例进行分析可以说明,采用金属盐协同栲胶的方法能够显著脱除污泥中的氨气和硫化氢气体,实现污泥的高效脱臭,并且脱臭效率远远高于单独使用金属盐(对比例一)或栲胶(对比例二)。其中,实施例七的处理方式对污泥脱臭的效果最优,在静置条件下可以去除84.06%的氨气和大于83.33%的硫化氢,在燃烧条件下可以去除78.01%的氨气和76.09%的硫化氢。经过综合比较分析可以发现,在本发明中采用落叶松栲胶进行污泥脱臭的效果要优于其余几种栲胶,采用硫酸亚铁进行污泥脱臭的效果要优于其余几种金属盐。
需要说明的是,尽管在本文中已经对上述各实施例进行了描述,但并非因此限制本发明的专利保护范围。因此,基于本发明的创新理念,对本文所述实施例进行的变更和修改,或利用本发明说明书内容所作的等效结构或等效流程变换,直接或间接地将以上技术方案运用在其他相关的技术领域,均包括在本发明的专利保护范围之内。

Claims (10)

  1. 金属盐协同栲胶脱除污泥臭味的方法,其特征在于,包括以下步骤:
    以重量份计,将9320份~9910份待除臭污泥与20份~100份金属盐处理溶液混合均匀,加入50份~500份栲胶处理溶液与20份~80份pH调节剂的混合物,得到污泥除臭反应体系,
    控制所述污泥除臭反应体系的pH值为6.2~7.5继续以15r/min~120r/min的速度搅拌1h~3h,静置12h~48h。
  2. 根据权利要求1所述的方法,其特征在于,以质量百分比计,所述金属盐处理溶液为硫酸亚铁、硫酸铁、硫酸铝、硝酸铁和硫酸亚铁铵中的一种或几种混合物的0.5%~2.5%水溶液。
  3. 根据权利要求1所述的方法,其特征在于,以质量百分比计,所述栲胶处理溶液为杨梅栲胶、落叶松栲胶、橡椀栲胶、坚木栲胶和荆树皮栲胶中的一种或几种混合物的5%~50%水溶液。
  4. 根据权利要求1所述的方法,其特征在于,以质量百分比计,所述pH调节剂为乙酸、氨基磺酸、硫酸、甲酸和草酸中的一种或几种混合物的2%~8%水溶液。
  5. 根据权利要求1所述的方法,其特征在于,控制所述污泥除臭反应体系的反应温度为25℃~80℃。
  6. 根据权利要求1所述的方法,其特征在于,所述将9320份~9910份待除臭污泥与20份~100份金属盐处理溶液混合均匀为以15r/min~120r/min的速度搅拌1h~3h。
  7. 根据权利要求1所述的方法,其特征在于,所述待除臭污泥包括生活污水污泥、工业废水污泥、排水管渠污泥和/或水体底泥。
  8. 根据权利要求1所述的方法,其特征在于,所述待除臭污泥包括未经处理的初沉淀污泥、二沉剩余污泥、未经处理的初沉淀污泥和二沉剩余污泥混合的原污泥、经过好氧消化或厌氧消化的消化污泥、脱水干化污泥中的一种或几种。
  9. 一种脱臭污泥,其特征在于,所述脱臭污泥采用权利要求1-8中任一项所述方法处理得到。
  10. 一种脱臭污泥的应用,其特征在于,所述脱臭污泥为权利要求9所述的脱臭污泥。
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