WO2022022090A1 - Method for recovering vivianite from sludge incineration ash - Google Patents

Method for recovering vivianite from sludge incineration ash Download PDF

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WO2022022090A1
WO2022022090A1 PCT/CN2021/099168 CN2021099168W WO2022022090A1 WO 2022022090 A1 WO2022022090 A1 WO 2022022090A1 CN 2021099168 W CN2021099168 W CN 2021099168W WO 2022022090 A1 WO2022022090 A1 WO 2022022090A1
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filtrate
incineration ash
sludge incineration
desorption
phosphorus
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PCT/CN2021/099168
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French (fr)
Chinese (zh)
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章骅
何品晶
杨怡君
邵立明
吕凡
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同济大学
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Priority to CN202010747296.9A priority patent/CN111792636B/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/37Phosphates of heavy metals
    • C01B25/375Phosphates of heavy metals of iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/34Regenerating or reactivating
    • B01J20/3483Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling

Abstract

The present invention relates to a method for recovering vivianite from sludge incineration ash, comprising the following steps: (1) mixing sludge incineration ash with acid liquor, heating to leach phosphorus, and then performing filtering and separating to obtain leached filtrate and leached filter residues; (2) adjusting the pH value of the leached filtrate with alkali liquor, adding an adsorbent for phosphorus adsorption, and then performing filtering and separating to obtain adsorbed filtrate and adsorbed filter residues; (3) mixing the adsorbed filter residues with alkali liquor to perform phosphorus desorption, and then performing filtering and separating to obtain desorbed filtrate and desorbed filter residues; and (4) in an anaerobic environment, adding ferrous ions into the desorbed filtrate, adjusting the pH value of the desorbed filtrate to carry out reaction, then performing filtering and separating to obtain filter residues and filtrate, and washing and drying the filter residues to obtain vivianite. Compared with the prior art, the present invention eliminates the interferences of other elements in the sludge incineration ash, obtains a high-quality vivianite product, can alleviate the problem of phosphorus resource shortage, and is simple in technological process and convenient in operation.

Description

一种从污泥焚烧灰中回收蓝铁矿的方法A kind of method for recovering blue iron ore from sludge incineration ash 技术领域technical field
本发明涉及固体废物资源化综合利用领域,具体涉及一种从污泥焚烧灰中回收蓝铁矿的方法。The invention relates to the field of comprehensive utilization of solid waste resources, in particular to a method for recovering blue iron ore from sludge incineration ash.
背景技术Background technique
磷(P)是生命有机体中必不可少的元素,在生命活动中起着至关重要的作用。随着全球人口的不断增加,农业和工业上对磷的需求量也在增长。但是,磷是有限且不可更新的资源,每年约有2000万吨磷矿被开采,磷的价格持续上涨。同时,优质易开采的磷矿石逐渐枯竭,高杂质高开采难度的磷矿石将被广泛使用,这将进一步提高磷产品的生产成本。按目前磷的开采和使用速度,具有开采经济效益的磷资源只能维持约50-100年。所以,有必要增强磷资源的回收利用,开发从含磷废物中回收磷资源的可持续方法,使磷资源在一个循环系统中流通,从而减少磷矿的开采。Phosphorus (P) is an essential element in living organisms and plays a vital role in life activities. As the global population continues to increase, so does the demand for phosphorus in agriculture and industry. However, phosphorus is a limited and non-renewable resource, about 20 million tons of phosphate rock is mined every year, and the price of phosphorus continues to rise. At the same time, the high-quality and easy-to-minable phosphate rock is gradually exhausted, and the phosphate rock with high impurities and high mining difficulty will be widely used, which will further increase the production cost of phosphorus products. According to the current rate of phosphorus exploitation and use, phosphorus resources with economic benefits of exploitation can only be maintained for about 50-100 years. Therefore, it is necessary to enhance the recycling and utilization of phosphorus resources, develop sustainable methods for recovering phosphorus resources from phosphorus-containing wastes, and make phosphorus resources circulate in a cyclic system, thereby reducing the mining of phosphorus mines.
污水处理厂污泥的主要处置途径包括农业和园林绿化利用、焚烧和填埋。在农业中直接使用是具有争议的,因为污泥汇集了污水中的污染物,含有病原体、重金属和有机污染物(例如药物和个人护理品)。焚烧可以破坏污泥中存在的有机污染物和消灭病原体,在这种情况下,会产生污泥焚烧灰,它具有浓缩的矿物质成分,通常具有较高的P 2O 5含量,质量百分比含量大约为13.7%~25.7%,因此,污泥焚烧灰被认为是潜在的磷资源。除P 2O 5外,污泥焚烧灰的主要成分是SiO 2、CaO、Al 2O 3、Fe 2O 3、MgO,且含有毒重金属,例如镉、铬、铜、铅、锰、锌、镍。因此,在回收污泥焚烧灰中的磷时,必须有效地去除这些元素。目前,常用的污泥磷回收方法主要包括:酸/碱浸出和沉淀法、吸附/解吸法、生物浸提、超临界萃取和热化学处理法,进而制备出无机磷肥、鸟粪石和磷酸。这些方法中,酸/碱浸出和沉淀法得到广泛的应用,通过添加试剂使污泥中溶出的磷形成不溶性的磷酸盐,例如鸟粪石。 The main disposal methods of sewage treatment plant sludge include agricultural and landscaping utilization, incineration and landfill. Direct use in agriculture is controversial because sludge collects pollutants in sewage, containing pathogens, heavy metals, and organic pollutants (eg, pharmaceuticals and personal care products). Incineration can destroy the organic pollutants present in the sludge and destroy pathogens, in this case, the sludge incineration ash is produced, which has a concentrated mineral composition, usually with a high P2O5 content , mass percent content About 13.7% to 25.7%, therefore, sludge incineration ash is considered as a potential phosphorus resource. Except for P 2 O 5 , the main components of sludge incineration ash are SiO 2 , CaO, Al 2 O 3 , Fe 2 O 3 , MgO, and contain toxic heavy metals such as cadmium, chromium, copper, lead, manganese, zinc, nickel. Therefore, these elements must be efficiently removed when recovering phosphorus from sludge incineration ash. At present, the commonly used sludge phosphorus recovery methods mainly include: acid/alkali leaching and precipitation, adsorption/desorption, biological leaching, supercritical extraction and thermochemical treatment, and then prepare inorganic phosphorus fertilizer, struvite and phosphoric acid. Among these methods, acid/alkali leaching and precipitation methods are widely used, by adding reagents to form insoluble phosphates, such as struvite, from phosphorus dissolved in sludge.
蓝铁矿(Vivianite,Fe 3(PO 4) 2·8H 2O)是一种非常稳定的磷铁化合物,主要天然存在于湖泊沉积物、富铁土壤和厌氧环境中。它是磷酸铁锂(LiFePO 4)锂离子电池的基本原料;也可以作为缓释磷肥。蓝铁矿的价格高达51-96欧元/kg磷,远 高于鸟粪石(9.8欧元/kg磷)和磷酸铝(3.4欧元/kg磷)。与鸟粪石相比,蓝铁矿可用于电子工业与农业中,经济价值高,具有更好的磷回收前景。 Vivianite (Fe 3 (PO 4 ) 2 ·8H 2 O) is a very stable phosphorus-iron compound that occurs naturally in lake sediments, iron-rich soils and anaerobic environments. It is the basic raw material for lithium iron phosphate (LiFePO 4 ) lithium-ion batteries; it can also be used as a slow-release phosphate fertilizer. The price of blue iron ore is as high as 51-96 euros/kg phosphorus, which is much higher than struvite (9.8 euros/kg phosphorus) and aluminum phosphate (3.4 euros/kg phosphorus). Compared with struvite, cyanite can be used in electronics industry and agriculture, with high economic value and better prospects for phosphorus recovery.
专利CN110691758A涉及一种用于从流诸如废物流、污水或另一污泥流中回收磷酸盐的方法和系统。该方法包括以下步骤:提供包含初始量的磷酸盐的进入流;-将铁盐定量给料到流中和/或控制到流中的铁盐,使得在流中形成沉淀物,其中沉淀物包含蓝铁矿样结构物,该蓝铁矿样结构物包含进入流中的初始量的磷酸盐的多于60%,并且优选地还包括以下步骤:从流中分离蓝铁矿样结构物;和从分离的蓝铁矿样结构物中回收磷酸盐。但该专利未对流中磷酸盐进行富集除杂,流中有较高的有机磷含量不能转化为蓝铁矿从而限制蓝铁矿的生成;硫化物以高浓度存在,需要过量供应铁盐,待所有硫化物反应转化为硫化铁后,蓝铁矿才开始生成;且实验中需要污泥在厌氧或缺氧条件下保持20天~30天,实验所用时间较长。Patent CN110691758A relates to a method and system for recovering phosphate from a stream such as a waste stream, sewage or another sludge stream. The method comprises the steps of: providing an incoming stream comprising an initial amount of phosphate; dosing and/or controlling iron salts into the stream so that a precipitate is formed in the stream, wherein the precipitate contains a cyanite-like structure comprising more than 60% of the initial amount of phosphate entering the stream, and preferably further comprising the steps of: separating the cyanite-like structure from the stream; and Phosphate recovery from isolated chromite-like structures. However, this patent does not carry out enrichment and impurity removal of phosphate in the flow, and the high content of organic phosphorus in the flow cannot be converted into blue iron ore, thereby limiting the formation of blue iron ore; After all the sulfides are converted into iron sulfide, the cyanite begins to form; and the sludge needs to be kept under anaerobic or anoxic conditions for 20 to 30 days in the experiment, and the experiment takes a long time.
发明内容SUMMARY OF THE INVENTION
本发明的目的就是为了提供一种从污泥焚烧灰中回收蓝铁矿的方法,消除了污泥焚烧灰中其它元素的干扰,获得高品质的蓝铁矿产品,可以缓解磷资源的短缺问题,工艺流程简单,操作方便。The purpose of this invention is to provide a kind of method of reclaiming blue iron ore from sludge incineration ash, eliminates the interference of other elements in the sludge incineration ash, obtains high-quality blue iron ore product, can alleviate the shortage problem of phosphorus resources , the process is simple and the operation is convenient.
本发明的目的通过以下技术方案实现:The object of the present invention is achieved through the following technical solutions:
一种从污泥焚烧灰中回收蓝铁矿的方法,所述方法包括以下步骤:A method for recycling blue iron ore from sludge incineration ash, the method comprises the following steps:
(1)污泥焚烧灰的浸提:将污泥焚烧灰与酸液混合并加热进行磷的浸出,后经过滤分离得到浸出滤液和浸出滤渣,浸出滤渣可作为一般固体废物处置,该浸出采用翻转浸出;(1) leaching of sludge incineration ash: the sludge incineration ash is mixed with acid solution and heated to carry out leaching of phosphorus, and then the leaching filtrate and leaching filter residue are obtained by filtration and separation, and the leaching filter residue can be disposed as general solid waste. inversion leaching;
(2)浸出滤液的吸附:用碱液调节浸出滤液的pH值,后加入吸附剂进行磷的吸附,再经过滤分离得到吸附滤液和吸附滤渣,吸附滤液回流再用于浸提步骤;(2) adsorption of the leaching filtrate: adjust the pH value of the leaching filtrate with alkali liquor, then add an adsorbent to carry out the adsorption of phosphorus, and then filter and separate to obtain the adsorption filtrate and the adsorption filter residue, and the adsorption filtrate is refluxed for the leaching step;
(3)吸附滤渣的脱附:将吸附滤渣与碱液混合并进行磷的脱附,后经过滤分离获得脱附滤液和脱附滤渣;(3) Desorption of the adsorption filter residue: the adsorption filter residue is mixed with the lye and the phosphorus is desorbed, and then the desorption filtrate and the desorption filter residue are obtained by filtration and separation;
(4)蓝铁矿的制备:在厌氧环境下,向脱附滤液中加入亚铁离子,并调节脱附滤液的pH值进行反应,反应过程中持续通入氮气,后经过滤分离获得滤渣和滤液,滤渣经清洗干燥后即得到蓝铁矿。过滤分离采用真空过滤。(4) Preparation of blue iron ore: in an anaerobic environment, add ferrous ions to the desorption filtrate, and adjust the pH value of the desorption filtrate to carry out the reaction. During the reaction, nitrogen gas is continuously introduced, and then the filter residue is obtained by filtration and separation. and the filtrate, and the filter residue is washed and dried to obtain blue iron ore. Filtration and separation were carried out by vacuum filtration.
优选地,步骤(1)中,所述的酸液为工业级无机酸溶液或有机酸溶液,所述无机酸溶液选自硫酸溶液、盐酸溶液或硝酸溶液中的一种或多种,所述有机酸溶液 选自柠檬酸溶液或草酸溶液中的一种或多种,所述酸液的浓度为0.2~1mol/L。Preferably, in step (1), the acid solution is an industrial grade inorganic acid solution or an organic acid solution, and the inorganic acid solution is selected from one or more of sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the The organic acid solution is selected from one or more of a citric acid solution or an oxalic acid solution, and the concentration of the acid solution is 0.2-1 mol/L.
优选地,步骤(1)中,酸液与污泥焚烧灰的液固比为0.01~0.02L/g,浸出的温度为25~55℃,浸出的时间为0.5~2h。Preferably, in step (1), the liquid-solid ratio of the acid solution to the sludge incineration ash is 0.01-0.02 L/g, the leaching temperature is 25-55°C, and the leaching time is 0.5-2 h.
优选地,步骤(2)中,所述的吸附剂为水滑石。进一步优选地,所述的水滑石选自工业级镁铁水滑石、镁铝水滑石、锌铝水滑石、镁锰水滑石或锌铁水滑石中的一种或多种。Preferably, in step (2), the adsorbent is hydrotalcite. Further preferably, the hydrotalcite is selected from one or more of industrial grade magnesium-iron hydrotalcite, magnesium-aluminum hydrotalcite, zinc-aluminum hydrotalcite, magnesium-manganese hydrotalcite or zinc-iron hydrotalcite.
优选地,步骤(2)中,所述的碱液为氢氧化钠水溶液,并采用工业级,所述氢氧化钠水溶液的浓度为0.2~0.3mol/L。Preferably, in step (2), the lye solution is an aqueous sodium hydroxide solution of technical grade, and the concentration of the aqueous sodium hydroxide solution is 0.2-0.3 mol/L.
优选地,步骤(2)中,吸附的同时进行搅拌,搅拌的转速为150~300r/min,搅拌的时间为3~8h。Preferably, in step (2), stirring is performed at the same time of adsorption, the stirring speed is 150-300 r/min, and the stirring time is 3-8 h.
优选地,步骤(2)中,调节浸出滤液的pH值至5~7,浸出滤液与吸附剂的液固比为0.025~0.05L/g,吸附的温度为25~35℃,吸附的时间为3~8h。Preferably, in step (2), the pH value of the leaching filtrate is adjusted to 5-7, the liquid-solid ratio of the leaching filtrate and the adsorbent is 0.025-0.05L/g, the adsorption temperature is 25-35°C, and the adsorption time is 3 to 8 hours.
优选地,步骤(3)中,所述的碱液为氢氧化钠水溶液,并采用工业级,所述氢氧化钠水溶液的浓度为0.1~1mol/L。Preferably, in step (3), the lye solution is an aqueous sodium hydroxide solution of technical grade, and the concentration of the aqueous sodium hydroxide solution is 0.1-1 mol/L.
优选地,步骤(3)中,脱附的同时进行搅拌,搅拌的转速为300~450r/min,搅拌的时间为12~36h。Preferably, in step (3), stirring is performed while desorption, the stirring speed is 300-450 r/min, and the stirring time is 12-36 h.
优选地,步骤(3)中,碱液与吸附滤渣的液固比为0.1~0.2L/g,脱附的温度为25~35℃,脱附的时间为12~36h。Preferably, in step (3), the liquid-solid ratio of the alkali solution to the adsorption filter residue is 0.1-0.2 L/g, the desorption temperature is 25-35°C, and the desorption time is 12-36 h.
优选地,步骤(3)中,脱附滤渣采用去离子水清洗后,在300~450℃下煅烧2.5~3.5h(优选3h)进行再生,后作为吸附剂返回到步骤(2)进行使用。Preferably, in step (3), the desorption filter residue is washed with deionized water, calcined at 300-450° C. for 2.5-3.5 h (preferably 3 h) for regeneration, and then returned to step (2) as an adsorbent for use.
优选地,步骤(4)中,所述亚铁离子来自氯化亚铁、氯化亚铁的结晶水合物、硫酸亚铁或硫酸亚铁的结晶水合物中的一种或多种,优选为氯化亚铁的结晶水合物。氯化亚铁、氯化亚铁的结晶水合物、硫酸亚铁和硫酸亚铁的结晶水合物均采用工业级。Preferably, in step (4), the ferrous ion comes from one or more of ferrous chloride, crystalline hydrate of ferrous chloride, ferrous sulfate or crystalline hydrate of ferrous sulfate, preferably Crystalline hydrate of ferrous chloride. Ferrous chloride, crystalline hydrate of ferrous chloride, ferrous sulfate and crystalline hydrate of ferrous sulfate are all industrial grades.
优选地,步骤(4)中,采用氢氧化钠溶液和盐酸溶液调节脱附滤液的pH值。氢氧化钠溶液为低浓度溶液,浓度为0.2mol/L,盐酸溶液的浓度也为0.2mol/L。Preferably, in step (4), sodium hydroxide solution and hydrochloric acid solution are used to adjust the pH value of the desorption filtrate. The sodium hydroxide solution is a low concentration solution with a concentration of 0.2mol/L, and the concentration of the hydrochloric acid solution is also 0.2mol/L.
优选地,步骤(4)中,采用充氮气制造厌氧环境。Preferably, in step (4), nitrogen gas is used to create an anaerobic environment.
优选地,步骤(4)中,反应的同时进行搅拌,搅拌的转速为100~150r/min,搅拌的时间为48~96h。Preferably, in step (4), stirring is performed at the same time as the reaction, the stirring speed is 100-150 r/min, and the stirring time is 48-96 h.
优选地,步骤(4)中,亚铁离子与磷的添加摩尔比为1.5~1.6,亚铁离子的投 加量根据脱附滤液中的磷浓度而定,调节脱附滤液的pH值至6~8,反应的温度为25~35℃,反应的时间为48~96h。1.5~1.6的摩尔比能够将脱附滤液中的磷元素完全生成蓝铁矿,且足量的铁元素能够避免其他干扰因素来干扰蓝铁矿的生成,脱附滤液的pH值保证亚铁离子不会变成其他价态(单质铁或三价铁)。Preferably, in step (4), the added molar ratio of ferrous ions to phosphorus is 1.5 to 1.6, the dosage of ferrous ions is determined according to the phosphorus concentration in the desorption filtrate, and the pH value of the desorption filtrate is adjusted to 6 ~8, the reaction temperature is 25~35°C, and the reaction time is 48~96h. The molar ratio of 1.5 to 1.6 can completely generate cyanite from phosphorus in the desorption filtrate, and a sufficient amount of iron can avoid other interference factors to interfere with the generation of cyanite. The pH value of the desorption filtrate ensures that ferrous ions Will not change to other valence states (elemental iron or ferric iron).
优选地,步骤(4)中,滤渣依次采用去离子水和乙醇进行清洗后,在25~35℃下真空干燥6~8h。乙醇的浓度为98wt%。Preferably, in step (4), the filter residue is washed with deionized water and ethanol in sequence, and then dried under vacuum at 25-35° C. for 6-8 hours. The concentration of ethanol was 98 wt%.
与现有技术相比,本发明具有以下优点:Compared with the prior art, the present invention has the following advantages:
1、本发明提出了一种污泥焚烧灰磷回收的工艺,采用磷吸附、磷脱附和蓝铁矿沉淀的方法,消除了污泥焚烧灰中其它元素的干扰,获得高品质的蓝铁矿产品,工艺流程简单,操作方便,获得的蓝铁矿是重要的工业原料,用途广泛,具有良好的市场潜力、显著的经济和环境效益。1. The present invention proposes a process for recycling ash phosphorus from sludge incineration, adopts the method of phosphorus adsorption, phosphorus desorption and cyanite precipitation, eliminates the interference of other elements in the sludge incineration ash, and obtains high-quality cyanite The product has simple technological process and convenient operation, and the obtained blue iron ore is an important industrial raw material, which is widely used and has good market potential and significant economic and environmental benefits.
2、水滑石吸附剂经过再生后可以重复使用,再生后的水滑石仍具有良好的磷吸附能力。2. The hydrotalcite adsorbent can be reused after regeneration, and the regenerated hydrotalcite still has good phosphorus adsorption capacity.
3、本发明提供了一种利用污泥焚烧灰中的磷制备蓝铁矿技术,可以缓解磷资源的短缺问题。3. The present invention provides a technology for preparing blue iron ore by utilizing phosphorus in sludge incineration ash, which can alleviate the shortage of phosphorus resources.
附图说明Description of drawings
图1为本发明的方法步骤示意图;Fig. 1 is the method step schematic diagram of the present invention;
图2为本发明的方法步骤具体图。FIG. 2 is a specific diagram of the method steps of the present invention.
具体实施方式detailed description
下面结合附图和具体实施例对本发明进行详细说明。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
本发明中所用的试剂均采用工业级材料。The reagents used in the present invention all adopt industrial grade materials.
实施例1Example 1
一种从污泥焚烧灰中回收蓝铁矿的方法,处理对象是某污水处理厂的污泥焚烧灰,X射线荧光光谱(XRF)检测显示该污泥焚烧灰中的磷质量百分比含量为5.2%。从该种污泥焚烧灰中回收磷,制备蓝铁矿,如图1、2所示,该方法具体包括如下步骤:A method for recovering blue iron ore from sludge incineration ash, the treatment object is the sludge incineration ash of a sewage treatment plant, and X-ray fluorescence spectroscopy (XRF) detection shows that the phosphorus mass percentage content in the sludge incineration ash is 5.2 %. Phosphorus is recovered from the sludge incineration ash to prepare blue iron ore, as shown in Figures 1 and 2, and the method specifically includes the following steps:
(1)将100g污泥焚烧灰与2L盐酸溶液(0.5mol/L)(即液固比为0.02L/g)混合加热,在30℃下翻转浸出(翻转浸出的频率参照现有技术中常采用的参数, 下同)0.5h后,将混合液过滤获得浸出滤液和浸出滤渣。(1) 100g of sludge incineration ash is mixed and heated with 2L of hydrochloric acid solution (0.5mol/L) (that is, the liquid-solid ratio is 0.02L/g), and at 30° C., the frequency of inversion leaching is often used with reference to the prior art. parameters, the same below) after 0.5h, the mixed solution was filtered to obtain leaching filtrate and leaching filter residue.
(2)取100mL步骤(1)得到的浸出滤液和4g镁铁水滑石(即液固比为0.025L/g)于反应器中,用0.2mol/L的氢氧化钠溶液调节混合液pH值至5,在30℃下以150r/min的转速机械搅拌4h(同时进行吸附,下同)后,将混合液过滤获得吸附滤液和吸附滤渣。(2) Take 100mL of the leaching filtrate obtained in step (1) and 4g of magnesium iron hydrotalcite (that is, the liquid-solid ratio is 0.025L/g) in the reactor, and adjust the pH value of the mixed solution with 0.2mol/L sodium hydroxide solution to 5. After mechanical stirring at 150 r/min for 4 hours at 30°C (simultaneous adsorption, the same below), the mixture is filtered to obtain adsorption filtrate and adsorption filter residue.
(3)取2g步骤(2)中得到的吸附滤渣于反应器中,加入1mol/L的氢氧化钠溶液200mL(即液固比为0.1L/g),在30℃下以300r/min的转速机械搅拌24h(同时进行脱附,下同)后,将混合液过滤获得脱附滤液和脱附滤渣,脱附滤渣采用去离子水清洗后,在450℃下煅烧3h进行再生,后作为吸附剂返回到步骤(2)进行使用。(3) Take 2 g of the adsorption filter residue obtained in step (2) in the reactor, add 200 mL of 1 mol/L sodium hydroxide solution (that is, the liquid-solid ratio is 0.1 L/g), and at 30° C. at 300 r/min After 24 hours of mechanical stirring at the speed of rotation (desorption is carried out at the same time, the same below), the mixture is filtered to obtain desorption filtrate and desorption filter residue. The agent is returned to step (2) for use.
(4)取180mL步骤(3)得到的脱附滤液,充入氮气至溶解氧浓度(DO)<2%,加入一定量FeCl 2·4H 2O,使得Fe/P摩尔比为1.5,用0.2mol/L盐酸溶液和0.2mol/L氢氧化钠溶液调节pH值于6~8之间。以100r/min的转速机械搅拌且进行反应,反应温度为30℃,反应时间为96h,反应过程中持续通入氮气。反应结束后过滤,获得滤液和滤渣。 (4) Take 180 mL of the desorption filtrate obtained in step (3), fill it with nitrogen until the dissolved oxygen concentration (DO) is less than 2%, add a certain amount of FeCl 2 ·4H 2 O to make the Fe/P molar ratio 1.5, and use 0.2 mol/L hydrochloric acid solution and 0.2 mol/L sodium hydroxide solution adjust the pH value between 6-8. Mechanical stirring was carried out at a rotational speed of 100 r/min and the reaction was carried out, the reaction temperature was 30° C., the reaction time was 96 h, and nitrogen was continuously introduced into the reaction process. After the reaction is completed, filter to obtain filtrate and filter residue.
(5)将步骤(4)中得到的滤渣用清水冲洗3次后用98%乙醇清洗3次,在30℃下真空干燥6~8h后,得蓝铁矿产品0.57g,磷的收率为78.2%(以脱附滤液中的磷含量为基准来计算,下同)。(5) The filter residue obtained in the step (4) was washed with clean water for 3 times, then washed with 98% ethanol for 3 times, and after being vacuum-dried at 30° C. for 6 to 8 hours, 0.57 g of cyanite product was obtained, and the yield of phosphorus was 78.2% (calculated based on the phosphorus content in the desorption filtrate, the same below).
对步骤(1)中得到的浸出滤液进行成分分析,结果表明,浸出滤液中磷浓度为2.49g/L,磷浸出率95.8%。The composition analysis of the leaching filtrate obtained in step (1) shows that the phosphorus concentration in the leaching filtrate is 2.49 g/L, and the phosphorus leaching rate is 95.8%.
对步骤(2)中得到的吸附滤液进行成分分析,结果表明,吸附滤液中的磷浓度为0.18g/L,磷吸附率为88.5%。Component analysis of the adsorption filtrate obtained in step (2) shows that the phosphorus concentration in the adsorption filtrate is 0.18 g/L, and the phosphorus adsorption rate is 88.5%.
对步骤(3)中得到的脱附滤液进行成分分析,结果表明,脱附滤液中的磷浓度为0.50g/L,磷脱附率为95.8%。Component analysis of the desorption filtrate obtained in step (3) shows that the phosphorus concentration in the desorption filtrate is 0.50 g/L, and the phosphorus desorption rate is 95.8%.
实施例2Example 2
一种从污泥焚烧灰中回收蓝铁矿的方法,处理对象是某污水处理厂的污泥焚烧灰。X射线荧光光谱(XRF)检测显示该污泥焚烧灰的磷含量为5.2wt%。从该种污泥焚烧灰中回收磷,制备蓝铁矿,具体包括如下步骤:A method for recovering blue iron ore from sludge incineration ash, and the treatment object is the sludge incineration ash of a sewage treatment plant. X-ray fluorescence spectroscopy (XRF) showed that the phosphorus content of the sludge incineration ash was 5.2 wt%. Recover phosphorus from the sludge incineration ash to prepare blue iron ore, which specifically includes the following steps:
(1)将100g污泥焚烧灰与2L盐酸溶液(0.3mol/L)(即液固比为0.02L/g)混合加热,在55℃下翻转浸出0.5h后,将混合液过滤获得浸出滤液和浸出滤渣。(1) Mix and heat 100g of sludge incineration ash with 2L of hydrochloric acid solution (0.3mol/L) (that is, the liquid-solid ratio is 0.02L/g), and after inversion and leaching at 55°C for 0.5h, filter the mixture to obtain the leaching filtrate and leaching filter residues.
(2)取150mL步骤(1)得到的浸出液、6g镁铁水滑石(即液固比为0.025L/g)于反应器中,用0.2mol/L的氢氧化钠溶液调节混合液pH值至5,在30℃下以150r/min的转速机械搅拌4h后,将混合液过滤获得吸附滤液和吸附滤渣。(2) Take 150mL of the leaching solution obtained in step (1), 6g of magnesium iron hydrotalcite (that is, the liquid-solid ratio is 0.025L/g) in the reactor, and adjust the pH value of the mixed solution to 5 with 0.2mol/L sodium hydroxide solution , after mechanical stirring at 150r/min for 4 hours at 30°C, the mixture was filtered to obtain adsorption filtrate and adsorption filter residue.
(3)取4g步骤(2)中得到的吸附滤渣于反应器中,加入1mol/L的氢氧化钠溶液400mL(即液固比为0.1L/g),在30℃下以300r/min的转速机械搅拌24h后,将混合液过滤获得脱附滤液和脱附滤渣,脱附滤渣采用去离子水清洗后,在450℃下煅烧3h进行再生,后作为吸附剂返回到步骤(2)进行使用。(3) Take 4 g of the adsorption filter residue obtained in step (2) in the reactor, add 400 mL of 1 mol/L sodium hydroxide solution (that is, the liquid-solid ratio is 0.1 L/g), and at 30° C. at 300 r/min After 24 hours of mechanical stirring at the rotational speed, the mixture was filtered to obtain desorption filtrate and desorption filter residue. The desorption filter residue was washed with deionized water, calcined at 450 ° C for 3 hours for regeneration, and then returned to step (2) as an adsorbent for use. .
(4)取326mL步骤(3)得到的脱附滤液,充入氮气至DO(溶解氧含量))<2%,加入一定量FeCl 2·4H 2O,使得Fe/P摩尔比为1.5,用0.2mol/L盐酸溶液和0.2mol/L氢氧化钠溶液调节pH值于6~8之间。以100r/min的转速机械搅拌且同时进行反应,反应温度为30℃,反应时间为48h,反应过程中持续通入氮气。反应结束后过滤,获得滤液和滤渣。 (4) Take 326 mL of the desorption filtrate obtained in step (3), fill with nitrogen until DO (dissolved oxygen content)) < 2%, add a certain amount of FeCl 2 ·4H 2 O to make the Fe/P molar ratio 1.5, use 0.2mol/L hydrochloric acid solution and 0.2mol/L sodium hydroxide solution adjust the pH value between 6-8. The reaction was carried out at the same time with mechanical stirring at a rotational speed of 100 r/min, the reaction temperature was 30° C., the reaction time was 48 h, and nitrogen was continuously introduced into the reaction process. After the reaction is completed, filter to obtain filtrate and filter residue.
(5)将步骤(4)中得到的滤渣用清水冲洗3次后用98%乙醇清洗3次,在30℃下真空干燥6~8h后,得蓝铁矿产品0.93g,磷的收率为76.6%。(5) The filter residue obtained in the step (4) was rinsed 3 times with clean water and then rinsed 3 times with 98% ethanol. After vacuum drying at 30° C. for 6 to 8 hours, 0.93 g of cyanite product was obtained, and the yield of phosphorus was 76.6%.
对步骤(1)中得到的浸出滤液进行成分分析,结果表明,浸出滤液中磷浓度为2.58g/L,磷浸出率99.2%。The composition analysis of the leaching filtrate obtained in step (1) shows that the phosphorus concentration in the leaching filtrate is 2.58 g/L, and the phosphorus leaching rate is 99.2%.
对步骤(2)中得到的吸附滤液进行成分分析,结果表明,吸附滤液中的磷浓度为0.23g/L,磷吸附率为90.0%。Component analysis of the adsorption filtrate obtained in step (2) shows that the phosphorus concentration in the adsorption filtrate is 0.23 g/L, and the phosphorus adsorption rate is 90.0%.
对步骤(3)中得到的脱附滤液进行成分分析,结果表明,脱附滤液中的磷浓度为0.46g/L,磷脱附率为84.5%。Component analysis of the desorption filtrate obtained in step (3) shows that the phosphorus concentration in the desorption filtrate is 0.46 g/L, and the phosphorus desorption rate is 84.5%.
实施例3Example 3
一种从污泥焚烧灰中回收蓝铁矿的方法,处理对象是某污水处理厂的污泥焚烧灰。X射线荧光光谱(XRF)检测显示该污泥焚烧灰的磷含量为5.3wt%。从该种污泥焚烧灰中回收磷,制备蓝铁矿,具体包括如下步骤:A method for recovering blue iron ore from sludge incineration ash, and the treatment object is the sludge incineration ash of a sewage treatment plant. X-ray fluorescence spectroscopy (XRF) showed that the phosphorus content of the sludge incineration ash was 5.3 wt%. Recover phosphorus from the sludge incineration ash to prepare blue iron ore, which specifically includes the following steps:
(1)将100g污泥焚烧灰与1L盐酸溶液(0.3mol/L)(即液固比为0.01L/g)混合加热,在55℃下翻转浸出2h后,将混合液过滤获得浸出滤液和浸出滤渣。(1) Mix and heat 100 g of sludge incineration ash with 1 L of hydrochloric acid solution (0.3 mol/L) (that is, the liquid-solid ratio is 0.01 L/g), and after inverting and leaching at 55°C for 2 hours, the mixed solution is filtered to obtain the leaching filtrate and Leach filter residue.
(2)取250mL步骤(1)得到的浸出液、10g镁铁水滑石(即液固比为0.025L/g)于反应器中,用0.2mol/L的氢氧化钠溶液调节混合液pH值至6,在35℃下以250r/min的转速机械搅拌6h后,将混合液过滤获得吸附滤液和吸附滤渣。(2) take 250mL of the leaching solution obtained in step (1), 10g of magnesium iron hydrotalcite (that is, the liquid-solid ratio is 0.025L/g) in the reactor, and adjust the pH value of the mixed solution to 6 with 0.2mol/L sodium hydroxide solution , after mechanical stirring at 250r/min for 6h at 35°C, the mixture was filtered to obtain adsorption filtrate and adsorption filter residue.
(3)取4g步骤(2)中得到的吸附滤渣于反应器中,加入1mol/L的氢氧化 钠溶液800mL(即液固比为0.2L/g),在35℃下以350r/min的转速机械搅拌36h后,将混合液过滤获得脱附滤液和脱附滤渣,脱附滤渣采用去离子水清洗后,在300℃下煅烧3h进行再生,后作为吸附剂返回到步骤(2)进行使用。(3) Take 4 g of the adsorption filter residue obtained in step (2) in the reactor, add 800 mL of 1 mol/L sodium hydroxide solution (that is, the liquid-solid ratio is 0.2 L/g), and at 35° C. at 350 r/min After 36 hours of mechanical stirring at the rotational speed, the mixture was filtered to obtain desorption filtrate and desorption filter residue. The desorption filter residue was washed with deionized water, calcined at 300 °C for 3 hours for regeneration, and then returned to step (2) as an adsorbent for use. .
(4)取420mL步骤(3)得到的脱附滤液,充入氮气至DO(溶解氧含量))<2%,加入一定量FeCl 2·4H 2O,使得Fe/P摩尔比为1.6,用0.2mol/L盐酸溶液和0.2mol/L氢氧化钠溶液调节pH值于6~8之间。以100r/min的转速机械搅拌且同时进行反应,反应温度为35℃,反应时间为96h,反应过程中持续通入氮气。反应结束后过滤,获得滤液和滤渣。 (4) Take 420 mL of the desorption filtrate obtained in step (3), fill it with nitrogen until DO (dissolved oxygen content)) <2%, add a certain amount of FeCl 2 ·4H 2 O to make the Fe/P molar ratio 1.6, use 0.2mol/L hydrochloric acid solution and 0.2mol/L sodium hydroxide solution adjust the pH value between 6-8. The reaction was carried out at the same time with mechanical stirring at a rotational speed of 100 r/min, the reaction temperature was 35° C., the reaction time was 96 h, and nitrogen was continuously introduced into the reaction process. After the reaction is completed, filter to obtain filtrate and filter residue.
(5)将步骤(4)中得到的滤渣用清水冲洗3次后用98%乙醇清洗3次,在30℃下真空干燥6~8h后,得蓝铁矿产品1.28g,磷的收率为78.4%。(5) The filter residue obtained in the step (4) was rinsed 3 times with clean water and then rinsed 3 times with 98% ethanol, and after being vacuum-dried at 30° C. for 6 to 8 hours, 1.28 g of cyanite product was obtained, and the yield of phosphorus was 78.4%.
对步骤(1)中得到的浸出滤液进行成分分析,结果表明,浸出滤液中磷浓度为4.86g/L,磷浸出率91.7%。The composition analysis of the leaching filtrate obtained in step (1) shows that the phosphorus concentration in the leaching filtrate is 4.86 g/L, and the phosphorus leaching rate is 91.7%.
对步骤(2)中得到的吸附滤液进行成分分析,结果表明,吸附滤液中的磷浓度为0.17g/L,磷吸附率为96.0%。Component analysis of the adsorption filtrate obtained in step (2) shows that the phosphorus concentration in the adsorption filtrate is 0.17 g/L, and the phosphorus adsorption rate is 96.0%.
对步骤(3)中得到的脱附滤液进行成分分析,结果表明,脱附滤液中的磷浓度为0.48g/L,磷脱附率为82.3%。Component analysis of the desorption filtrate obtained in step (3) shows that the phosphorus concentration in the desorption filtrate is 0.48 g/L, and the phosphorus desorption rate is 82.3%.
实施例4Example 4
一种从污泥焚烧灰中回收蓝铁矿的方法,处理对象是某污水处理厂的污泥焚烧灰。X射线荧光光谱(XRF)检测显示该污泥焚烧灰的磷含量为5.3%。从该种污泥焚烧灰中回收磷,制备蓝铁矿,具体包括如下步骤:A method for recovering blue iron ore from sludge incineration ash, and the treatment object is the sludge incineration ash of a sewage treatment plant. X-ray fluorescence spectroscopy (XRF) showed that the phosphorus content of the sludge incineration ash was 5.3%. Recover phosphorus from the sludge incineration ash to prepare blue iron ore, which specifically includes the following steps:
(1)将100g污泥焚烧灰与1L硝酸溶液(0.6mol/L)(即液固比为0.02L/g)混合加热,在25℃下翻转浸出2h后,将混合液过滤获得浸出滤液和浸出滤渣。(1) Mix and heat 100 g of sludge incineration ash with 1 L of nitric acid solution (0.6 mol/L) (that is, the liquid-solid ratio is 0.02 L/g), and after inverting and leaching at 25 ° C for 2 hours, the mixed solution is filtered to obtain the leaching filtrate and Leach filter residue.
(2)取250mL步骤(1)得到的浸出液、5g镁铝水滑石(即液固比为0.05L/g)于反应器中,用0.2mol/L的氢氧化钠溶液调节混合液pH值至7,在25℃下以300r/min的转速机械搅拌3h后,将混合液过滤获得吸附滤液和吸附滤渣。(2) Take 250 mL of the leaching solution obtained in step (1) and 5 g of magnesium-aluminum hydrotalcite (that is, the liquid-solid ratio is 0.05 L/g) in the reactor, and adjust the pH value of the mixed solution with 0.2 mol/L sodium hydroxide solution to 7. After mechanical stirring at 300r/min for 3 hours at 25°C, filter the mixture to obtain adsorption filtrate and adsorption filter residue.
(3)取4g步骤(2)中得到的吸附滤渣于反应器中,加入1mol/L的氢氧化钠溶液800mL(即液固比为0.2L/g),在25℃下以450r/min的转速机械搅拌12h后,将混合液过滤获得脱附滤液和脱附滤渣,脱附滤渣采用去离子水清洗后,在350℃下煅烧2.5h进行再生,后作为吸附剂返回到步骤(2)进行使用。(3) Take 4 g of the adsorption filter residue obtained in step (2) in the reactor, add 800 mL of 1 mol/L sodium hydroxide solution (that is, the liquid-solid ratio is 0.2 L/g), and at 25 ° C with 450 r/min After 12 hours of mechanical stirring at the rotational speed, the mixture was filtered to obtain desorption filtrate and desorption filter residue. The desorption filter residue was washed with deionized water, calcined at 350 ° C for 2.5 hours for regeneration, and then returned to step (2) as an adsorbent for use.
(4)取460mL步骤(3)得到的脱附滤液,充入氮气至DO(溶解氧含量)) <2%,加入一定量FeSO 4·7H 2O,使得Fe/P摩尔比为1.6,用0.2mol/L盐酸溶液和0.2mol/L氢氧化钠溶液调节pH值于6~8之间。以100r/min的转速机械搅且同时进行反应,反应温度为25℃,反应时间为48h,反应过程中持续通入氮气。反应结束后过滤,获得滤液和滤渣。 (4) Take 460 mL of the desorption filtrate obtained in step (3), fill with nitrogen until DO (dissolved oxygen content)) <2%, add a certain amount of FeSO 4 ·7H 2 O to make the Fe/P molar ratio 1.6, use 0.2mol/L hydrochloric acid solution and 0.2mol/L sodium hydroxide solution adjust the pH value between 6-8. The reaction was carried out at the same time with mechanical stirring at a rotational speed of 100 r/min, the reaction temperature was 25° C., the reaction time was 48 h, and nitrogen was continuously introduced into the reaction process. After the reaction is completed, filter to obtain filtrate and filter residue.
(5)将步骤(4)中得到的滤渣用清水冲洗3次后用98%乙醇清洗3次,在25℃下真空干燥8h,得蓝铁矿产品。(5) The filter residue obtained in step (4) is washed with clean water for 3 times, then washed with 98% ethanol for 3 times, and vacuum-dried at 25° C. for 8 hours to obtain a blue iron ore product.
实施例5Example 5
一种从污泥焚烧灰中回收蓝铁矿的方法,处理对象是某污水处理厂的污泥焚烧灰。X射线荧光光谱(XRF)检测显示该污泥焚烧灰的磷含量为5.3%。从该种污泥焚烧灰中回收磷,制备蓝铁矿,具体包括如下步骤:A method for recovering blue iron ore from sludge incineration ash, and the treatment object is the sludge incineration ash of a sewage treatment plant. X-ray fluorescence spectroscopy (XRF) showed that the phosphorus content of the sludge incineration ash was 5.3%. Recover phosphorus from the sludge incineration ash to prepare blue iron ore, which specifically includes the following steps:
(1)将100g污泥焚烧灰与1L硫酸溶液(0.3mol/L)(即液固比为0.02L/g)混合加热,在35℃下翻转浸出2h后,将混合液过滤获得浸出滤液和浸出滤渣。(1) Mix and heat 100g of sludge incineration ash with 1L of sulfuric acid solution (0.3mol/L) (that is, the liquid-solid ratio is 0.02L/g), and after leaching at 35°C for 2 hours, filter the mixture to obtain the leaching filtrate and Leach filter residue.
(2)取250mL步骤(1)得到的浸出液、5g锌铝水滑石(即液固比为0.05L/g)于反应器中,用0.2mol/L的氢氧化钠溶液调节混合液pH值至7,在35℃下以300r/min的转速机械搅拌3h后,将混合液过滤获得吸附滤液和吸附滤渣。(2) Take 250mL of the leaching solution obtained in step (1) and 5g of zinc-aluminum hydrotalcite (that is, the liquid-solid ratio is 0.05L/g) in the reactor, and adjust the pH value of the mixed solution with 0.2mol/L sodium hydroxide solution to 7. After mechanical stirring at 300r/min for 3 hours at 35°C, filter the mixture to obtain adsorption filtrate and adsorption filter residue.
(3)取4g步骤(2)中得到的吸附滤渣于反应器中,加入1mol/L的氢氧化钠溶液800mL(即液固比为0.2L/g),在35℃下以450r/min的转速机械搅拌12h后,将混合液过滤获得脱附滤液和脱附滤渣,脱附滤渣采用去离子水清洗后,在300℃下煅烧3.5h进行再生,后作为吸附剂返回到步骤(2)进行使用。(3) Take 4 g of the adsorption filter residue obtained in step (2) in the reactor, add 800 mL of 1 mol/L sodium hydroxide solution (that is, the liquid-solid ratio is 0.2 L/g), at 35 ° C with 450 r/min After 12 hours of mechanical stirring at the rotational speed, the mixture was filtered to obtain desorption filtrate and desorption filter residue. The desorption filter residue was washed with deionized water, calcined at 300 ° C for 3.5 hours for regeneration, and then returned to step (2) as an adsorbent for regeneration. use.
(4)取460mL步骤(3)得到的脱附滤液,充入氮气至DO(溶解氧含量))<2%,加入一定量FeSO 4,使得Fe/P摩尔比为1.6,用0.2mol/L盐酸溶液和0.2mol/L氢氧化钠溶液调节pH值于6~8之间。以100r/min的转速机械搅拌且同时进行反应,反应温度为35℃,反应时间为48h,反应过程中持续通入氮气。反应结束后过滤,获得滤液和滤渣。 (4) Take 460 mL of the desorption filtrate obtained in step (3), fill it with nitrogen until DO (dissolved oxygen content)) <2%, add a certain amount of FeSO 4 to make the Fe/P molar ratio 1.6, use 0.2 mol/L Hydrochloric acid solution and 0.2mol/L sodium hydroxide solution adjust the pH value between 6-8. The reaction was carried out simultaneously with mechanical stirring at a rotational speed of 100 r/min, the reaction temperature was 35° C., the reaction time was 48 h, and nitrogen was continuously introduced into the reaction process. After the reaction is completed, filter to obtain filtrate and filter residue.
(5)将步骤(4)中得到的滤渣用清水冲洗3次后用98%乙醇清洗3次,在35℃下真空干燥6h,得蓝铁矿产品。(5) The filter residue obtained in step (4) is washed with clean water for 3 times, then washed with 98% ethanol for 3 times, and vacuum-dried at 35° C. for 6 hours to obtain a blue iron ore product.
实施例6Example 6
一种从污泥焚烧灰中回收蓝铁矿的方法,除了步骤(1)中采用的是柠檬酸溶液,步骤(2)中采用的是镁锰水滑石,步骤(4)中加入的是FeCl 2之外,其余均与实施例1相同。 A method for recycling blue iron ore from sludge incineration ash, except that what is adopted in step (1) is citric acid solution, what is adopted in step (2) is magnesium-manganese hydrotalcite, and what is added in step (4) is FeCl Except for 2 , the rest are the same as in Example 1.
实施例7Example 7
一种从污泥焚烧灰中回收蓝铁矿的方法,除了步骤(1)中采用的是草酸溶液,步骤(2)中采用的是锌铁水滑石之外,其余均与实施例1相同。A method for recovering blue iron ore from sludge incineration ash, except that what is adopted in step (1) is oxalic acid solution, and what is adopted in step (2) is zinc-iron hydrotalcite, all the other are the same as in Example 1.
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The foregoing description of the embodiments is provided to facilitate understanding and use of the invention by those of ordinary skill in the art. It will be apparent to those skilled in the art that various modifications to these embodiments can be readily made, and the generic principles described herein can be applied to other embodiments without inventive step. Therefore, the present invention is not limited to the above-mentioned embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should all fall within the protection scope of the present invention.

Claims (10)

  1. 一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,所述方法包括以下步骤:A method for recovering blue iron ore from sludge incineration ash, it is characterized in that, described method comprises the following steps:
    (1)污泥焚烧灰的浸提:将污泥焚烧灰与酸液混合并加热进行磷的浸出,后经过滤分离得到浸出滤液和浸出滤渣;(1) leaching of sludge incineration ash: the sludge incineration ash is mixed with acid solution and heated to carry out the leaching of phosphorus, and then the leaching filtrate and the leaching filter residue are obtained by filtration and separation;
    (2)浸出滤液的吸附:用碱液调节浸出滤液的pH值,后加入吸附剂进行磷的吸附,再经过滤分离得到吸附滤液和吸附滤渣;(2) adsorption of leaching filtrate: adjust the pH value of leaching filtrate with alkali solution, then add adsorbent to carry out phosphorus adsorption, and then filter and separate to obtain adsorption filtrate and adsorption filter residue;
    (3)吸附滤渣的脱附:将吸附滤渣与碱液混合并进行磷的脱附,后经过滤分离获得脱附滤液和脱附滤渣;(3) Desorption of the adsorption filter residue: the adsorption filter residue is mixed with the lye and the phosphorus is desorbed, and then the desorption filtrate and the desorption filter residue are obtained by filtration and separation;
    (4)蓝铁矿的制备:在厌氧环境下,向脱附滤液中加入亚铁离子,并调节脱附滤液的pH值进行反应,后经过滤分离获得滤渣和滤液,滤渣经清洗干燥后即得到蓝铁矿。(4) Preparation of blue iron ore: in an anaerobic environment, add ferrous ions to the desorption filtrate, and adjust the pH value of the desorption filtrate to react, and then filter and separate to obtain a filter residue and a filtrate, and the filter residue is washed and dried That is to get blue iron ore.
  2. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(1)中,所述的酸液为无机酸溶液或有机酸溶液,所述无机酸溶液选自硫酸溶液、盐酸溶液或硝酸溶液中的一种或多种,所述有机酸溶液选自柠檬酸溶液或草酸溶液中的一种或多种。A kind of method that reclaims blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (1), described acid solution is mineral acid solution or organic acid solution, and described mineral acid The solution is selected from one or more of sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the organic acid solution is selected from one or more of citric acid solution or oxalic acid solution.
  3. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(1)中,酸液与污泥焚烧灰的液固比为0.01~0.02L/g,浸出的温度为25~55℃,浸出的时间为0.5~2h。A kind of method for reclaiming blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (1), the liquid-solid ratio of acid solution and sludge incineration ash is 0.01~0.02L/g , the leaching temperature is 25~55℃, and the leaching time is 0.5~2h.
  4. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(2)中,所述的吸附剂为水滑石;所述的碱液为氢氧化钠水溶液。A kind of method of reclaiming blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (2), described adsorbent is hydrotalcite; Described lye is sodium hydroxide aqueous solution.
  5. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(2)中,调节浸出滤液的pH值至5~7,浸出滤液与吸附剂的液固比为0.025~0.05L/g,吸附的温度为25~35℃,吸附的时间为3~8h;A kind of method of reclaiming blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (2), adjust the pH value of leaching filtrate to 5~7, leaching filtrate and adsorbent liquid The solid ratio is 0.025~0.05L/g, the adsorption temperature is 25~35℃, and the adsorption time is 3~8h;
    吸附的同时进行搅拌,搅拌的转速为150~300r/min,搅拌的时间为3~8h。Stirring is carried out at the same time of adsorption, the stirring speed is 150~300r/min, and the stirring time is 3~8h.
  6. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(3)中,所述的碱液为氢氧化钠水溶液;A kind of method that reclaims blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (3), described lye is sodium hydroxide aqueous solution;
    碱液与吸附滤渣的液固比为0.1~0.2L/g,脱附的温度为25~35℃,脱附的时间为12~36h;The liquid-solid ratio of the alkali solution to the adsorption filter residue is 0.1~0.2L/g, the desorption temperature is 25~35℃, and the desorption time is 12~36h;
    脱附的同时进行搅拌,搅拌的转速为300~450r/min,搅拌的时间为12~36h。While desorption is carried out, the stirring speed is 300~450r/min, and the stirring time is 12~36h.
  7. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(3)中,脱附滤渣采用去离子水清洗后,在300~450℃下煅烧2.5~3.5h进行再生,后作为吸附剂返回到步骤(2)进行使用。A method for recovering blue iron ore from sludge incineration ash according to claim 1, characterized in that, in step (3), after the desorption filter residue is washed with deionized water, calcined at 300~450 ℃ for 2.5 ~3.5h for regeneration, and then returned to step (2) for use as an adsorbent.
  8. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(4)中,所述亚铁离子来自氯化亚铁、氯化亚铁的结晶水合物、硫酸亚铁或硫酸亚铁的结晶水合物中的一种或多种;A kind of method that reclaims blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (4), described ferrous ion comes from the crystal hydration of ferrous chloride, ferrous chloride one or more of ferrous sulfate, ferrous sulfate or crystalline hydrate of ferrous sulfate;
    采用氢氧化钠溶液和盐酸溶液调节脱附滤液的pH值。The pH of the desorption filtrate was adjusted with sodium hydroxide solution and hydrochloric acid solution.
  9. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(4)中,亚铁离子与磷的添加摩尔比为1.5~1.6,调节脱附滤液的pH值至6~8,反应的温度为25~35℃,反应的时间为48~96h;A kind of method of reclaiming blue iron ore from sludge incineration ash according to claim 1, is characterized in that, in step (4), the added molar ratio of ferrous ion and phosphorus is 1.5~1.6, adjusts desorption filtrate The pH value is 6~8, the temperature of reaction is 25~35 ℃, and the time of reaction is 48~96h;
    反应的同时进行搅拌,搅拌的转速为100~150r/min,搅拌的时间为48~96h。During the reaction, stirring is performed, the stirring speed is 100-150 r/min, and the stirring time is 48-96 h.
  10. 根据权利要求1所述的一种从污泥焚烧灰中回收蓝铁矿的方法,其特征在于,步骤(4)中,滤渣依次采用去离子水和乙醇进行清洗后,在25~35℃下真空干燥6~8h。A kind of method for reclaiming blue iron ore from sludge incineration ash according to claim 1, it is characterized in that, in step (4), after filter residue is cleaned successively with deionized water and ethanol, at 25~35 ℃ Vacuum dry for 6-8h.
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