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CN103232103A - Method for removing phosphorus from reclaimed water by using ferric hydroxide produced through iron salt coagulant in-situ hydrolysis - Google Patents

Method for removing phosphorus from reclaimed water by using ferric hydroxide produced through iron salt coagulant in-situ hydrolysis Download PDF

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CN103232103A
CN103232103A CN201310120436XA CN201310120436A CN103232103A CN 103232103 A CN103232103 A CN 103232103A CN 201310120436X A CN201310120436X A CN 201310120436XA CN 201310120436 A CN201310120436 A CN 201310120436A CN 103232103 A CN103232103 A CN 103232103A
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孙丽华
张雅君
齐晓璐
冯萃敏
许萍
俞天敏
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Beijing University of Civil Engineering and Architecture
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Beijing University of Civil Engineering and Architecture
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Abstract

本发明涉及再生水处理领域,特别涉及一种利用铁盐混凝剂原位水解生成羟基氧化铁用于去除再生水中磷的方法。本发明针对城市污水厂二级出水磷超标的问题,提出了一种利用碱盐与铁盐的共同作用提高再生水厂混凝、沉淀、过滤单元对磷去除效果的方法。其中,碱盐和铁盐溶液按一定摩尔比投加,二者反应原位生成羟基氧化铁(In situ FeOxHy)可凝聚吸附水中的磷并提高絮体的沉降性能,进一步通过固液分离反应器实现对磷的去除。本发明可应用于城市污水厂二级出水深度净化,也可应用于以城市污水厂出水或雨水为水源的再生水处理工程。The invention relates to the field of regenerated water treatment, in particular to a method for removing phosphorus in regenerated water by using an iron salt coagulant to hydrolyze in situ to generate iron oxyhydroxide. The invention aims at the problem that the phosphorus in the secondary effluent of the urban sewage plant exceeds the standard, and proposes a method for improving the phosphorus removal effect of the coagulation, precipitation and filtration units of the reclaimed water plant by using the joint action of the alkali salt and the iron salt. Among them, alkali salt and iron salt solution are added in a certain molar ratio, and the two react in situ to generate iron oxyhydroxide (In situ FeO x H y ), which can coagulate and adsorb phosphorus in water and improve the settling performance of flocs, and further pass solid-liquid A separate reactor achieves phosphorus removal. The invention can be applied to the deep purification of the secondary effluent of urban sewage plants, and can also be applied to reclaimed water treatment projects using the effluent of urban sewage plants or rainwater as water sources.

Description

A kind of iron salt coagulant in-situ hydrolysis that utilizes generates the method that hydrous iron oxide is used for removing reuse water phosphorus
Technical field
The invention belongs to the reused water processing technical field, particularly a kind of iron salt coagulant in-situ hydrolysis that utilizes generates the method that hydrous iron oxide is used for removing reuse water phosphorus.
Background technology
The body eutrophication that the discharging of source of students such as nitrogen, phosphorus key element causes pollutes and becomes the current important water environment pollution problem of China, and phosphorus is the limiting factor of many body eutrophications.There is the phosphorus problem that exceeds standard in many municipal effluent plant effluents, and take economically viable reinforced phosphor-removing measure to guarantee the Sewage Plant qualified discharge, and this is significant for the control body eutrophication.
The coagulant sedimentation phosphor-removing effect is remarkable, stable, also can effectively remove colourity in the water, turbidity, SS, COD Cr, BOD 5Deng pollutent.In addition, adopt the Coagulation Method dephosphorization not need additionally significantly purification facility, and have that technology is simple, floor space is little, advantage such as investment and running cost are low.Contrast, ferric flocculants such as iron trichloride, ferrous sulfate, ferric sulfate have better phosphor-removing effect than aluminium salt.But, in the municipal effluent plant effluent phosphorus often with coexistences such as organism, suspended particulate, above-mentioned pollutent also can consume coagulating agent and significantly improve molysite throwing amount.The sewage effluents lower for basicity, that surge capability is more weak, tend to occur iron salt hydrolysis not thoroughly, problems such as iron level rising in little, the water outlet of flco particle diameter, colourity increase, sedimentation and filtration weak effect.Adopt adsorbents adsorb dephosphorization such as hydrous iron oxide, calcium phosphate powder, tripolite loading iron carbonyl, compound hydroxyl ferro-aluminum can avoid the disadvantageous effect of coagulation, but have problems such as cost height, performance of the adsorbent are low, regenerative operation complexity.How improving generation and the phosphor-removing effect of sorbent materials such as hydrous iron oxide, is to expand the important way that coagulation technology is used in the reuse water dephosphorization is handled.
The present invention is directed to the problems referred to above, with trivalent iron salt (Fe 3+) with the OH of certain mol proportion -Mix, its appropriate hydrolysis is formed hydrous iron oxide, take full advantage of the active height of its dephosphorization, the abundant advantage of adsorption site, to improve the removal effect of reuse water ferric salt coagulation for phosphorus removal.The present invention can be applicable to municipal wastewater treatment plant secondary effluent deep purifying, and also can be applicable to municipal effluent plant effluent or rainwater is the reused water processing engineering at water source.
Summary of the invention
The objective of the invention is, be the not good enough regeneration water factory of water source and coagulation for phosphorus removal effect at the municipal wastewater treatment plant secondary effluent that exceeds standard with phosphorus, provide a kind of economy, effectively, the method that is easy in engineering, use, with effective phosphor-removing effect that improves, thereby improve the problem of body eutrophication.
Know-why of the present invention is, adds molysite and alkali salt solution and phosphorus in the municipal wastewater treatment plant secondary effluent and reacts, and molysite and alkali salt solution reaction original position generate hydrous iron oxide (In situ FeO xH y) can condense absorption phosphorus and improve its settling property.Molysite can directly improve the phosphorus surface potential by the charge neutrality effect, and generated in-situ In situ FeO xH yAlso adsorbable phosphorus improves its surface potential and settling property; Further, adopt the solid-liquid separation reactor to remove particulate form phosphorus.Through above-mentioned processing, the phosphorus removal effect will significantly improve.
In order to realize improving the purpose of phosphorus removal effect in the reuse water, the present invention takes following technical scheme:
1, the dissolving under fully stirring with alkali salt and molysite respectively forms alkali salt solution and iron salt solutions.Wherein the mol ratio of ferro element is 0.02: 1~3: 1 in the hydroxide radical in the alkali salt and the molysite.
The mixing salt of one or more in the optional sodium hydroxide of described alkali salt, calcium hydroxide, the potassium hydroxide etc.; Described molysite can be selected from one or more the mixing salt in iron(ic) chloride, ferric sulfate, iron nitrate, poly-ferric chloride, bodied ferric sulfate, the polymerization iron nitrate etc.
The mol ratio of ferro element is determined according to following principle in hydroxide radical in the alkali salt and the molysite:
When former water pH less than 6.5 and water in total alkalinity during less than 250mg/L, the mol ratio of ferro element is 2: 1 (not containing 2: 1)~3: 1 (containing 3: 1) in the hydroxide radical in the alkali salt and the molysite; When former water pH greater than 6.5 and less than 7.5 and water in total alkalinity during less than 250mg/L, the mol ratio of ferro element is 1: 1 (not containing 1: 1)~2: 1 (containing 2: 1) in the hydroxide radical in the alkali salt and the molysite; When former water pH greater than 6.5 and less than 7.5 and water in total alkalinity during greater than 250mg/L, the mol ratio of ferro element is 0.2: 1 (not containing 0.2: 1)~1: 1 (containing 1: 1) in the hydroxide radical in the alkali salt and the molysite; When former water pH greater than 7.5 and water in total alkalinity during less than 250mg/L, the mol ratio of ferro element is 0.05: 1 (not containing 0.05: 1)~0.2: 1 (containing 0.2: 1) in the hydroxide radical in the alkali salt and the molysite; When former water pH greater than 7.5 and water in total alkalinity during greater than 250mg/L, the mol ratio of ferro element is 0.02: 1 (not containing 1: 1)~0.05: 1 (containing 0.05: 1) in the hydroxide radical in the alkali salt and the molysite.
2, certain density alkali salt and molysite are added to pending water, add that to select can be the position of any one the added liquid preparation before the regeneration water factory mixed cell.Alkali salt and molysite dosage are for the original position that adds to the pending water generates hydrous iron oxide In sim FeO xH yIn the concentration of iron between 20~100mg/L.
3, after alkali salt and iron salt solutions add to the water, the In situ FeO that reaction generates xH yCan give full play to the active height of its dephosphorization, the abundant advantage of adsorption site, more phosphorus are adsorbed on its surface in the water.The In situ FeO that has adsorbed phosphorus xH yFurther take off steady cohesion in the coagulation unit, and finally removed by solid-liquid separation unit.
In situ FeO xH yCan adopt the dystopy preparation method or adopt in-situ preparation method to be prepared, it is characterized in that: with iron salt solutions as solution A, with alkali salt solution as solution B; In above-mentioned solution, the molar ratio range between hydroxide radical and the iron is 0.02: 1~3: 1.
Adopt the dystopy preparation method to be prepared In situ FeO xH yThe time, solution A added in the solution B fully mix, or solution B added in the solution A fully mix, or solution A and solution B added in the container simultaneously mix; The mixing time scope is 10s~3min;
Adopt in-situ preparation method to be prepared In situ FeO xH yThe time, solution A and solution B are added respectively in the phosphorous water, the two adds time order and function is one of following mode in proper order: add solution A earlier, add solution B after fully mixing; Add solution B earlier, add solution A after fully mixing; Solution A adds the back simultaneously with solution B and fully mixes; When solution A and solution B are not when adding simultaneously, solution A and solution B add that successively the timed interval is 5s~60s.
Described pending water refers to that phosphorus concentration refers in particular to municipal wastewater treatment plant secondary effluent or rainwater as the regeneration water source greater than the water of 0.5mg/L in the regeneration water source.
Described mixed cell is one or more the combination in waterpower mixing reactor, aeration mixing reactor, the mechanically mixing reactor.
Described solid-liquid separation unit is selected from one or more the combination in horizontal sedimentation tank, inclined tube/inclined-plate clarifying basin, media filtration, the ultrafiltration/micro-filtrate membrane filtration.
The technique effect that the present invention realizes is as follows:
1. need not to carry out the large-scale engineering transformation and get final product the treatment effect that efficient hardening improves phosphorus in the municipal wastewater treatment plant secondary effluent, method is simple, and the construction investment cost is low, is easy to realize in engineering;
2. use operating process easy, need not to increase complicated operation bidirectional on water factory daily operation management basis;
3. adopt medicament to be water purification medicament or water-purifying material commonly used in the water treatment, with low cost;
4. can obviously improve the removal effect of phosphorus in the water, and reduce settled water turbidity and particle concentration, reduce the filter tank operating load, prolong filtration cycle.
Embodiment
Embodiment 1
Certain regeneration water factory is the water source with the municipal wastewater treatment plant secondary effluent, and the treatment process of employing is waterpower hybrid reaction-advection sedimentation-quartz sand filtration.Phosphorus content is 3mg/L in the former water, and turbidity is 20NTU, and the flocculation agent of employing is iron trichloride, flocculation agent throwing amount is 50mg/L, but treatment effect is undesirable, shows as heavy back water, filter back water turbidity is higher, heavy back water tp removal rate only is 50%, and the filter cycle is 20 hours.
Adopt method reinforced phosphor-removing of the present invention: the 1) dissolving under fully stirring with sodium hydroxide and iron trichloride obtains sodium hydroxide solution and liquor ferri trichloridi respectively.2) sodium hydroxide solution and the liquor ferri trichloridi mol ratio according to 2: 1 is added simultaneously to the medicament filler place of water factory's mixed cell tubular static mixer front end, and added amount of chemical is for to count 50mg/L with the throwing amount of iron trichloride.3) after sodium hydroxide solution and liquor ferri trichloridi add to the water, the In situ FeO that reaction generates xH yAdsorbable more phosphorus has adsorbed the In situ FeO of phosphorus xH yFurther take off steady cohesion in the coagulation unit, and final remove by precipitation, filtering unit, heavy back water tp removal rate significantly improves to 70%, filter cycle stretch-out to 24 hour.
Embodiment 2
Certain regeneration water factory is the water source with the municipal wastewater treatment plant secondary effluent, and the treatment process of employing is mechanically mixing reaction-sloping plate deposition-multi-medium filtering.Phosphorus content is 4mg/L in the former water, and turbidity is 25NTU, and the flocculation agent of employing is poly-ferric chloride, flocculation agent throwing amount is 40mg/L, but treatment effect is undesirable, shows as heavy back water, filter back water turbidity is higher, heavy back water tp removal rate only is 50%, and the filter cycle is 22 hours.
Adopt method reinforced phosphor-removing of the present invention: the 1) dissolving under fully stirring with potassium hydroxide and poly-ferric chloride obtains potassium hydroxide solution and poly-ferric chloride solution respectively.2) potassium hydroxide solution and the poly-ferric chloride solution mol ratio according to 3: 1 is successively added to the medicament filler place of water factory's mixed cell tubular static mixer front end, and added amount of chemical is for to count 40mg/L with the throwing amount of poly-ferric chloride.3) after potassium hydroxide solution and poly-ferric chloride solution add to the water, the In situ FeO that reaction generates xH yAdsorbable more phosphorus has adsorbed the In situ FeO of phosphorus xH yFurther take off steady cohesion in the coagulation unit, and final remove by precipitation, filtering unit, heavy back water tp removal rate significantly improves to 75%, filter cycle stretch-out to 24 hour.
Embodiment 3
Certain regeneration water factory is the water source with the municipal wastewater treatment plant secondary effluent, and the treatment process of employing is that waterpower hybrid reaction-tube settling-submerged ultrafiltration filters.Phosphorus content is 5mg/L in the former water, and turbidity 30NTU, the flocculation agent of employing are ferric sulfate, flocculation agent throwing amount is 60mg/L, but treatment effect is undesirable, shows as heavy back water, filter back water turbidity is higher, heavy back water tp removal rate only is 50%, and the ultra-filtration membrane backwash cycle is 20 hours.
Adopt method reinforced phosphor-removing of the present invention: the 1) dissolving under fully stirring with calcium hydroxide and ferric sulfate obtains aqua calcis and ferrum sulfuricum oxydatum solutum respectively.2) aqua calcis and the ferrum sulfuricum oxydatum solutum mol ratio according to 1: 1 is added simultaneously to the medicament filler place of water factory's mixed cell tubular static mixer front end, and added amount of chemical is for to count 60mg/L with the throwing amount of ferric sulfate.3) after aqua calcis and ferrum sulfuricum oxydatum solutum add to the water, the In situ FeO that reaction generates xH yAdsorbable more phosphorus has adsorbed the In situ FeO of phosphorus xH yFurther take off steady cohesion in the coagulation unit, and final remove by precipitation, filtering unit, heavy back water tp removal rate significantly improves to 70%, ultra-filtration membrane backwash cycle stretch-out to 24 hour.

Claims (5)

1.一种利用原位生成羟基氧化铁In situ FeOxHy去除再生水中磷的方法,其特征是,所述的方法包括以下步骤:  1. a method utilizing in situ to generate iron oxyhydroxide In situ FeO x H y to remove phosphorus in regenerated water, is characterized in that, described method comprises the following steps: (1)向待处理水中投加铁盐水溶液和碱盐水溶液,在混合反应器中充分反应,使待处理水中的游离态磷转化为络合态磷;其中,碱盐溶液中的氢氧根与铁盐溶液中的铁元素的摩尔比为0.02∶1~3∶1;  (1) Add iron salt solution and alkali salt solution to the water to be treated, and fully react in the mixing reactor, so that the free phosphorus in the water to be treated is converted into complex phosphorus; wherein, the hydroxide in the alkali salt solution and The molar ratio of the iron element in the iron salt solution is 0.02:1~3:1; 所述的碱盐可选氢氧化钠、氢氧化钙、氢氧化钾等中的一种或一种以上的混合盐;  The alkali salt can be selected from one or more mixed salts of sodium hydroxide, calcium hydroxide, potassium hydroxide, etc.; 所述的铁盐可选自氯化铁、硫酸铁、硝酸铁、聚合氯化铁、聚合硫酸铁、聚合硝酸铁等中的一种或一种以上的混合盐;  The iron salt can be selected from one or more mixed salts of ferric chloride, ferric sulfate, ferric nitrate, polyferric chloride, polyferric sulfate, polyferric nitrate, etc.; (2)利用固液分离反应器去除步骤(1)反应后的混合反应器出水中的颗粒态磷以及其它杂质颗粒物。  (2) Using a solid-liquid separation reactor to remove particulate phosphorus and other impurity particles in the effluent of the mixed reactor after the reaction in step (1). the 2.根据权利要求1所述的原位生成羟基氧化铁In situ FeOxHy的制备方法,其特征在于包括异位制备方法或原位制备方法,具体包括如下步骤:  2. the preparation method of generating iron oxyhydroxide In situ FeO x H y in situ according to claim 1, is characterized in that comprising ex-situ preparation method or in-situ preparation method, specifically comprises the steps: 分别将碱盐和铁盐在充分搅拌下溶解,形成碱盐溶液和铁盐溶液;且碱盐溶液中的氢氧根与铁盐溶液中的铁元素的摩尔比为0.02∶1~3∶1;  The alkali salt and the iron salt are dissolved under sufficient stirring respectively to form an alkali salt solution and an iron salt solution; and the molar ratio of the hydroxide in the alkali salt solution to the iron element in the iron salt solution is 0.02:1 to 3:1 ; 将铁盐溶液作为溶液A,将碱盐溶液作为溶液B;  Iron salt solution is used as solution A, and alkali salt solution is used as solution B; 采用异位制备方法进行制备In situ FeOxHy时,将溶液A加入溶液B中进行充分混合,或将溶液B加入溶液A中进行充分混合,或将溶液A与溶液B同时加入一个容器中进行混合;混合时间范围为10s~3min;  When using the ex-situ preparation method to prepare In situ FeO x H y , add solution A to solution B for thorough mixing, or add solution B to solution A for full mixing, or add solution A and solution B to a container at the same time Mixing; the mixing time ranges from 10s to 3min; 采用原位制备方法进行制备In situ FeOxHy时,将溶液A与溶液B分别投加入含磷水中,二者投加时间先后顺序是以下方式之一:先投加溶液A,充分混合后投加溶液B;先投加溶液B,充分混合后投加溶液A;溶液A与溶液B同时投加后充分混合;当溶液A与溶液B不是同时投加时,溶液A与溶液B投加先后时间间隔为5s~60s。  When using the in-situ preparation method to prepare In situ FeO x H y , add solution A and solution B into phosphorus-containing water respectively. Add solution B; add solution B first, then add solution A after fully mixing; add solution A and solution B at the same time and then mix thoroughly; when solution A and solution B are not added at the same time, solution A and solution B should be added The successive time interval is 5s~60s. 3.根据权利要求1所述的原位生成羟基氧化铁In situ FeOxHy的制备方法,其特征是碱盐中的氢氧根与铁盐中铁元素的摩尔比按照如下原则确定:  3. the preparation method of generating iron oxyhydroxide In situ FeO x H y in situ according to claim 1 is characterized in that the mol ratio of the hydroxide radical in the alkali salt and the iron element in the iron salt is determined according to the following principles: 当原水pH小于6.5且水中总碱度小于250mg/L时,碱盐中的氢氧根与铁盐中铁元素的摩尔比为2∶1(不含2∶1)~3∶1(含3∶1);当原水pH大于6.5且小于7.5且水中总碱度小于250mg/L时,碱盐中的氢氧根与铁盐中铁元素的摩尔比为1∶1(不含1∶1)~2∶1(含2∶1);当原水pH大于6.5且小于7.5且水中总碱度大于250mg/L时,碱盐中的氢氧根与铁盐中铁元素的摩尔比为0.2∶1(不含0.2∶1)~1∶1(含1∶1);当原水pH大于7.5且水中总碱度小于250mg/L时,碱盐中的氢氧根与铁盐中铁元素的摩尔比为0.05∶1(不含0.05∶1)~0.2∶1(含0.2∶1);当原水pH大于7.5且水中总碱度大于250mg/L时,碱盐中的氢氧根与铁盐中铁元素的摩尔比为0.02∶1(不含1∶1)~0.05∶1(含0.05∶1)。  When the pH of the raw water is less than 6.5 and the total alkalinity in the water is less than 250mg/L, the molar ratio of the hydroxide in the alkali salt to the iron element in the iron salt is 2:1 (excluding 2:1) to 3:1 (including 3:1) 1); when the pH of the raw water is greater than 6.5 and less than 7.5 and the total alkalinity in the water is less than 250mg/L, the molar ratio of the hydroxide in the alkali salt to the iron element in the iron salt is 1:1 (excluding 1:1)~2 : 1 (including 2: 1); when the pH of the raw water is greater than 6.5 and less than 7.5 and the total alkalinity in the water is greater than 250 mg/L, the molar ratio of the hydroxide in the alkali salt to the iron element in the iron salt is 0.2: 1 (excluding 0.2:1) ~ 1:1 (including 1:1); when the pH of the raw water is greater than 7.5 and the total alkalinity in the water is less than 250mg/L, the molar ratio of the hydroxide in the alkali salt to the iron element in the iron salt is 0.05:1 (excluding 0.05:1) ~ 0.2:1 (including 0.2:1); when the pH of the raw water is greater than 7.5 and the total alkalinity in the water is greater than 250mg/L, the molar ratio of the hydroxide in the alkali salt to the iron element in the iron salt is 0.02:1 (excluding 1:1) to 0.05:1 (including 0.05:1). the 4.根据权利要求1所述的利用原位生成羟基氧化铁In situ FeOxHy去除再生水中磷的方法,其特征是原位生成羟基氧化铁In situ FeOxHy的投加量为使得投加至待处理水中的原位生成羟基氧化铁In situFeOxHy中的铁的浓度在20~100mg/L之间。  4. the method for removing phosphorus in regenerated water utilizing in situ generation of iron oxyhydroxide In situ FeO x H y according to claim 1, characterized in that the dosage of in situ generation of iron oxyhydroxide In situ FeO x H y is such that The iron concentration in the in-situ-formed iron oxyhydroxide In situFeO x H y added to the water to be treated is between 20 and 100 mg/L. 5.根据权利要求1所述的利用原位生成羟基氧化铁In situ FeOxHy去除再生水中磷的方法,其特征是所述的混合单元是水力混合反应器、曝气混合反应器、机械混合反应器中的一种或一种以上的组合;所述的固液分离单元选自平流沉淀池、斜管/斜板沉淀池、介质过滤、超滤/微滤膜过滤中的一种或一种以上的组合。  5. Utilize in situ to generate iron oxyhydroxide In situ FeO x H y to remove the method for phosphorus in regenerated water according to claim 1, it is characterized in that described mixing unit is a hydraulic mixing reactor, an aeration mixing reactor, a mechanical One or more than one combination in the mixed reactor; the solid-liquid separation unit is selected from one or more than one combination.
CN201310120436XA 2013-04-09 2013-04-09 Method for removing phosphorus from reclaimed water by using ferric hydroxide produced through iron salt coagulant in-situ hydrolysis Pending CN103232103A (en)

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CN108033653A (en) * 2018-01-08 2018-05-15 浙江利欧环境科技有限公司 A kind of addition method of city domestic sewage dephosphorization agent and alkali
CN111039658A (en) * 2019-12-31 2020-04-21 广东省水利水电科学研究院 Phosphorus removal ceramsite and preparation method thereof
CN113185024A (en) * 2021-04-25 2021-07-30 吉林梅基特环保科技有限公司 Method for purifying condensed water
CN114835303A (en) * 2022-06-07 2022-08-02 西安交通大学 Coral reef-like floc induction forming method for improving removal efficiency of small molecular organic matters

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