WO2011015041A1 - Procédé de traitement des eaux usées et système utilisant ledit procédé - Google Patents

Procédé de traitement des eaux usées et système utilisant ledit procédé Download PDF

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Publication number
WO2011015041A1
WO2011015041A1 PCT/CN2010/001210 CN2010001210W WO2011015041A1 WO 2011015041 A1 WO2011015041 A1 WO 2011015041A1 CN 2010001210 W CN2010001210 W CN 2010001210W WO 2011015041 A1 WO2011015041 A1 WO 2011015041A1
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WO
WIPO (PCT)
Prior art keywords
sewage
unit
nanofiltration membrane
sewage treatment
reverse osmosis
Prior art date
Application number
PCT/CN2010/001210
Other languages
English (en)
Chinese (zh)
Inventor
刘继斌
汲江
丁志伟
胡晓宏
单德生
谭清
陆海锋
Original Assignee
无锡尚德太阳能电力有限公司
无锡江天高新纳米技术材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 无锡尚德太阳能电力有限公司, 无锡江天高新纳米技术材料有限公司 filed Critical 无锡尚德太阳能电力有限公司
Publication of WO2011015041A1 publication Critical patent/WO2011015041A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2643—Crystallisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/02—Elements in series
    • B01D2317/022—Reject series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to the field of industrial wastewater treatment, and more particularly to a method for treating heavy metal ion-containing sewage in the solar industry, electroplating industry, semiconductor and microelectronics industries.
  • the present invention relates to a sewage treatment method and a system for use in the treatment method.
  • nanofiltration membranes or reverse osmosis membranes have been introduced into the sewage treatment process, but they are generally used alone.
  • the interception rate of metal ions such as copper ions is too low due to a large flux, and the ion removal rate is not greatly improved.
  • the reverse osmosis membrane alone uses a low flux, a low flux, a high operating pressure, and a high energy consumption, so the overall efficiency is low and uncompetitive.
  • the method of separately using membrane filtration not only fails to achieve the purpose of completely removing heavy metal ions, but also causes membrane fouling, and therefore is not practical.
  • the reverse osmosis membrane is generally selected for the purpose of concentration without selecting the nanofiltration membrane, but this will seriously contaminate the reverse osmosis membrane.
  • the solar, electroplating, semiconductor and microelectronics industries there is an urgent need to develop a treatment that achieves zero discharge of wastewater.
  • the present invention provides a sewage treatment method capable of effectively achieving zero discharge of sewage in the solar energy industry and related industries. Another object of the present invention is to provide a system capable of effectively implementing the above sewage treatment method.
  • Technical Solution In order to achieve the above object, the present invention provides a sewage treatment method, which comprises the following steps:
  • the nanofiltration membrane is not particularly limited, and any commercially available nanofiltration membrane having a sodium chloride intercept rate of 40% or more can be used as the nanofiltration membrane of the present invention. Further, in the range of pH 3 to 10, the higher the pH, the higher the shutoff rate for various ions. The best separation results when the pH is in the range of 6 to 10.
  • the concentration is concentrated by about 40 to 20 times after being filtered by the nanofiltration membrane.
  • the final concentration of copper ions is about 8 wt%, which is close to saturation.
  • the nickel-containing wastewater when the initial concentration of nickel ions is about 0.8 wt% 1.6 wt%, the concentration is concentrated about 10 to 5 times after filtration through the nanofiltration membrane, and the final concentration of nickel ions is about It is 8 wt%, close to saturation.
  • the seed crystal is one or several chemicals, and the substances are added to the solution containing heavy metal ions, so that the concentration of the heavy metal ions is close to saturation, so that the solution is crystallized and precipitated to be heavy metal ions. separate from.
  • sodium hydroxide can be used as a heavy metal ion Seed crystal.
  • the seed crystal which can be used in the present invention is not limited to sodium hydroxide, such as lithium hydroxide, potassium hydroxide, iron chloride, aluminum chloride or the like.
  • the separated heavy metal precipitate can be post-treated for recycling.
  • the temperature (room temperature) and the pH (pH value of 3 to 10) are substantially determined, it can be determined according to the solubility product constant of the heavy metal ion to be removed, the concentration, the volume of the raw sewage water, and the pH value.
  • the amount of seed crystal to be added is close to saturation or the pH of the precipitate is different.
  • the pH required to precipitate different metal ions can be determined according to Figure 1; when the solution contains different metal ions at the same time, A suitable pH can be chosen to simultaneously precipitate multiple metal ions.
  • the reverse osmosis membrane is not particularly limited, and any commercially available reverse osmosis membrane having a sodium chloride intercept rate of 90% or more can be used as the reverse osmosis membrane of the present invention.
  • the higher the pH value the higher the shutoff rate for various ions.
  • the sewage treatment method of the present invention further includes the following steps according to the concentration of the metal ions in the raw water of the sewage:
  • the nanofiltration membrane of the first step 1) may be filtered one or more times after the solution of the induced crystallization step 2) and/or the step 4). Times.
  • the sewage treatment method of the present invention may further comprise any one or two of steps 5) and 5):
  • the ion exchange resin is not particularly limited, and any commercially available anion/cation exchange resin can be used as the ion exchange resin of the present invention.
  • the sewage treatment method of the present invention further comprises the following steps: filtering the suspended particles in the sewage by using a filtering unit before the step 1) and/or the step 3) to protect the corresponding filter membrane .
  • the filter unit achieves the corresponding protection purpose by adding a protective filter medium (such as sand filter, polypropylene filter, etc.).
  • another aspect of the present invention provides a system for the above sewage treatment method, the system comprising: a primary feed water tank unit for storing raw sewage water, the unit may be included as needed One or more inlet water storage tanks; a nanofiltration membrane unit connected to the first-stage water storage tank unit for performing the first-stage nanofiltration membrane concentration filtration on the sewage, wherein there is no particular limitation on the nanofiltration membrane, As long as it is a commercial nanofiltration membrane having a sodium chloride intercept rate of 40% or more, it can be used as the nanofiltration membrane of the present invention; the first stationary storage tank unit is connected to the nanofiltration membrane unit for passing Seed crystals are added to the concentrated sewage of the nanofiltration membrane to induce crystallization.
  • the unit may include one or more static storage tanks as needed; a secondary water storage tank unit connected to the nanofiltration membrane unit for storing the above
  • the sewage filtered by the nanofiltration membrane is a water inlet tank for secondary reverse osmosis filtration.
  • the unit may include one or more inlet water storage tanks as needed; reverse osmosis membrane single And the second inlet water storage tank unit is connected to the second reverse osmosis filtration of the sewage filtered by the nanofiltration membrane, and the reverse osmosis membrane is not particularly limited as long as the sodium chloride intercept rate is More than 90% of commercially available reverse osmosis membranes can be used as the reverse osmosis membrane of the present invention; the effluent tank unit is connected to the reverse osmosis membrane unit for storing water filtered through two stages, the water Recycling standards can be recycled.
  • the sewage treatment system of the present invention further comprises: a second stationary storage tank unit connected to the reverse osmosis membrane unit for passing Seed crystals are added to the sewage filtered by the reverse osmosis membrane to induce crystallization, and the metal ions are crystallized and precipitated to separate the metal ions.
  • the unit may include one or more static storage tanks as needed.
  • the first stationary storage tank unit and/or the second stationary storage tank unit may be connected to the primary water storage tank unit through The pump introduces the solution remaining after the induced crystallization into the primary feed water tank unit to repeat the nanofiltration membrane filtration one or more times.
  • the sewage treatment system of the present invention may further comprise any one or two of the following two units: an ion exchange treatment unit, which The effluent tank unit is connected, the unit comprising a cation exchange resin or/and an anion exchange resin, wherein any commercially available anion/cation exchange resin can be used as the ion exchange resin of the present invention; and an activated carbon treatment unit, which is combined with an effluent storage tank The unit or ion exchange processing unit is connected.
  • an ion exchange treatment unit which The effluent tank unit is connected, the unit comprising a cation exchange resin or/and an anion exchange resin, wherein any commercially available anion/cation exchange resin can be used as the ion exchange resin of the present invention
  • an activated carbon treatment unit which is combined with an effluent storage tank The unit or ion exchange processing unit is connected.
  • the sewage treatment system of the present invention may further comprise: a filtration unit, which may be disposed before the nanofiltration membrane unit and/or the reverse osmosis membrane unit for removing suspended particles and corresponding
  • the filter membrane provides protection and may include a sand filter and/or a polypropylene depth filter.
  • the filter unit achieves the corresponding protection purpose by adding a protective filter medium (such as sand filter, polypropylene filter, etc.).
  • the sewage treatment method provided by the present invention has the following advantages: First, the raw water of the sewage is concentrated by using a nanofiltration membrane, so that the concentration of the metal ions of two or more valences is close to a saturated state, and then the seed crystal is added to induce crystallization. This can remove the divalent or multivalent heavy metal ions in the sewage more effectively than the traditional precipitation method, and can also avoid the contamination of the reverse osmosis membrane by the next enthalpy; secondly, the reverse osmosis membrane is used to further filter the residue.
  • the treatment can realize the purpose of producing ultrapure water from the sewage industry containing heavy metal ions. Therefore, the method and system provided by the present invention can not only effectively remove heavy metal ions from sewage, thereby achieving zero discharge of sewage in the solar industry and related industries, but also providing recyclable water (recycling:) and ultrapure water. Reduce production costs accordingly.
  • FIG. 1 is a graph showing a relationship between a pH value and a metal concentration when a metal hydroxide forms a precipitate
  • FIG. 2 is a schematic view of a system for sewage treatment according to a preferred embodiment of the present invention
  • Figure 4 is a schematic illustration of a system for wastewater treatment provided by a further preferred embodiment of the present invention.
  • 1 is the water inlet pipeline
  • 2 and 3 are the first-stage water storage tank
  • 4 is the control valve
  • 5 is the first stationary storage tank
  • 6 is the second stationary storage tank
  • 7 is the pump
  • 10 and 11 are secondary feed water storage tanks
  • 19A is a cation exchange resin
  • 19B is an anion exchange resin
  • 19C is an activated carbon treatment unit
  • 20 is a water outlet line.
  • FIG. 2 is a schematic diagram of a system for sewage treatment provided by the present invention.
  • the sewage treatment system of the present invention comprises: a first-stage water storage tank 2 and 3 for storing sewage raw water; a nanofiltration membrane unit 9 connected to the primary feed water storage tanks 2, 3 for performing the sewage
  • the nanofiltration membrane is concentrated and filtered, wherein the nanofiltration membrane uses a commercially available commercial nanofiltration membrane with a sodium chloride intercept rate of 40% or more;
  • the first stationary storage tank 5 is connected to the nanofiltration membrane unit 9 for Seed crystals are added to the sewage concentrated by the nanofiltration membrane to induce crystallization;
  • secondary water storage tanks 10 and 11 are connected to the nanofiltration membrane unit 9 for storing the above-mentioned sewage filtered through the nanofiltration membrane, which is a reverse osmosis filtration water inlet tank; a reverse osmosis membrane unit 15 connected to the secondary water storage tanks 10, 11 for performing secondary reverse osmosis filtration on the sewage filtered by the nanofiltration membrane, wherein
  • the reverse osmosis membrane adopts a commercially available reverse osmos
  • the sewage treatment system of the present embodiment further comprises: a second stationary storage tank 6 connected to the reverse osmosis membrane unit 15 for reverse osmosis filtration according to the concentration of the metal ions in the raw water of the sewage. Seed crystals are added to the membrane-filtered sewage to induce crystallization, and the metal ions are crystallized and precipitated to separate the metal ions.
  • the first stationary storage tank 5 and/or the second stationary storage tank 6 described above are connected to the primary water storage tanks 2, 3, The solution remaining after the induced crystallization is introduced into the primary feed water tank 2, 3 by a pump, and the nanofiltration membrane is repeatedly filtered one or more times.
  • the sewage treatment system of the present embodiment further includes filters 8 and/or 14 disposed before the nanofiltration membrane unit 9 and/or the reverse osmosis membrane unit 15, depending on the degree of contamination of the sewage to be treated, It is used to remove suspended particles to protect the filter behind it, including sand filters and/or polypropylene depth filters.
  • the sewage treatment system of the present embodiment first concentrates the raw sewage water to be treated with a nanofiltration membrane to make it saturated or nearly saturated, and then induces crystallization by using ferric chloride, sodium hydroxide or the like to make it from the solution. The crystals are precipitated; the water passing through the nanofiltration membrane is filtered by a reverse osmosis membrane to remove residual metal ions and other impurities.
  • FIG. 3 is a schematic view of another sewage treatment system provided by the present invention.
  • the sewage treatment system shown in Fig. 3 further includes a cation exchange resin 19A, an anion exchange resin 19B, and a water discharge line 20, and a cation exchange resin 19A is connected to the water discharge tank 16 through a line 18, anion, as compared with the system shown in Fig. 2.
  • the exchange resin 19B is connected to the water outlet line 20.
  • FIG. 4 is a schematic view of still another sewage treatment system according to the present invention.
  • the sewage treatment system shown in Fig. 4 further includes an activated carbon treatment unit 19C in which the cation is separated
  • the sub-exchange resin 19A is connected to the outlet tank 16 via a line 18, the cation exchange resin 19A, the anion exchange resin 19B and the activated carbon treatment unit 19C are connected, and the activated carbon treatment unit 19C is connected to the outlet line 20.
  • the activated carbon treatment unit 19C of the present embodiment and the cation exchange resin 19A and the anion exchange resin 19B of the embodiment 1.2 may be used at different times, that is, the activated carbon treatment unit 19C of the present embodiment may be separately combined with the system shown in FIG. In conjunction with.
  • Example 2.1 shows an example of the results of treatment of copper-containing wastewater in the solar industry using the sewage treatment system of Example 1.1.
  • the raw water of the sewage has a pH of 5 to 8.
  • the NF270 nanofiltration membrane of Dow Chemical Company is used to concentrate the raw sewage water, so that the concentration of copper ions in the sewage is close to saturation, wherein the pressure during filtration is 0.1 ⁇ 2 MPa, and the seed crystal added to the sewage is Sodium hydroxide, using sodium hydroxide to adjust the pH of the sewage to about 9.5, thereby inducing the crystallization of copper ions to crystallize out of the sewage.
  • Example 2.2 Table 2 below shows an example of the results of treatment of wastewater containing various metal ions in the solar industry using the sewage treatment system of Example 1.1.
  • the raw water of the sewage has a pH of 5 to 6, and the raw water of the sewage is concentrated at room temperature using the NF270 nanofiltration membrane of the Dow Chemical Company, so that the concentration of the metal ions in the sewage is close to saturation, wherein when filtering
  • the pressure is 0.1 ⁇ 2 MPa
  • the seed crystal added to the sewage is sodium hydroxide
  • the pH of the sewage is adjusted to about 10.2 by using sodium hydroxide, thereby inducing crystallization of each ion to crystallize it out from the sewage.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Dans le procédé de traitement des eaux usées ci-décrit, lesdites eaux usées sont d'abord concentrées par une membrane de nanofiltration, de façon à obtenir une concentration d'ions métalliques divalents ou polyvalents dans les eaux usées proche de l'état de saturation, puis un germe cristallin est ajouté pour induire la cristallisation. Les ions métalliques résiduels et autres impuretés contenus dans les eaux usées sont, en outre, filtrés par une membrane à osmose inverse, pour récupérer une eau apte à la réutilisation. Un système utilisant ledit procédé est également décrit. Le procédé selon l'invention permet d'éliminer plus efficacement les ions métalliques divalents ou polyvalents contenus dans les eaux usées, avec une décharge nulle.
PCT/CN2010/001210 2009-08-07 2010-08-09 Procédé de traitement des eaux usées et système utilisant ledit procédé WO2011015041A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2009101640767A CN101987765B (zh) 2009-08-07 2009-08-07 一种污水处理方法以及该处理方法所用的系统
CN200910164076.7 2009-08-07

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CN102583831A (zh) * 2012-03-09 2012-07-18 广西宇达水处理设备工程有限公司 废水处理与回用膜分离处理工艺技术
WO2020053375A1 (fr) 2018-09-14 2020-03-19 Fermentalg Procede d'extraction d'une huile riche en acides gras polyunsatures (agpi)

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CN105859010B (zh) * 2016-06-08 2019-01-22 浙江奇彩环境科技股份有限公司 一种含酸废水的处理工艺
CN109867389A (zh) * 2019-04-16 2019-06-11 芜湖沃泰环保科技有限公司 一种矿山土壤淋洗污水的处理系统及其方法
CN116573741A (zh) * 2023-07-13 2023-08-11 济南山源环保科技有限公司 一种基于物联网的工业循环排污水处理系统

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FR3085962A1 (fr) 2018-09-14 2020-03-20 Fermentalg Procede d'extracton d'une huile riche en pufa

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