TW201731775A - Treatment method of high-hardness water drainage which is to contain the process to add the coagulant, the coarse filtration process, the membrane filtration process, and the reverse cleaning process - Google Patents
Treatment method of high-hardness water drainage which is to contain the process to add the coagulant, the coarse filtration process, the membrane filtration process, and the reverse cleaning process Download PDFInfo
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- TW201731775A TW201731775A TW106107821A TW106107821A TW201731775A TW 201731775 A TW201731775 A TW 201731775A TW 106107821 A TW106107821 A TW 106107821A TW 106107821 A TW106107821 A TW 106107821A TW 201731775 A TW201731775 A TW 201731775A
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- 238000001914 filtration Methods 0.000 title claims abstract description 206
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000011282 treatment Methods 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 90
- 238000004140 cleaning Methods 0.000 title claims abstract description 41
- 230000008569 process Effects 0.000 title claims abstract description 20
- 239000000701 coagulant Substances 0.000 title claims abstract description 15
- 238000005374 membrane filtration Methods 0.000 title abstract description 66
- 239000012528 membrane Substances 0.000 claims abstract description 210
- 230000002378 acidificating effect Effects 0.000 claims abstract description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 239000010865 sewage Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000005086 pumping Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
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- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
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- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
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- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D24/00—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
- B01D29/01—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with flat filtering elements
-
- 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
- B01D61/04—Feed pretreatment
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- 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
- B01D61/58—Multistep processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
Abstract
Description
本發明是關於高硬度排水之處理方法。本案主張的優先權是根據2016年3月14日在日本申請專利的特許出願第2016-049605號，因此，是援用上述日本申請案所記載之全部的記載內容。 The present invention relates to a method of treating high hardness drainage. The priority of the present invention is based on the Japanese Patent Application No. 2016-049605, filed on Jan. 14, 2016, the entire disclosure of which is incorporated herein by reference.
已知的排水之處理方法，係有：在進行過生物處理之類的一次處理之後，再使用限外超過濾膜或精密過濾膜來將排水進行過濾的方法。藉由使用限外超過濾膜或精密過濾膜來進行過濾，可將排水中的有機物等的浮游物質幾乎都全部除去。然而，這種開口直徑比較小的過濾膜，比較容易堵塞而降低處理能力，因此，必須經常地將清洗水朝逆方向進行通水，藉以進行逆清洗來恢復處理能力。 A known method of treating drainage is a method of filtering drainage by using an external ultrafiltration membrane or a precision filtration membrane after one treatment such as biological treatment. By using an ultra-filtration membrane or a microfiltration membrane to filter, almost all of the floating matter such as organic matter in the drainage can be removed. However, such a filter membrane having a relatively small opening diameter is relatively easy to clog and reduces the processing ability. Therefore, it is necessary to constantly pass the washing water in the reverse direction to perform reverse washing to restore the processing ability.
在排水的種類當中，也會有硬度高的排水。使用限外超過濾膜或精密過濾膜來對於硬度高的排水進行過濾的話，鎂和鈣將會析出在這些過濾膜的表面，會有助長過濾膜堵塞的問題。因此，有人提出的可作為處理高硬 度排水的方法的技術方案，是藉由添加鹼來使得溶解在水中的金屬析出之後，才利用限外超過濾膜進行過濾的方法(請參考日本實開平6-72691號公報)。 Among the types of drainage, there is also a high-density drainage. When an ultra-filtration membrane or a precision filtration membrane is used to filter the high-durability drainage, magnesium and calcium will precipitate on the surface of these filtration membranes, which may contribute to the clogging of the filtration membrane. Therefore, some people have proposed to deal with high hardness. In the method of the method of the degree of drainage, the method of filtering the metal dissolved in the water by the addition of a base is carried out by using an ultrafiltration membrane (see Japanese Unexamined Patent Publication No. Hei 6-72691).
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本實開平6-72691號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. Hei 6-72691
上述公報所揭示的處理方法，是將藉由添加入鹼而析出的金屬利用過濾膜進行分離，因此，在較短時間內，過濾膜的壓力損失會增大，必須頻繁地進行過濾膜的清洗。特別是在水中係有機物存在的情況，因添加入鹼而析出的金屬會將有機物予以吸附而形成浮游物質，而會助長過濾膜的堵塞。 In the treatment method disclosed in the above publication, the metal precipitated by the addition of the alkali is separated by the filtration membrane. Therefore, the pressure loss of the filtration membrane is increased in a short period of time, and the filtration membrane must be frequently cleaned. . In particular, in the case where an organic substance is present in the water, the metal precipitated by the addition of the alkali adsorbs the organic substance to form a floating substance, which contributes to clogging of the filtration membrane.
一般而言，想要將已經附著有機物的過濾膜重新利用，係使用可溶解蛋白質等的鹼性的清洗液比較有利。然而，如果是對於處理高硬度排水的過濾膜，沖洗鹼性的清洗液的話，將導致排水中的金屬的更為析出，反而會產生使得過濾膜堵塞的問題。 In general, it is advantageous to use an alkaline cleaning solution that dissolves proteins or the like in order to reuse a filter membrane to which an organic substance has been attached. However, in the case of a filter membrane for treating high-hardness drainage, rinsing an alkaline cleaning solution causes a more precipitation of metal in the drainage, which in turn causes a problem of clogging of the filtration membrane.
[用以解決課題之技術方案] [Technical solution to solve the problem]
本發明之一種態樣的高硬度排水之處理方法，是鈣硬度為100以上的高硬度排水之處理方法，其具備：將凝集劑添加入上述高硬度排水的工序；將上述凝集 劑添加工序後的高硬度排水利用過濾層進行粗過濾的工序；將上述粗過濾工序後的高硬度排水利用精密過濾膜或限外超過濾膜進行膜過濾的工序；將上述精密過濾膜或限外超過濾膜利用酸性水進行逆清洗的工序。 The method for treating high-hardness drainage according to an aspect of the present invention is a method for treating high-hardness drainage having a calcium hardness of 100 or more, comprising: a step of adding a coagulant to the high-hardness drainage; and agglutinating the above a step of coarsely filtering the high-hardness drainage after the agent addition step by the filtration layer; a step of filtering the high-hardness drainage after the coarse filtration step by using a precision filtration membrane or an ultrafiltration membrane; and the above-mentioned precision filtration membrane The outer ultrafiltration membrane is subjected to a reverse cleaning step using acidic water.
本發明之一種態樣的高硬度排水之處理方法，過濾膜的清洗比較容易。 In the method of treating high-hardness drainage of an aspect of the present invention, the cleaning of the filtration membrane is relatively easy.
1、11‧‧‧凝集槽 1, 11‧‧‧ agglutination tank
2、12‧‧‧凝集劑添加裝置 2, 12‧‧‧ agglutinating agent adding device
3‧‧‧過濾泵浦 3‧‧‧Filter pump
4、14‧‧‧過濾塔 4, 14‧ ‧ filter tower
5、19‧‧‧膜過濾單元 5, 19‧‧‧ membrane filtration unit
6、23‧‧‧清洗水槽 6, 23‧‧‧ cleaning sink
7、25‧‧‧清洗用泵浦 7, 25 ‧ ‧ cleaning pump
13‧‧‧粗過濾泵浦 13‧‧‧ coarse filter pump
15‧‧‧粗過濾受水槽 15‧‧‧ coarse filter sink
16‧‧‧移送用泵浦 16‧‧‧Transfer pump
17‧‧‧膜過濾供水槽 17‧‧‧ membrane filtration water supply tank
18‧‧‧膜過濾泵浦 18‧‧‧ membrane filtration pump
20‧‧‧膜處理供水槽 20‧‧‧membrane treatment water supply tank
21‧‧‧膜處理泵浦 21‧‧‧ membrane treatment pump
22‧‧‧膜處理單元 22‧‧‧Film processing unit
24‧‧‧酸添加裝置 24‧‧‧acid addition device
第1圖是顯示本發明之一種實施方式的高硬度排水之處理方法所使用的排水處理裝置的構成之示意圖。 Fig. 1 is a schematic view showing the configuration of a wastewater treatment apparatus used in a method for treating high-hardness drainage according to an embodiment of the present invention.
第2圖是顯示與本發明的第1圖不同的實施方式的高硬度排水之處理方法所使用的排水處理裝置的構成之示意圖。 Fig. 2 is a schematic view showing the configuration of a wastewater treatment apparatus used in the method for treating high-hardness drainage which is different from the first embodiment of the present invention.
第3圖是顯示高硬度排水之處理方法的各處理例中的精密過濾膜的流束變化之圖表。 Fig. 3 is a graph showing a change in the flow of the fine filtration membrane in each treatment example of the treatment method for high-hardness drainage.
第4圖是顯示高硬度排水之處理方法的處理例8中的精密過濾膜的流束變化之圖表。 Fig. 4 is a graph showing a change in the flow of the fine filtration membrane in the treatment example 8 of the treatment method for high-hardness drainage.
[本發明所欲解決之技術課題] [Technical Problem to be Solved by the Invention]
本發明的技術課題是要提供：過濾膜的清洗比較容易的高硬度排水之處理方法。 A technical object of the present invention is to provide a method for treating high-hardness drainage which is relatively easy to clean a filtration membrane.
[發明之效果] [Effects of the Invention]
本發明的高硬度排水之處理方法，過濾膜的清洗比較容易。 In the method for treating high hardness drainage of the present invention, the cleaning of the filtration membrane is relatively easy.
[本發明的實施方式的說明] [Description of Embodiments of the Present Invention]
本發明之一種態樣的高硬度排水之處理方法，是鈣硬度為100以上的高硬度排水之處理方法，其具備：將凝集劑添加入上述高硬度排水的工序；將上述凝集劑添加工序後的高硬度排水利用過濾層進行粗過濾的工序；將上述粗過濾工序後的高硬度排水利用精密過濾膜或限外超過濾膜進行膜過濾的工序；將上述精密過濾膜或限外超過濾膜利用酸性水進行逆清洗的工序。 The method for treating a high-hardness drainage according to an aspect of the present invention is a method for treating a high-hardness drainage having a calcium hardness of 100 or more, comprising: a step of adding a coagulant to the high-hardness drainage; and the step of adding the aggregating agent a step of coarsely filtering the high-hardness drainage by the filtration layer; a step of filtering the high-hardness drainage after the coarse filtration step by using a precision filtration membrane or an ultra-ultrafiltration membrane; and the above-mentioned precision filtration membrane or ultra-filtration membrane The step of performing reverse cleaning using acidic water.
該高硬度排水之處理方法，在使用上述精密過濾膜或限外超過濾膜的膜過濾工序之前，係具備：使高硬度排水中的有機物凝集在一起之凝集劑添加工序、以及將凝集後的有機物予以分離的粗過濾工序，如此一來，有機物難以附著到上述過濾膜。因此，該高硬度排水之處理方法，在過濾膜上，主要是附著了金屬或金屬化合物，因此，在逆清洗工序中，可利用酸性水比較容易就將過濾膜的附著物除去。換言之，該高硬度排水之處理方法，過濾膜的清洗比較容易。 The method for treating the high-hardness drainage includes a coagulant addition step of aggregating the organic substances in the high-hardness drainage and a coagulation process before the membrane filtration step using the above-described fine filtration membrane or the ultra-ultrafiltration membrane. The coarse filtration step in which the organic matter is separated, so that it is difficult for the organic substance to adhere to the filtration membrane. Therefore, in the treatment method of the high-hardness drainage, the metal or the metal compound is mainly adhered to the filtration membrane. Therefore, in the reverse cleaning step, the deposit of the filtration membrane can be removed relatively easily by the acidic water. In other words, the treatment method of the high-hardness drainage is relatively easy to clean the filtration membrane.
上述凝集劑係可採用聚合氯化鋁。是以，該高硬度排水之處理方法，藉由採用聚合氯化鋁作為上述凝 集劑，可以較低的成本並且確實將有機物凝集分離，減少有機物附著到精密過濾膜或限外超過濾膜，如此一來，可提昇利用酸性水來清洗精密過濾膜或限外超過濾膜時的清洗效果。 The above aggregating agent may be a polyaluminum chloride. Therefore, the high hardness drainage treatment method uses the polyaluminum chloride as the above condensation Collecting agent can lower the cost of the organic matter and agglomerate and separate the organic matter, and reduce the adhesion of organic substances to the ultrafiltration membrane or the ultrafiltration membrane. Therefore, when the acidic water is used to clean the precision filtration membrane or the outer superfiltration membrane Cleaning effect.
上述酸性水係可含有鹽酸或檸檬酸。是以，該高硬度排水之處理方法，藉由採用含有鹽酸或檸檬酸的上述酸性水，可以較低的成本並且確實地對於精密過濾膜或限外超過濾膜進行逆清洗，而且也不容易與高硬度排水中的鈣等的離子結合來生成析出物。 The above acidic water system may contain hydrochloric acid or citric acid. Therefore, the method for treating the high-hardness drainage can be carried out by using the above-mentioned acidic water containing hydrochloric acid or citric acid, and can be used for the reverse cleaning of the fine filtration membrane or the ultra-filtration membrane without limitation, and is not easy. It is combined with ions such as calcium in high-hardness drainage to form precipitates.
上述過濾槽，是以保留粒子直徑為1μm的過濾層來進行過濾即可。該高硬度排水之處理方法，藉由使用保留粒子直徑為1μm的過濾層，可抑制在過濾膜上的析出，而可減少過濾膜的清洗頻度。 The filter tank may be filtered by a filter layer having a particle diameter of 1 μm. In the method of treating high-hardness drainage, by using a filtration layer having a particle diameter of 1 μm, precipitation on the filtration membrane can be suppressed, and the cleaning frequency of the filtration membrane can be reduced.
上述過濾槽，是以有效直徑為0.4mm以上且0.7mm以下的過濾層來進行過濾即可。該高硬度排水之處理方法，藉由使用有效直徑為0.4mm以上且0.7mm以下的過濾層，當污水中的硬度較低的情況下，可以處理量做優先考量而暫不考量過濾，因而可更增大處理量。 The filter tank may be filtered by a filter layer having an effective diameter of 0.4 mm or more and 0.7 mm or less. The high-hardness drainage treatment method uses a filter layer having an effective diameter of 0.4 mm or more and 0.7 mm or less. When the hardness in the sewage is low, the treatment amount can be prioritized and the filtration is temporarily not considered. Increase the throughput.
亦可又具備：將上述膜過濾後的高硬度排水，利用逆滲透膜進行膜處理的工序。是以，該高硬度排水之處理方法，藉由又具備：將上述膜過濾後的高硬度排水，利用逆滲透膜進行膜處理的工序，可將溶存在膜過濾後的高硬度排水中的金屬離子等予以除去，可獲得更少雜質之高利用價值的水。 Further, the method further includes a step of subjecting the membrane to high-durability drainage after filtration, and performing membrane treatment using a reverse osmosis membrane. In the method of treating the high-hardness drainage, the high-hardness drainage of the membrane is filtered, and the membrane is treated by the reverse osmosis membrane to remove the metal in the high-hardness drainage after the membrane is filtered. The ions and the like are removed, and water having a high use value of less impurities can be obtained.
形成上述粒子層的粒子，係可採用無煙煤。是以，該高硬度排水之處理方法，藉由使用無煙煤作為形成上述粒子層的粒子，可以較低成本來形成能夠很有效率地捕集由有機物凝集而成的絮凝物之粒子層。 As the particles forming the above particle layer, anthracite may be used. In the method for treating the high-hardness drainage, by using anthracite as the particles forming the particle layer, a particle layer capable of efficiently collecting the floc aggregated by the organic substance can be formed at a low cost.
上述高硬度排水可以是已經過生物處理後的排放污水(下水)。是以，該高硬度排水之處理方法，藉由是以已經過生物處理後的排放污水(下水)來作為上述高硬度排水，可在自來水(上水)的硬度較高的地域，可以比較容易且穩定地獲得例如：自來水(上水)、工業用水等的水。 The above high-hardness drainage may be discharged sewage (sewage) that has been biologically treated. Therefore, the high-hardness drainage treatment method can be used as the high-hardness drainage water by the discharged sewage (sewage) which has been biologically treated, and can be easily used in a region where the hardness of the tap water (water supply) is high. Water such as tap water (water supply), industrial water, and the like is stably obtained.
此處，在本案中所稱的「鈣硬度」係指：依據日本工業規格JIS-K0101(1998)來測定的數值。又，「精密過濾膜」係指：空孔的平均直徑為高於0.1μm且10μm以下之過濾膜；「限外超過濾膜」係指：空孔的平均直徑為高於0.002μm且0.1μm以下之過濾膜；「逆滲透膜」係指：空孔的平均直徑為2nm以下之過濾膜。此外，空孔的平均直徑係指：在過濾膜的表面的空孔的平均直徑，係可利用：細孔直徑分布測定裝置(例如：Porous Materials公司製造的多孔質材料自動細孔徑分布測定系統)來進行測定。此外，所稱的「主成分」係指：質量含有率最大的成分，優選是含量為90質量%以上的成分。 Here, the term "calcium hardness" as used in the present invention means a value measured in accordance with Japanese Industrial Standard JIS-K0101 (1998). In addition, "precision filter membrane" means a membrane having an average pore diameter of more than 0.1 μm and 10 μm or less; "extra-limit ultrafiltration membrane" means that the average diameter of the pores is more than 0.002 μm and 0.1 μm. The following filter membrane; "reverse osmosis membrane" means a membrane having an average pore diameter of 2 nm or less. In addition, the average diameter of the pores means the average diameter of the pores on the surface of the filtration membrane, and a pore diameter distribution measuring apparatus (for example, a porous pore size distribution measuring system made of Porous Materials) To carry out the measurement. In addition, the term "main component" means a component having the largest mass content, and is preferably a component having a content of 90% by mass or more.
[本發明之實施方式的詳細說明] [Detailed Description of Embodiments of the Present Invention]
以下，將佐以圖面詳細說明本發明的高硬度排水之處 理方法的實施方式。 Hereinafter, the high hardness drainage area of the present invention will be described in detail with reference to the drawings. The implementation of the method.
[第一實施方式] [First Embodiment]
本發明之一種實施方式的高硬度排水之處理方法，其具備：將凝集劑添加入高硬度排水的工序<凝集劑添加工序>；將上述凝集劑添加工序後的高硬度排水利用粒子層進行粗過濾的工序<粗過濾工序>；將上述粗過濾工序後的高硬度排水利用精密過濾膜或限外超過濾膜進行膜過濾的工序<膜過濾工序>；將上述精密過濾膜或限外超過濾膜利用酸性水進行逆清洗的工序<逆清洗工序>。 A method for treating a high-hardness drainage according to an embodiment of the present invention includes a step of adding a flocculating agent to a high-hardness drainage step, a "aggregating agent adding step", and a high-hardness drainage using a particle layer after the aggregating agent adding step Filtration step <crude filtration step>; a step of performing membrane filtration using a fine filtration membrane or an ultrafiltration membrane after the above-mentioned coarse filtration step <membrane filtration step>; superfiltration of the above-mentioned precision filtration membrane or outer limit The step of backwashing the film by acidic water <reverse cleaning step>.
該高硬度排水之處理方法，係使用於處理鈣硬度為100以上的高硬度排水，尤其是特別適用於鈣硬度為150以上的情況。 The high hardness drainage treatment method is used for treating high hardness drainage having a calcium hardness of 100 or more, and is particularly suitable for a case where the calcium hardness is 150 or more.
(高硬度排水) (high hardness drainage)
可被該高硬度排水之處理方法所處理的高硬度排水，係可舉出例如：自來水(上水)的硬度較高的地域之排放污水(下水)的一次處理排水。換言之，該高硬度排水之處理方法，係可用來針對於排放污水(下水)已經過例如：利用活性污泥法等進行過生物處理後的一次處理排水，做更進一步的高度處理，而生成可作為例如：自來水(上水)、工業用水等來予以再利用的水。 For the high-hardness drainage which can be treated by the method of the high-durability drainage, for example, the primary treatment drainage of the discharged sewage (sewage) in the region where the hardness of the tap water (water supply) is high is mentioned. In other words, the high-hardness drainage treatment method can be used for the discharge of sewage (sewage), for example, after treatment with a biological sludge treatment by an activated sludge method, for further processing, and further For example, tap water (water supply), industrial water, and the like are reused.
<凝集劑添加工序> <aggregating agent addition process>
上述凝集劑添加工序，是將凝集劑添加入高硬度排水中，使有機物凝集。此時，高硬度排水中的有機物，將會吸附高硬度排水中的金屬或金屬化合物而凝集形成絮凝物。 In the aggregating agent addition step, a coagulant is added to the high-hardness drainage to cause the organic matter to aggregate. At this time, the organic matter in the high-hardness drainage will adsorb the metal or metal compound in the high-hardness drainage and agglomerate to form a floc.
(凝集劑) (aggregating agent)
在這個凝集劑添加工序添加到高硬度排水內的凝集劑，係可使用例如：聚合氯化鋁(PAC)、硫酸礬土、聚硫酸鐵、氯化鐵等的無機凝集劑；例如：陽離子性凝集劑、陰離子性凝集劑等的高分子凝集劑。其中，尤其是以比較價廉而且添加量的管理比較簡單的聚合氯化鋁特別適用。此外，亦可併用複數種類的凝集劑。 In the aggregating agent addition step, the aggregating agent added to the high hardness drainage water may be, for example, an inorganic aggregating agent such as polyaluminum chloride (PAC), barium sulfate, polyferric sulfate, or ferric chloride; for example, cationic A polymer aggregating agent such as an aggregating agent or an anionic aggregating agent. Among them, in particular, polyaluminum chloride which is relatively inexpensive and has a relatively simple management of added amount is particularly suitable. Further, a plurality of types of aggregating agents may be used in combination.
在這個凝集劑添加工序，是以對於高硬度排水以一定的比率，添加凝集劑為宜。使用聚合氯化鋁作為凝集劑的話，凝集劑的添加量的下限，是以對高硬度排水達到5質量ppm為宜，10質量ppm更好。另一方面，作為凝集劑之聚合氯化鋁的添加量的上限，是以500質量ppm為宜，300質量ppm更好。作為凝集劑之聚合氯化鋁的添加量低於上述下限的話，因為無法將高硬度排水中的有機物充分地凝集，而有導致精密過濾膜或限外超過濾膜很容易被有機物堵塞之虞慮、或者因為在精密過濾膜或限外超過濾膜附著了有機物，而有變得難以利用酸性水來清洗精密過濾膜或限外超過濾膜之虞慮。相反地，作為凝集劑之聚合氯化鋁的添加量高於上述上限的話，則會有處理 成本過度增大之虞慮，並且會有導致粒子層很快就被堵塞之虞慮，還有導致已經通過粒子層後的凝集劑使得精密過濾膜或限外超過濾膜被堵塞之虞慮。 In the aggregating agent addition step, it is preferred to add a flocculating agent at a certain ratio to the high hardness drainage. When the polyaluminum chloride is used as the aggregating agent, the lower limit of the amount of the aggregating agent added is preferably 5 ppm by mass for the high hardness drainage, and more preferably 10 ppm by mass. On the other hand, the upper limit of the amount of the polyaluminum chloride to be added as the aggregating agent is preferably 500 ppm by mass, more preferably 300 ppm by mass. When the amount of the polyaluminum chloride to be added as the aggregating agent is less than the above lower limit, the organic matter in the high-hardness drainage cannot be sufficiently aggregated, and there is a concern that the fine filtration membrane or the ultrafiltration membrane is easily blocked by the organic substance. Or, because the organic matter is attached to the ultrafiltration membrane or the ultrafiltration membrane, it is difficult to clean the precision filtration membrane or the ultrafiltration membrane with acidic water. On the contrary, if the amount of the polyaluminum chloride added as the aggregating agent is higher than the above upper limit, there is a treatment. The cost is excessively increased, and there is a concern that the particle layer is quickly clogged, and there is a concern that the fine filter film or the outer ultrafiltration membrane is blocked by the aggregating agent that has passed through the particle layer.
<粗過濾工序> <Coarse filtration process>
在上述粗過濾工序中，是將在凝集劑添加工序中已經凝集了有機物的高硬度排水(被處理水)，使用過濾層來進行過濾，藉此，從高硬度排水中除去有機物以及被吸附在絮凝物中的金屬或金屬化合物。依據高硬度排水中的有機物的種類而有所不同，例如：高硬度排水中的初期總有機碳TOC約為4.0mg/L的情況下，這個粗過濾工序後的高硬度排水中的TOC會被減少3.6mg/L至3.7mg/L。此外，「TOC」係指：依據日本工業規格JIS-K0805(1988)所測定的數值。 In the above-described coarse filtration step, the high-hardness drainage (treated water) in which the organic matter has been aggregated in the aggregating agent addition step is filtered using a filtration layer, thereby removing organic matter from the high-hardness drainage and being adsorbed thereon. a metal or metal compound in a floc. Depending on the type of organic matter in the high-hardness drainage, for example, if the initial total organic carbon TOC in the high-hardness drainage is about 4.0 mg/L, the TOC in the high-hardness drainage after this coarse filtration process will be Reduce 3.6mg / L to 3.7mg / L. Further, "TOC" means a value measured in accordance with Japanese Industrial Standard JIS-K0805 (1988).
這個粗過濾工序中進行粗過濾的方法，係可採用：在上下具有流路，使高硬度排水通過較上側的流路更上側，並且使用織布、不織布或濾紙作為過濾層，或者將過濾粒子投入具有可阻止粒子通過的支承構件的容器內，使其堆積在支承構件上形成過濾層而作為過濾層來使用，並且是從上側的流路供給高硬度排水，從下側的流路進行排水之下降流式過濾方法。 The coarse filtration method in the coarse filtration step may be such that a flow path is provided on the upper and lower sides, the high-hardness drainage is passed through the upper flow path, and a woven fabric, a non-woven fabric or a filter paper is used as the filtration layer, or the filtration particles are used. The inside of the container which has a support member which can block the passage of the particles is placed, and the filter layer is deposited on the support member to be used as a filter layer, and high-hardness drainage is supplied from the upper flow path, and drainage is performed from the lower flow path. The downflow filtering method.
此外，在這個粗過濾工序中作為過濾層使用的上述粗過濾，如果是在利用保留粒子徑為1μm的過濾層來執行的高硬度排水之處理方法中的話，則是使用：織 布、不織布、或者濾紙當作過濾層。不織布，係可採用例如：聚酯、尼龍、聚乙烯、聚丙烯、聚胺酯、聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)。作為高流量處理時，係採用：聚乙烯對苯二甲酸酯之類的聚酯所製作的不織布為宜。此外，在這個粗過濾工序中作為過濾層使用的濾紙，係可舉出具有與無煙煤粒子層近乎同等過濾能力的5C濾紙(日本工業規格JIS-P3801(1995))。 Further, the above-described coarse filtration used as the filtration layer in this coarse filtration step is used in the treatment method of high-hardness drainage performed by using a filtration layer having a retained particle diameter of 1 μm. Cloth, non-woven, or filter paper is used as a filter. For non-woven fabrics, for example, polyester, nylon, polyethylene, polypropylene, polyurethane, polytetrafluoroethylene (PTFE), and polyvinylidene fluoride (PVDF) can be used. When processing at a high flow rate, a nonwoven fabric made of a polyester such as polyethylene terephthalate is preferably used. In addition, the filter paper used as a filter layer in this coarse filtration process is a 5C filter paper which has the similar filtering ability with an anthracite particle layer (Japanese Industrial Standard JIS-P3801 (1995)).
上述粗過濾如果是在利用有效直徑為0.4mm以上且0.7mm以下的過濾層來執行的高硬度排水之處理方法中的話，係可將過濾粒子投入具有可阻止粒子通過的支承構件的容器內，使其堆積在支承構件上形成過濾層而作為過濾層使用。用來形成在這個粗過濾工序中作為過濾層來使用的粒子層之過濾粒子，係可採用：公知的過濾處理用的粒子，係可採用例如：以小石子、天然砂、無機物粒子、陶瓷、聚合物(高分子化合物)、天然有機素材等作為主成分之粒子，其中，最適合採用比較廉價的天然砂。此處所稱的「主成分」係指：質量含有率最大的成分之意。 If the coarse filtration is a high-hardness drainage treatment method using a filtration layer having an effective diameter of 0.4 mm or more and 0.7 mm or less, the filtration particles can be placed in a container having a support member capable of preventing particles from passing therethrough. It is deposited on a support member to form a filter layer, and is used as a filter layer. The filter particles for forming the particle layer used as the filter layer in the coarse filtration step may be any known particles for filtration treatment, and may be, for example, pebbles, natural sand, inorganic particles, ceramics, or the like. A particle containing a polymer (polymer compound), a natural organic material or the like as a main component, and among them, a natural sand which is relatively inexpensive is most suitable. The term "principal component" as used herein means the meaning of the component having the highest mass content.
上述天然砂，係可舉出例如：無煙煤、石榴子石、錳砂、矽砂等。其中，尤其是以無煙煤特別適用，因為其比較廉價，而且在形狀上比較多稜角，因而具有較大的粒子層的空隙率以及比表面積，從而具有優異的除去有機物所凝集的絮凝物的能力。此外，因為無煙煤的比重較小，在逆清洗時的攪拌效率很優異，因此也具有比較容 易逆清洗的優點。此外，這些的天然砂亦可採用單一種或混合兩種以上來使用。其中，尤其是以石英砂與無煙煤的混合物，比較容易形成過濾層，因此特別合宜。 Examples of the natural sand include anthracite, garnet, manganese sand, strontium sand, and the like. Among them, in particular, anthracite is particularly suitable because it is relatively inexpensive and has a relatively large angular shape, and thus has a large void ratio of a particle layer and a specific surface area, thereby having an excellent ability to remove flocs aggregated by organic matter. In addition, because the proportion of anthracite is small, the mixing efficiency in the reverse cleaning is excellent, so it is also comparable. The advantage of easy reverse cleaning. Further, these natural sands may be used singly or in combination of two or more. Among them, a mixture of quartz sand and anthracite, in particular, is relatively easy to form a filter layer, and thus is particularly suitable.
至於上述無機物粒子，基於可比較容易取得粒徑及比重上的差異小的粒子之觀點考量，優選是玻璃彈珠。特別優選的玻璃彈珠，係可舉出例如：含有氧化鋁的球狀玻璃彈珠。 The inorganic particles are preferably glass beads based on the viewpoint that particles having a small difference in particle diameter and specific gravity can be relatively easily obtained. Particularly preferred glass beads are, for example, spherical glass beads containing alumina.
至於上述陶瓷，係可採用例如：以氧化矽、氧化鋁、玻璃等作為主成分的陶瓷粒子。至於上述天然有機素材，係可使用將天然有機物經過篩選而湊齊相近的粒子大小的素材，係可舉出例如：核桃的殼、鋸屑、麻之類的天然纖維等。 As the ceramic, for example, ceramic particles containing ruthenium oxide, aluminum oxide, glass or the like as a main component can be used. As for the above-mentioned natural organic material, a material having a particle size similar to that of a natural organic substance can be used, and examples thereof include a shell of walnut, a sawdust, and a natural fiber such as hemp.
至於上述聚合物的主成分，係可舉出例如：氟系樹脂、乙烯基樹脂、聚烯烴、聚胺酯、環氧樹脂、丙烯酸樹脂、聚酯、聚醯胺、聚醯亞胺、美耐皿樹脂、聚碳酸酯等。這些當中尤其是：耐水性以及耐酸性、耐腐蝕性優異的氟系樹脂、乙烯基樹脂以及聚烯烴為佳，吸附性優異的聚烯烴更好。又，在聚烯烴之中，則是以吸附能力優異的聚丙烯特優。 The main component of the above polymer may, for example, be a fluorine resin, a vinyl resin, a polyolefin, a polyurethane, an epoxy resin, an acrylic resin, a polyester, a polyamide, a polyimide, or a melamine resin. , polycarbonate, etc. Among these, a fluorine-based resin, a vinyl resin, and a polyolefin which are excellent in water resistance, acid resistance, and corrosion resistance are preferable, and a polyolefin excellent in adsorption property is more preferable. Further, among the polyolefins, polypropylene which is excellent in adsorption ability is excellent.
上述過濾粒子的有效直徑的下限，是以0.5mm為宜，0.7mm更好。另一方面，上述過濾粒子的有效直徑的上限，是以2mm為宜，1.5mm更好。上述過濾粒子的有效直徑低於上述下限的話，粒子層很容易堵塞，因此會有必須頻繁地進行逆清洗之虞慮。相反地，上述過 濾粒子的有效直徑超過上述上限的話，會有無法充分去除金屬粒子之虞慮。又，所稱的「有效直徑」係指：使用日本工業規格JIS-Z8801-1(2006)所規定的篩網，從目網較大的篩網依序地進行篩選，來測定通過網目後的粒子的質量比率，在以篩網的通稱網目作為粒徑而作成的粒徑分布中，積算質量達到10%的粒徑之意。 The lower limit of the effective diameter of the above-mentioned filter particles is preferably 0.5 mm, more preferably 0.7 mm. On the other hand, the upper limit of the effective diameter of the above-mentioned filter particles is preferably 2 mm, more preferably 1.5 mm. When the effective diameter of the above-mentioned filter particles is less than the above lower limit, the particle layer is easily clogged, and therefore there is a concern that the reverse cleaning must be performed frequently. On the contrary, the above When the effective diameter of the filter particles exceeds the above upper limit, there is a concern that the metal particles cannot be sufficiently removed. In addition, the term "effective diameter" refers to the use of a screen specified in Japanese Industrial Standard JIS-Z8801-1 (2006), which is sequentially screened from a larger screen of the mesh net to measure the passage through the mesh. The mass ratio of the particles is defined by the particle size distribution obtained by using the mesh of the mesh as the particle diameter, and the mass of the particle is 10%.
上述過濾粒子的均等係數的下限，是以1.1為宜，1.2更好。另一方面，上述過濾粒子的均等係數的上限，是以1.7為宜，1.5更好。上述過濾粒子的均等係數低於上述下限的話，會有上述過濾粒子的成本過度增大之虞慮。相反地，上述過濾粒子的均等係數超過上述上限的話，粒子層很容易堵塞，因而會有必須頻繁地進行逆清洗之虞慮。此外，所稱的「均等係數」係指：使用日本工業規格JIS-Z8801-1(2006)所規定的篩網，從目網較大的篩網依序地進行篩選，來測定通過網目後的粒子的質量比率，在以篩網的通稱網目作為粒徑而作成的粒徑分布中，積算質量達到60%的粒徑對上述有效直徑的比值之意。 The lower limit of the equalization coefficient of the above-mentioned filter particles is preferably 1.1, and more preferably 1.2. On the other hand, the upper limit of the uniform coefficient of the above-mentioned filter particles is preferably 1.7, and more preferably 1.5. When the equal coefficient of the filter particles is less than the lower limit, the cost of the filter particles may be excessively increased. On the other hand, when the equal coefficient of the above-mentioned filter particles exceeds the above upper limit, the particle layer is easily clogged, and there is a concern that the reverse cleaning must be performed frequently. In addition, the term "equal coefficient" refers to the use of a screen specified in Japanese Industrial Standard JIS-Z8801-1 (2006), which is sequentially screened from a larger screen of the mesh net to measure the passage through the mesh. The mass ratio of the particles is defined by the ratio of the particle diameter of 60% of the mass to the effective diameter in the particle size distribution obtained by using the mesh of the mesh as the particle diameter.
粒子層的平均厚度的下限，是以10cm為宜，15cm更好。另一方面，粒子層的平均厚度的上限，是以80cm為宜，60cm更好。粒子層的平均厚度低於上述下限的話，會有無法充分去除金屬粒子之虞慮。相反地，粒子層的平均厚度超過上述上限的話，會有設備成本過度增大之虞慮。 The lower limit of the average thickness of the particle layer is preferably 10 cm, more preferably 15 cm. On the other hand, the upper limit of the average thickness of the particle layer is preferably 80 cm, more preferably 60 cm. When the average thickness of the particle layer is less than the above lower limit, there is a concern that the metal particles cannot be sufficiently removed. Conversely, if the average thickness of the particle layer exceeds the above upper limit, there is a concern that the equipment cost is excessively increased.
<膜過濾工序> <Film filtration process>
上述膜過濾工序，係使用精密過濾膜或限外超過濾膜(以下的說明中，有時候是簡稱為「過濾膜」作為包含這兩者的概念)，從粗過濾工序後的高硬度排水(被處理水)中除去在粗過濾工序無法除去之以細微的金屬化合物為主的浮游物質。又，使用限外超過濾膜的話，不僅是浮游物質，就連較大的溶質也可以除去。 In the membrane filtration step, a fine filtration membrane or an ultra-ultrafiltration membrane is used (in the following description, abbreviated as "filtration membrane" as a concept including both), and high-hardness drainage after the coarse filtration step ( In the water to be treated, a floating substance mainly composed of a fine metal compound which cannot be removed in the coarse filtration step is removed. Moreover, when an ultra-filtration membrane is used, not only a floating substance but also a large solute can be removed.
上述過濾膜的空孔的平均直徑，是可因應例如：後工序的有無、處理後的水的使用目的等因素來做合宜的選擇，可設定為例如：0.005μm以上且0.5μm以下。 The average diameter of the pores of the filtration membrane can be appropriately selected depending on factors such as the presence or absence of a post-process and the purpose of use of the treated water, and can be set, for example, to 0.005 μm or more and 0.5 μm or less.
又，膜過濾工序的過濾膜的流束，係可設定為例如：30LMH以上且100LMH以下。 Further, the flow rate of the filtration membrane in the membrane filtration step can be set to, for example, 30 LMH or more and 100 LMH or less.
(精密過濾膜或限外超過濾膜) (Precision filter membrane or extra-superfiltration membrane)
過濾膜的材質，是以例如：氟系樹脂、乙烯基樹脂、聚烯烴等之不易劣化的樹脂為宜，其中尤其是以強度比較優異的聚四氟乙烯特別優選。此外，逆滲透膜亦可含有例如：主成分以外的聚合物、潤滑劑等地添加劑等。又，過濾膜係可採用：將以聚四氟乙烯為主成分的薄片狀材料經過單軸或雙軸延伸處理，而形成有細微的龜裂之多孔性的過濾膜。 The material of the filtration membrane is preferably a resin which is not easily deteriorated, such as a fluorine resin, a vinyl resin or a polyolefin, and particularly preferably polytetrafluoroethylene which is excellent in strength. Further, the reverse osmosis membrane may contain, for example, a polymer other than the main component, an additive such as a lubricant, or the like. Further, the filtration membrane may be formed by subjecting a sheet-like material containing polytetrafluoroethylene as a main component to a uniaxial or biaxial stretching treatment to form a porous membrane having a fine crack.
上述過濾膜的形狀，係可舉出例如：中空紗型、薄片型、螺旋型、中空管型等，基於可將膜模組之每單位容積的膜面積做得比較大的理由，是以中空紗型特別 適用。 The shape of the filtration membrane may be, for example, a hollow fiber type, a sheet type, a spiral type, a hollow tube type, or the like, and the reason why the membrane area per unit volume of the membrane module can be made relatively large is Hollow yarn type special Be applicable.
使用中空紗膜作為過濾膜的話，係可使用：具有朝單一方向拉湊整齊的複數支中空紗膜、以及可保持這些複數支中空紗膜的兩端並且具有與各中空紗膜的內腔相連通的流路之一對保持構件的過濾模組。 When a hollow fiber membrane is used as the filtration membrane, it is possible to use a plurality of hollow fiber membranes which are drawn in a single direction and which can hold both ends of the plurality of hollow fiber membranes and have a lumen connected to each hollow fiber membrane. One of the flow paths to the filter module of the holding member.
使用中空紗膜的過濾方式，係可適用例如：對於中空紗膜的外側供給經過加壓的高硬度排水，使其穿透到中空紗膜的內腔之外壓式；將中空紗膜浸泡在未加壓的高硬度排水中，利用浸透壓或內腔側的負壓，使高硬度排水穿透到中空紗膜的內腔之浸泡式；對於中空紗膜的內腔供給經過加壓的高硬度排水，使其穿透到中空紗膜的外側之內壓式等的方式。 The filtration method using the hollow fiber membrane can be applied, for example, to the pressurized outer high pressure drainage of the outer side of the hollow fiber membrane to penetrate into the inner cavity of the hollow fiber membrane; the hollow fiber membrane is immersed in In the unpressurized high-hardness drainage, the impregnation pressure or the negative pressure on the inner cavity side is used to make the high-hardness drainage penetrate into the inner cavity of the hollow fiber membrane; the inner cavity of the hollow fiber membrane is pressurized and high. The hardness is drained so as to penetrate into the inner side of the hollow fiber membrane or the like.
<逆清洗工序> <Reverse cleaning process>
上述逆清洗工序，是針對於在上述膜過濾工序時已經堵塞或壓力損失(通水阻力)增大後的過濾膜，朝向與上述膜過濾工序時的通水方向相反的方向，將酸性水進行通水，以資從過濾膜除去附著物。 In the above-described reverse cleaning step, the filtration membrane is clogging or the pressure loss (water resistance) is increased in the membrane filtration step, and the acidic water is applied in a direction opposite to the water flow direction in the membrane filtration step. Water is passed to remove the deposit from the filter membrane.
在這個逆清洗工序，係使用酸性水來作為清洗水，因此，可較容易將以金屬或金屬化合物為主的過濾膜上的附著物予以溶解而除去。 In this reverse washing step, acidic water is used as the washing water. Therefore, it is possible to easily dissolve and remove the deposit on the filter film mainly composed of a metal or a metal compound.
酸性水所使用的酸，雖然是具有酸性的話即可，但是特別適合使用鹽酸以及檸檬酸。鹽酸以及檸檬酸比較廉價，而且不易與高硬度排水中的鈣等產生結合，可 防止不想要的析出物的生成。因此，藉由使用含有鹽酸以及檸檬酸的酸性水，可較容易清洗過濾膜。 The acid used for the acidic water may be acidic, but hydrochloric acid and citric acid are particularly suitable. Hydrochloric acid and citric acid are relatively inexpensive, and are not easily combined with calcium in high-hardness drainage. Prevent the formation of unwanted precipitates. Therefore, the filtration membrane can be easily washed by using acidic water containing hydrochloric acid and citric acid.
在逆清洗工序中作為清洗水使用的酸性水的pH值的下限，是以2為宜，4更好。另一方面，作為清洗水使用的酸性水的pH值的上限，是以6.5為宜，6更好。酸性水的pH值低於上述下限的話，會有導致：用來調整酸性水的酸的成本以及清洗後的酸性水的處理成本過度增大之虞慮、排水處理設備的壽命短縮之虞慮。相反地，酸性水的pH值超過上述上限的話，會有不易除去附著在過濾膜上的金屬或金屬化合物之虞慮。 The lower limit of the pH of the acidic water used as the washing water in the reverse washing step is preferably 2, and more preferably 4. On the other hand, the upper limit of the pH of the acidic water used as the washing water is preferably 6.5, and more preferably 6. When the pH of the acidic water is lower than the lower limit, there is a concern that the cost of the acid for adjusting the acidic water and the treatment cost of the acidic water after the cleaning are excessively increased, and the life of the wastewater treatment equipment is shortened. On the other hand, when the pH of the acidic water exceeds the above upper limit, there is a concern that it is difficult to remove the metal or metal compound adhering to the filtration membrane.
逆清洗工序的平均間隔，可設定在例如：30分鐘以上且40分鐘以下。又，一次的逆清洗工序的通水時間，可設定在例如：30秒鐘以上且60秒鐘以下。又，清洗工序中之對於過濾膜供給酸性水時的供給壓力，係可設在例如：60kPa以上且100kPa以下。又，清洗工序中之對於過濾膜供給酸性水的供給量(通水量)，係可設在例如：上述膜過濾工序的過濾水量的一倍以上且兩倍以下。其結果，該高硬度排水之處理方法係可回收高硬度排水的90質量%以上來當作可再利用的已處理水。 The average interval of the reverse washing step can be set, for example, to 30 minutes or longer and 40 minutes or shorter. Further, the water passing time of the primary reverse washing step can be set, for example, to 30 seconds or longer and 60 seconds or shorter. In addition, the supply pressure when the acidic water is supplied to the filtration membrane in the washing step may be, for example, 60 kPa or more and 100 kPa or less. In addition, the supply amount (water supply amount) of the acidic water supplied to the filtration membrane in the washing step may be, for example, one or more times and not more than twice the amount of the filtered water in the membrane filtration step. As a result, the high-hardness drainage treatment method can recover 90% by mass or more of the high-hardness drainage as the reusable treated water.
作為具體例，當高硬度排水的浮游物質(SS)的含量為5mg/L、總有機碳(TOC)的含量為5mg/L、鈣硬度為100的情況下，將逆清洗工序的間隔(膜過濾工序的連續時間)設為30分鐘、將逆清洗工序的通水時間設為30秒鐘、將清洗工序中對於過濾膜供給酸性水的供給壓力設 為60kPa、將清洗工序中對於過濾膜供給酸性水的供給量設為膜過濾工序中的過濾水量的1.2倍的話，就可防止過濾膜堵塞而可穩定地進行運轉，可將已處理水的回收率高達95%。如果對於相同的高硬度排水，將逆清洗工序的間隔(膜過濾工序的連續時間)設為30分鐘、將逆清洗工序的通水時間設為60秒鐘、將清洗工序中對於過濾膜供給酸性水的供給壓力設為60kPa、將清洗工序中對於過濾膜供給酸性水的供給量設為膜過濾工序中的過濾水量的1.2倍的話，則已處理水的回收率變成93%。 As a specific example, when the content of the high-hardness drainage suspended matter (SS) is 5 mg/L, the total organic carbon (TOC) content is 5 mg/L, and the calcium hardness is 100, the interval of the reverse washing step (film) The continuous time of the filtration step is 30 minutes, the water passing time of the reverse washing step is 30 seconds, and the supply pressure of the acidic water to the filtration membrane is set in the washing step. When the supply amount of the acidic water supplied to the filtration membrane in the washing step is set to 1.2 times the amount of the filtered water in the membrane filtration step, the filtration membrane can be prevented from being clogged and the operation can be stably performed, and the treated water can be recovered. The rate is as high as 95%. For the same high-hardness drainage, the interval of the reverse washing step (continuous time of the membrane filtration step) is set to 30 minutes, the water passing time of the reverse washing step is set to 60 seconds, and the filtration membrane is supplied with acidity in the washing step. When the supply pressure of the water is set to 60 kPa and the supply amount of the acidic water supplied to the filtration membrane in the washing step is 1.2 times the amount of the filtered water in the membrane filtration step, the recovery rate of the treated water is 93%.
相對於此，高硬度排水的浮游物質(SS)的含量為3mg/L、總有機碳(TOC)的含量為1mg/L、鈣硬度為150的情況下，即使將逆清洗工序的間隔(膜過濾工序的連續時間)設為40分鐘、將逆清洗工序的通水時間設為30秒鐘、將清洗工序中對於過濾膜供給酸性水的供給壓力設為60kPa、將清洗工序中對於過濾膜供給酸性水的供給量設為膜過濾工序中的過濾水量的1.2倍，亦可防止過濾膜堵塞而穩定地進行運轉，並且將已處理水的回收率提昇到達97%。又，針對於相同的高硬度排水，若將逆清洗工序的間隔(膜過濾工序的連續時間)設為40分鐘、將逆清洗工序的通水時間設為60秒鐘、將清洗工序中對於過濾膜供給酸性水的供給壓力設為60kPa、將清洗工序中對於過濾膜供給酸性水的供給量設為膜過濾工序中的過濾水量的1.2倍的話，則已處理水的回收率是96%。 On the other hand, when the content of the suspended matter (SS) of the high-hardness drainage is 3 mg/L, the content of the total organic carbon (TOC) is 1 mg/L, and the calcium hardness is 150, the interval of the reverse washing step (film) The continuous time of the filtration step is 40 minutes, the water supply time of the reverse washing step is 30 seconds, and the supply pressure of the acidic water to the filtration membrane in the washing step is 60 kPa, and the filtration membrane is supplied in the washing step. The supply amount of the acidic water was set to 1.2 times the amount of the filtered water in the membrane filtration step, and the filtration membrane was prevented from being clogged and stably operated, and the recovery rate of the treated water was increased to 97%. In addition, for the same high-hardness drainage, the interval of the reverse washing step (continuous time of the membrane filtration step) is 40 minutes, the water passing time of the reverse washing step is 60 seconds, and the filtration is performed for the cleaning step. When the supply pressure of the membrane-assisted acidic water is 60 kPa and the supply amount of the acidic water supplied to the filtration membrane in the washing step is 1.2 times the amount of the filtered water in the membrane filtration step, the recovery rate of the treated water is 96%.
又，在這個清洗工序中，更好是對於酸性水 中，或者對於與過濾膜之被供給酸性水的這一側的相反側供給氣泡，可以促進過濾膜的清洗。 Also, in this cleaning process, it is better for acidic water In the middle, or in the case of supplying bubbles to the side opposite to the side of the filtration membrane to which the acidic water is supplied, the cleaning of the filtration membrane can be promoted.
<優點> <advantage>
該高硬度排水之處理方法，是在使用精密過濾膜或限外超過濾膜的膜過濾工序之前，具備：使用凝集劑來使高硬度排水中的有機物凝集在一起之凝集劑添加工序；以及利用過濾層將已凝集的有機物予以分離之粗過濾工序，如此一來，有機物就難以附著在過濾膜上。因此，根據該高硬度排水之處理方法，可縮小過濾膜的差壓而進行定常運轉。又，該高硬度排水之處理方法係可減少有機物附著到過濾膜，因此過濾膜的清洗比較容易。 The high hardness drainage treatment method includes a coagulant addition step of agglomerating the organic substances in the high hardness drainage using a flocculating agent before the membrane filtration step using the fine filtration membrane or the outer ultrafiltration membrane; and utilizing The filtration layer separates the agglomerated organic matter into a coarse filtration step, so that it is difficult for the organic substance to adhere to the filtration membrane. Therefore, according to the treatment method of the high-hardness drainage, the differential pressure of the filtration membrane can be made small, and the steady operation can be performed. Moreover, the high hardness drainage treatment method can reduce the adhesion of organic substances to the filtration membrane, and therefore the filtration membrane is relatively easy to clean.
又，該高硬度排水之處理方法，主要是金屬或金屬化合物附著到過濾膜，因此，在逆清洗工序中，可利用酸性水比較容易除去過濾膜的附著物，所以過濾膜的清洗比較容易。 Moreover, since the method of treating the high-hardness drainage mainly involves the adhesion of the metal or the metal compound to the filtration membrane, in the reverse cleaning step, the deposit of the filtration membrane can be easily removed by the acidic water, so that the filtration of the filtration membrane is relatively easy.
又，利用該高硬度排水之處理方法來對於已經過生物處理後的排放污水(下水)，做進一步處理，藉此，可以比較容易且穩定地獲得例如：自來水(上水)、工業用水等。 Further, the high-hardness drainage treatment method is used to further treat the discharged sewage (sewage) that has been biologically treated, whereby it is possible to obtain, for example, tap water (water supply), industrial water, and the like relatively easily and stably.
[排水處理設備] [Drainage treatment equipment]
第1圖是顯示可用來實施第1圖的高硬度排水之處理方法的排水處理設備之一例。 Fig. 1 is a view showing an example of a drainage treatment apparatus which can be used to carry out the treatment method of high-hardness drainage in Fig. 1.
第1圖的排水處理設備，是具備：被供給處理對象也就是高硬度排水之凝集槽1；用來將凝集劑投入到這個凝集槽1之凝集劑添加裝置2；用來從凝集槽1送出高硬度排水之過濾泵浦3；被從過濾泵浦3供給高硬度排水，並且在內部收容著過濾粒子之過濾塔4；利用精密過濾膜或限外超過濾膜對於通過了過濾塔4的高硬度排水，進行膜過濾處理之膜過濾單元5；用來貯留從膜過濾單元5排出的高硬度排水之清洗水槽6；以及用來將貯留在清洗水槽6內的高硬度排水壓送到膜過濾單元5之清洗用泵浦7。 The drainage treatment apparatus of Fig. 1 includes an agglutination tank 1 to which a treatment target, that is, a high-hardness drainage, is supplied; a flocculant addition device 2 for introducing a flocculating agent into the aggregating tank 1; and is used for discharging from the aggregating tank 1 a high-durability drainage filter pump 3; a filter tower 4 which is supplied with high-durability drainage from the filtration pump 3 and contains filter particles therein; and a high filtration filter or an ultra-filtration membrane for passing the filtration tower 4 Hardness drainage, membrane filtration unit 5 for membrane filtration treatment; cleaning tank 6 for storing high-hardness drainage discharged from membrane filtration unit 5; and for pumping high-hardness drainage water stored in washing tank 6 to membrane filtration The cleaning of unit 5 is pumped 7.
<凝集槽> <Aggregation tank>
凝集槽1是用來進行該高硬度排水之處理方法的凝集劑添加工序之水槽或貯水池。在對於凝集槽1或調整層1供給高硬度排水的水路中設有用來檢測出水量的流量感測器為佳。 The aggregating tank 1 is a water tank or a water tank for performing a coagulant addition process of the high hardness drainage treatment method. It is preferable to provide a flow rate sensor for detecting the amount of water in the water path for supplying the high hardness drainage to the agglutination tank 1 or the adjustment layer 1.
<凝集劑添加裝置> <aggregating agent adding device>
凝集劑添加裝置2係可做成具有例如：用來收容凝集劑之收容料斗；以及用來將凝集劑供給到凝集槽1之例如：供給用螺旋桿、振動型給料機等的供給機構。這個凝集劑添加裝置2是控制成：可與供給到凝集槽1的高硬度排水的供給量成正比地自動供給凝集劑為佳。 The aggregating agent addition device 2 can be, for example, a storage hopper for accommodating the aggregating agent, and a supply mechanism for supplying the aggregating agent to the aggregating tank 1, for example, a supply auger, a vibrating feeder, or the like. This aggregating agent addition device 2 is controlled so as to be automatically supplied to the aggregating agent in proportion to the supply amount of the high-hardness drainage supplied to the coagulation tank 1.
<過濾泵浦> <Filter pump>
過濾泵浦3是將高硬度排水從凝集槽1經由過濾塔4以及膜過濾單元5之後，送出到清洗水槽6。 The filtration pump 3 sends the high-hardness drainage from the condensation tank 1 through the filtration tower 4 and the membrane filtration unit 5, and then sends it to the washing water tank 6.
<過濾塔> <Filter tower>
過濾塔4，係製作成：在上下具有流路，並且將複數個過濾粒子封入在被這些流路與例如：金屬網之類的支承構件所區劃的內部空間內，將這些過濾粒子堆積在支承構件上而形成過濾層。亦可先將碎石粒堆積在支承構件上，然後在這些碎石粒上堆積過濾粒子來形成過濾層。又，亦可使用織布、不織布或濾紙來取代由過濾粒子所形成的過濾層。此外，過濾塔4的內部空間，是具有較之複數個過濾粒子的虛表體積更為充分夠大的容積為佳，因而能夠當從下側的流路將清洗水進行通水時，可以使得過濾粒子往上浮起飄揚。 The filtration tower 4 is formed to have a flow path on the upper and lower sides, and to enclose a plurality of filter particles in an internal space partitioned by the flow path and a support member such as a metal mesh, and to deposit the filter particles on the support. A filter layer is formed on the member. The crushed stone particles may first be deposited on the support member, and then the filter particles are deposited on the crushed stone particles to form a filter layer. Further, a woven fabric, a non-woven fabric, or a filter paper may be used instead of the filter layer formed of the filter particles. Further, the internal space of the filtration tower 4 is preferably a volume which is more sufficiently large than the virtual surface volume of the plurality of filtration particles, and therefore can be made when the washing water is passed through the flow path from the lower side. The filter particles float up and flutter.
<膜過濾單元> <membrane filter unit>
膜過濾單元5係製作成：具有精密過濾膜或限外超過濾膜，利用這個精密過濾膜或限外超過濾膜，來將被供給的高硬度排水進行過濾，而將被過濾後的水當作已處理水流出去。舉出一具體例而言，膜過濾單元5係可採用：具有被供給高硬度排水的密閉容器；以及具有被配設在這個密閉容器內的中空紗膜之過濾模組，利用高硬度排水的供給壓力來使其通過中空紗膜之外壓式過濾裝置。 The membrane filtration unit 5 is manufactured by: having a precision filtration membrane or an ultra-ultrafiltration membrane, and using the precision filtration membrane or the ultra-filtration membrane to filter the supplied high-hardness drainage, and filtering the filtered water as The treated water flows out. As a specific example, the membrane filtration unit 5 may be: a sealed container having a high-hardness drainage; and a filter module having a hollow fiber membrane disposed in the sealed container, using a high-hardness drainage The pressure is supplied to pass the pressure filter device outside the hollow fiber membrane.
又，膜過濾單元5是具有對於過濾膜供給氣泡的氣泡供給裝置為佳。藉由在膜過濾工序中對於過濾膜供給氣泡，可抑制金屬或金屬化合物附著到過濾膜上。又，藉由在逆清洗工序中對於過濾膜供給氣泡，可利用氣泡的摩擦效果來促進已附著在過濾膜上的附著物的剝離。例如：膜過濾單元5是外壓式過濾裝置的話，氣泡供給裝置就是對於中空紗膜的外周面供給氣泡。 Further, the membrane filtration unit 5 is preferably a bubble supply device that supplies air bubbles to the filtration membrane. By supplying bubbles to the filtration membrane in the membrane filtration step, adhesion of the metal or the metal compound to the filtration membrane can be suppressed. Further, by supplying bubbles to the filtration membrane in the reverse washing step, it is possible to promote the peeling of the adhering matter adhering to the filtration membrane by the friction effect of the bubbles. For example, when the membrane filtration unit 5 is an external pressure type filtration device, the bubble supply device supplies bubbles to the outer peripheral surface of the hollow fiber membrane.
<清洗水槽> <cleaning sink>
清洗水槽6，是為了將高硬度排水利用過濾塔4以及膜過濾單元5進行過濾後的已處理水的一部分，作為膜過濾單元5的清洗水來利用，而予以貯留起來的水槽。這個清洗水槽6是被投入酸劑，將因此調製而得的酸性水作為膜過濾單元5的清洗水來使用。 The water tank 6 is a water tank that is used as a part of the treated water filtered by the filtration tower 4 and the membrane filtration unit 5, and is used as the washing water of the membrane filtration unit 5 to be stored. This cleaning water tank 6 is used as an acid agent, and the acidic water thus prepared is used as the washing water of the membrane filtration unit 5.
<清洗用泵浦> <cleaning pump>
清洗用泵浦7，係將在清洗水槽6中所調製的酸性水對於過濾膜單元5，朝向與進行過濾時的相反方向進行通水。通過了過濾單元5之後的酸性水，係被排出到系統之外而被當作排水來處理。 The cleaning pump 7 pumps the acidic water prepared in the washing tank 6 to the filtration membrane unit 5 in the opposite direction to the filtration. The acidic water that has passed through the filtration unit 5 is discharged to the outside of the system and treated as drainage.
[第二實施方式] [Second Embodiment]
本發明的另一種實施方式的高硬度排水之處理方法，其具備：將凝集劑添加入高硬度排水的工序<凝集劑添加 工序>；將上述凝集劑添加工序後的高硬度排水利用粒子層進行粗過濾的工序<粗過濾工序>；將上述粗過濾工序後的高硬度排水利用精密過濾膜或限外超過濾膜進行膜過濾的工序<膜過濾工序>；將上述精密過濾膜或限外超過濾膜利用酸性水進行逆清洗的工序<逆清洗工序>；將上述膜過濾工序後的高硬度排水利用逆滲透膜進行膜處理的工序<膜處理工序>。 A method for treating a high-hardness drainage according to another embodiment of the present invention, comprising: a step of adding a coagulant to a high-hardness drainage; adding a coagulant Step> a step of coarsely filtering the high-hardness drainage particle layer after the aggregating agent addition step <crude filtration step>; and performing high-hardness drainage after the coarse filtration step using a fine filtration membrane or an outer ultrafiltration membrane Step of filtration <membrane filtration step>; step of backwashing the above-mentioned fine filtration membrane or ultra-superfiltration membrane by acidic water <reverse cleaning step>; and performing high-hardness drainage after the membrane filtration step by reverse osmosis membrane Process of treatment <film treatment process>.
本實施方式的高硬度排水之處理方法中的凝集劑添加工序、粗過濾工序以及膜過濾工序是與第一實施方式的高硬度排水之處理方法中的凝集劑添加工序、粗過濾工序以及膜過濾工序相同。因此，針對於本實施方式的高硬度排水之處理方法，係省略了關於凝集劑添加工序、粗過濾工序以及膜過濾工序的說明。 The aggregating agent addition step, the coarse filtration step, and the membrane filtration step in the method for treating a high-hardness drainage according to the present embodiment are the aggregating agent addition step, the coarse filtration step, and the membrane filtration in the high hardness drainage treatment method according to the first embodiment. The process is the same. Therefore, the description of the method for treating the high-hardness drainage of the present embodiment is omitted for the aggregating agent addition step, the coarse filtration step, and the membrane filtration step.
<膜處理工序> <Film treatment process>
上述膜處理工序，係將被處理水分離成：逆滲透膜的透過水、以及溶質等被濃縮後的濃縮水。透過水係當作已處理水來再利用，而濃縮水則是當作排水被另外進行處理。 In the film treatment step, the water to be treated is separated into permeated water of a reverse osmosis membrane and concentrated water obtained by concentrating the solute or the like. It is reused as treated water through the water system, while concentrated water is treated as drainage.
(逆滲透膜) (reverse osmosis membrane)
逆滲透膜亦可以是：空孔直徑較大的奈米過濾膜。此外，所稱的「奈米過濾膜」係指：在逆滲透膜當中，空孔平均直徑大於1nm的逆滲透膜之意。逆滲透膜當中，空 孔平均直徑小於等於1nm的逆滲透膜(未被分類到奈米過濾膜)，其總硬度除去率及通量比較穩定，可獲得較大的總硬度除去率(例如：99%以上)。 The reverse osmosis membrane may also be a nanofiltration membrane having a large pore diameter. Further, the term "nanofiltration membrane" means a reverse osmosis membrane having an average pore diameter of more than 1 nm in a reverse osmosis membrane. In the reverse osmosis membrane, empty A reverse osmosis membrane having an average pore diameter of 1 nm or less (not classified into a nanofiltration membrane) has a stable total hardness removal rate and a flux, and a large total hardness removal rate (for example, 99% or more) can be obtained.
逆滲透膜的材質係可舉出例如：聚醯胺系高分子、聚碸系高分子、纖維素系高分子等。 The material of the reverse osmosis membrane may, for example, be a polyamine polymer, a polyfluorene polymer or a cellulose polymer.
上述逆滲透膜的形狀係可舉出例如：中空紗型、螺旋型，基於具有較大的膜模組之每單位容積的膜面積之理由考量，是以螺旋型特別適用。 The shape of the reverse osmosis membrane is, for example, a hollow yarn type or a spiral type, and is particularly suitable for use in the spiral type based on the reason of having a large membrane area per unit volume of the membrane module.
這種逆滲透膜的具體例，係可舉出例如：日東電工公司的「ES-20」、「ESPA2」、「NTR-7400」、「NTR-729HF」以及「NTR-7250」、東麗公司的「SU-710」、「SU-720」、「SU-610」以及「SU-210S」、還有道化學(DOW CHEMICAL)公司的「BW30LE」、「NF-90」以及「NF-70」等。 Specific examples of such a reverse osmosis membrane include, for example, "ES-20", "ESPA2", "NTR-7400", "NTR-729HF", and "NTR-7250" of Nitto Denko Corporation, Toray Corporation "SU-710", "SU-720", "SU-610" and "SU-210S", and "BW30LE", "NF-90" and "NF-70" from Dow Chemical Company Wait.
<優點> <advantage>
該高硬度排水之處理方法，因為是具備：將膜過濾工序後的高硬度排水，進一步利用逆滲透膜(包含奈米過濾膜在內)進行膜處理的工序，因此，可獲得雜質更少之清淨的水。 The method of treating the high-hardness drainage includes a step of performing a membrane treatment by using a high-hardness drainage after the membrane filtration step and further using a reverse osmosis membrane (including a nanofiltration membrane), so that less impurities can be obtained. Clean water.
[排水處理設備] [Drainage treatment equipment]
第2圖係顯示可用來實施第二實施方式的高硬度排水之處理方法的排水處理設備之一例。 Fig. 2 is a view showing an example of a drainage treatment apparatus which can be used to carry out the treatment method of the high hardness drainage of the second embodiment.
第2圖的排水處理設備，是具備：被供給處理對象也就是高硬度排水之凝集槽11；用來將凝集劑投入到這個凝集槽11之凝集劑添加裝置12；用來從凝集槽11送出高硬度排水之粗過濾泵浦13；被從粗過濾泵浦13供給高硬度排水，並且在內部收容著過濾粒子之過濾塔14；用來回收已通過了過濾塔14之後的高硬度排水之粗過濾受水槽15。又，第2圖的排水處理設備，係具備：從粗過濾受水槽15送出高硬度排水之移送用泵浦16；用來貯留從移送用泵浦16供給的高硬度排水(被處理水)之膜過濾供水槽17；用來從膜過濾供水槽17送出高硬度排水之膜過濾泵浦18；利用精密過濾膜或限外超過濾膜對於膜過濾泵浦18所供給的高硬度排水進行過濾之膜過濾單元19。又，第2圖的排水處理設備，係具備：用來貯留從膜過濾單元19排出的高硬度排水之膜處理供水槽20；用來送出膜處理供水槽20中的高硬度排水之膜處理泵浦21；利用逆滲透膜將膜處理泵浦21所供給的高硬度排水分離成透過水與濃縮水之膜處理單元22。此外，第2圖的排水處理設備，係具備：可用來貯留從膜處理單元22排出的透過水的一部分之清洗水槽23；用來將酸投入清洗水槽23內之酸添加裝置24；用來將清洗水槽23內之對於膜處理單元22的透過水(已處理水)添加酸之後的酸性水供給到膜過濾單元19之清洗用泵浦25。此外，第2圖中以虛線顯示的流程，係代表：用來對於過濾塔14或膜處理單元22進行逆清洗時的高硬度排水的流動方 式。具體而言，其中的流路，是除了經過上述清洗水槽23的流路之外，也包含了可將移送用泵浦16所吐出的高硬度排水，朝向過濾塔14之與粗過濾泵浦13所執行的通水方向相反的方向進行通水之流路。 The drainage treatment apparatus of Fig. 2 includes an agglutination tank 11 to which a treatment target, that is, a high-hardness drainage, is supplied; a flocculant addition device 12 for introducing a flocculating agent into the aggregating tank 11; and is used for discharging from the aggregating tank 11 a coarse filter pump 13 for high-hardness drainage; a filter tower 14 that is supplied with high-hardness drainage from the coarse filter pump 13 and contains filter particles therein; and is used for recovering the high-hardness drainage after passing through the filter tower 14 The water receiving tank 15 is filtered. Moreover, the drainage processing apparatus of FIG. 2 is provided with the pumping pump 16 which sent the high-hardness drainage from the coarse filtration receiving water tank 15 and the high hardness drainage (processed water) supplied from the transfer pump 16 Membrane filtration water supply tank 17; membrane filtration pump 18 for sending high hardness drainage from the membrane filtration water supply tank 17; filtering the high hardness drainage water supplied by the membrane filtration pump 18 by using a precision filtration membrane or an outer ultrafiltration membrane Membrane filtration unit 19. Further, the wastewater treatment apparatus of Fig. 2 includes a membrane treatment water supply tank 20 for storing high-hardness drainage discharged from the membrane filtration unit 19, and a membrane treatment pump for feeding high-hardness drainage in the membrane treatment water supply tank 20. Pu 21; the high-hardness drainage supplied from the membrane treatment pump 21 is separated into a membrane treatment unit 22 that permeates water and concentrated water by a reverse osmosis membrane. Further, the wastewater treatment apparatus of Fig. 2 includes a washing tank 23 for storing a part of the permeated water discharged from the membrane processing unit 22, and an acid adding device 24 for introducing the acid into the washing tank 23; The acidic water after the acid is added to the permeated water (treated water) of the membrane processing unit 22 in the washing tank 23 is supplied to the cleaning pump 25 of the membrane filtration unit 19. Further, the flow shown by a broken line in Fig. 2 represents a flow side of high-hardness drainage for performing reverse cleaning on the filtration tower 14 or the membrane processing unit 22. formula. Specifically, the flow path therein includes a high-hardness drainage that can be discharged from the transfer pump 16 in addition to the flow path through the washing water tank 23, and the coarse filter pump 13 toward the filter tower 14 The water flow path is performed in the opposite direction of the water flow direction.
第2圖的排水處理設備的凝集槽11、凝集劑添加裝置12、粗過濾泵浦13、過濾塔14、膜過濾單元19以及清洗水槽23，係可採用與第1圖的排水處理設備的凝集槽1、凝集劑添加裝置2、過濾泵浦3、過濾塔4、膜過濾單元5以及清洗水槽6相同的結構。 The agitation tank 11, the aggregating agent addition device 12, the coarse filtration pump 13, the filtration tower 14, the membrane filtration unit 19, and the washing water tank 23 of the wastewater treatment equipment of Fig. 2 can be agglomerated with the drainage treatment equipment of Fig. 1 . The tank 1, the aggregating agent addition device 2, the filtration pump 3, the filtration tower 4, the membrane filtration unit 5, and the washing water tank 6 have the same structure.
粗過濾受水槽15、膜過濾供水槽17以及膜處理供水槽20，是用來貯留高硬度排水的水槽。又，粗過濾泵浦13、移送用泵浦16、膜過濾泵浦18、膜處理泵浦21以及清洗用泵浦25，只要是可將水予以壓送的泵浦即可，並未特別限定。 The coarse filtration receiving water tank 15, the membrane filtration water supply tank 17, and the membrane processing water supply tank 20 are water tanks for storing high hardness drainage. Further, the coarse filtration pump 13, the transfer pump 16, the membrane filtration pump 18, the membrane treatment pump 21, and the cleaning pump 25 are not particularly limited as long as they are capable of pumping water. .
酸添加裝置24，係可採用：具有例如：用來貯留酸劑的貯留槽；以及用來將酸劑供給到清洗水槽23的酸劑注入用泵浦的結構。更優是具有：用來測定清洗水槽23所貯留的水之pH值的pH值檢測器，而且酸添加裝置24係控制成可自動地供給酸劑來使得清洗水槽23中貯留的水保持為中性。 The acid addition device 24 may have, for example, a storage tank for storing an acid agent, and a structure for pumping an acid agent for supplying an acid agent to the washing water tank 23. More preferably, it has a pH detector for measuring the pH value of the water stored in the washing tank 23, and the acid adding device 24 is controlled to automatically supply the acid agent so that the water stored in the washing tank 23 is kept in the middle. Sex.
第2圖的排水處理設備，係將在過濾塔14進行了粗過濾後的高硬度排水，先暫時地貯留在粗過濾受水槽15以及膜過濾供水槽17。因此，過濾塔14與膜過濾單元19係可互相獨立地進行運轉或進行清洗。又，貯留 在粗過濾受水槽15內的高硬度排水，可當作用來清洗過濾塔14內的過濾粒子的清洗水來使用。換言之，移送用泵浦16也具有可作為用來將清洗水供給到過濾塔14之泵浦的功能。 The drainage treatment equipment of Fig. 2 is a high-hardness drainage which has been coarsely filtered in the filtration tower 14, and is temporarily stored in the coarse filtration receiving water tank 15 and the membrane filtration water supply tank 17. Therefore, the filtration tower 14 and the membrane filtration unit 19 can be operated independently or cleaned independently of each other. Again, storage The high-hardness drainage in the coarse filtration receiving water tank 15 can be used as washing water for cleaning the filter particles in the filtration tower 14. In other words, the transfer pump 16 also has a function as a pump for supplying wash water to the filter tower 14.
又，第2圖的排水處理設備，係製作成：可以將已經過過濾之後的水，分別對於過濾塔14以及膜過濾單元19朝向與其進行過濾時的相反方向通水來做逆清洗，當過濾塔14的粒子層以及膜過濾單元19的過濾膜發生了堵塞時，可比較容易就將過濾塔14的粒子層以及膜過濾單元19的過濾膜予以清洗而恢復其過濾性能。 Further, the wastewater treatment apparatus of Fig. 2 is constructed such that water that has been filtered can be backwashed by the water in the opposite direction to the filtration tower 14 and the membrane filtration unit 19 in the opposite direction, and filtered. When the particle layer of the column 14 and the filtration membrane of the membrane filtration unit 19 are clogged, the particle layer of the filtration tower 14 and the filtration membrane of the membrane filtration unit 19 can be washed relatively easily, and the filtration performance can be restored.
[其他的實施方式] [Other embodiments]
本次所揭示的實施方式中的所有各方面，都只是例示而已，並非只能限制於這種實施方式。本發明的範圍，並不受到上述實施方式的結構的限定，而是涵蓋由申請專利範圍所揭示的內容，以及與申請專利範圍均等的含意以及在該範圍內的所有的變更。 All aspects of the embodiments disclosed herein are illustrative only and are not intended to be limiting. The scope of the present invention is not limited by the structure of the above-described embodiments, but is intended to cover the scope of the claims and the equivalents of the scope of the claims.
該高硬度排水之處理方法，亦可在凝集劑添加工序與粗過濾工序之間，又具有沉降分離工序。 The method for treating the high-hardness drainage may have a sedimentation separation step between the aggregating agent addition step and the coarse filtration step.
該高硬度排水之處理方法中，無論是否具有膜處理工序，都可以在每個工序中自由地決定：是否要在各工序間，先暫時將高硬度排水貯留在受水槽或供水槽？或者是否要經由管路連續地執行各工序。 In the method for treating high-hardness drainage, whether or not there is a membrane treatment step, it is possible to freely determine in each step whether or not to temporarily store the high-hardness drainage in the water receiving tank or the water supply tank between the respective steps. Or whether it is necessary to continuously perform each process via a pipe.
用於該高硬度排水之處理方法的排水處理設 備，也可以是將過濾塔、膜過濾單元以及膜處理單元的其中任何一種構成要素，予以做複數個並列配設。並列配設的構成要素，係可以同時並列運轉，亦可只選擇其中一部進行運轉或者針對休止中的構成要素進行清洗。 Drainage treatment system for the treatment method of the high hardness drainage In addition, any one of the filter tower, the membrane filtration unit, and the membrane processing unit may be arranged in parallel. The components arranged in parallel can be operated in parallel at the same time, or only one of them can be operated or cleaned for the components in the rest.
又，用於該高硬度排水之處理方法的粒子層或過濾膜的清洗水，亦可使用：對於處理中或已處理後的高硬度排水(被處理水或已處理水)以外的水添加了酸之後的清洗水。 Further, the washing water for the particle layer or the filtration membrane used in the treatment method of the high-hardness drainage may be used for adding water other than the high-hardness drainage (treated water or treated water) during or after the treatment. Washing water after acid.
[實施例] [Examples]
以下，將佐以實施例來詳細說明本發明，但並非根據這個實施例的記載內容來限制性的解釋本發明。 In the following, the present invention will be described in detail by way of examples, but the invention is not to be construed restrictively.
為了驗證本發明的效果，乃將自來水(上水)的硬度較高地區的排放污水(下水)已經過了生物處理後的水，當作處理對象之高硬度排水的原水，以燒杯規模(實驗室規模)進行了本發明的處理例1~7的模擬試驗。 In order to verify the effect of the present invention, the discharged sewage (sewage) in a region where the hardness of the tap water (water supply) is high has passed the biologically treated water, and the raw water of the high hardness drainage to be treated is used as a beaker scale (experiment) Room size) The simulation tests of Treatment Examples 1 to 7 of the present invention were carried out.
<處理例1> <Processing Example 1>
處理例1，是以聚合氯化鋁作為凝集劑，並且是以對原水為300質量ppm的濃度比例添加到鈣硬度為170且pH值為7.0的高硬度排水內，將該被處理水，利用具有與無煙煤粒子層近乎同等的過濾能力之5C濾紙(日本工業規格JIS-P3801(1995))當作過濾層來進行粗過濾，將所獲得的過濾水，以5psi的壓力，利用直徑為47mm、平均細 孔徑為0.1μm的精密過濾膜進行膜過濾，每5分鐘就進行測定過濾水的量，並且計算出時間經過與流束變化之間的關係。 In the treatment example 1, the aluminum chloride was used as the aggregating agent, and it was added to a high-hardness drainage having a calcium hardness of 170 and a pH of 7.0 in a concentration ratio of 300 ppm by mass of raw water, and the treated water was used. The 5C filter paper (Japanese Industrial Standard JIS-P3801 (1995)) having a filtration capacity almost equivalent to that of the anthracite particle layer was used as a filtration layer for coarse filtration, and the obtained filtered water was used at a pressure of 5 psi, using a diameter of 47 mm. Average fine Membrane filtration was carried out on a fine filtration membrane having a pore diameter of 0.1 μm, and the amount of filtered water was measured every 5 minutes, and the relationship between the passage of time and the change of the flow was calculated.
<處理例2~5> <Processing Examples 2 to 5>
處理例2~5，高硬度排水的鈣硬度是120，凝集劑的添加量分別是50質量ppm、30質量ppm、20質量ppm、10質量ppm，除此之外的其他條件都是與上述處理例1相同條件，並且計算出時間經過與精密過濾膜的流束變化之間的關係。 In Treatment Examples 2 to 5, the calcium hardness of the high hardness drainage was 120, and the addition amount of the aggregating agent was 50 ppm by mass, 30 ppm by mass, 20 ppm by mass, and 10 ppm by mass, respectively, and other conditions were the same as the above treatment. Example 1 was the same condition, and the relationship between the passage of time and the change of the flow of the fine filtration membrane was calculated.
<處理例6> <Processing Example 6>
處理例6，係將鈣硬度為110且pH值為7.0的高硬度排水的原水，未添加凝集劑，直接以5psi的壓力，利用直徑為47mm、平均細孔徑為0.1μm的精密過濾膜進行膜過濾，每5分鐘就進行測定過濾水的量，並且計算出時間經過與流束變化之間的關係。 Treatment Example 6 is a high-hardness drainage raw water having a calcium hardness of 110 and a pH of 7.0, without adding a coagulant, directly using a precision filtration membrane having a diameter of 47 mm and an average pore diameter of 0.1 μm at a pressure of 5 psi. The amount of filtered water was measured every 5 minutes by filtration, and the relationship between the passage of time and the change of the stream was calculated.
<處理例7> <Processing Example 7>
處理例7，係將鈣硬度為100且pH值為7.0的高硬度排水的原水，使用5C濾紙作為過濾層來進行粗過濾，將所獲得的過濾水，以5psi的壓力，利用直徑為47mm、平均細孔徑為0.1μm的精密過濾膜進行膜過濾，每5分鐘就進行測定過濾水的量，並且計算出時間經過與流束變化 之間的關係。 Treatment Example 7 is a raw water having a high hardness drainage having a calcium hardness of 100 and a pH of 7.0, and coarse filtration was carried out using 5C filter paper as a filtration layer, and the obtained filtered water was used at a pressure of 5 psi, using a diameter of 47 mm. Membrane filtration was carried out on a fine filtration membrane having an average pore diameter of 0.1 μm, and the amount of filtered water was measured every 5 minutes, and time passage and flow change were calculated. The relationship between.
(流束變化) (flow change)
第3圖係顯示上述處理例1~7之隨著時間經過之流束的變化。如圖所示，每一個例子都是在開始進行膜過濾後，隨即流束的降低比較大，約30分鐘後，流束略呈一定。處理例6以及處理例7，30分鐘後的每單位壓力的流束約為6LMH/kPa(L/m2/H/kPa)，相對於此，處理例2~5，30分鐘後的每單位壓力的流束約為10~12LMH/kPa，處理例1，30分鐘後的每單位壓力的流束約為29LMH/kPa。由此結果可以得知：藉由具有凝集劑添加工序、粗過濾工序以及膜過濾工序的處理方法，可使過濾膜的清洗頻度變得比較少。 Fig. 3 is a view showing changes in the flow of the above-described processing examples 1 to 7 over time. As shown in the figure, each example is after the membrane filtration is started, and then the flow reduction is relatively large. After about 30 minutes, the flow is slightly constant. In Treatment Example 6 and Treatment Example 7, the flow rate per unit pressure after 30 minutes was about 6 LMH/kPa (L/m 2 /H/kPa), whereas in the treatment examples 2 to 5, each unit after 30 minutes. The flow of the pressure was about 10 to 12 LMH/kPa, and in the treatment example 1, the flow per unit pressure after 30 minutes was about 29 LMH/kPa. As a result, it was found that the cleaning frequency of the filtration membrane can be made relatively small by the treatment method including the aggregating agent addition step, the coarse filtration step, and the membrane filtration step.
(過濾膜附著物) (filter membrane attachment)
此外，針對於上述處理例1~7，使用傅立葉轉換紅外線分光光度計(FT-IR)對於已經進行了30分鐘的高硬度排水過濾處理後的過濾膜的表面，根據衰減全反射法所測定到的光譜；以及針對於新品過濾膜進行相同的測定所測定到的光譜，從兩種光譜的差值推算出各過濾膜的附著物的組成分。處理例6以及7的過濾膜的附著物的光譜(差值光譜)，是顯示出具有：以頻率3300cm-1為中心之寬廣的峰值，還有在頻率1540cm-1以及頻率1650cm-1的附近具有峰值，表示係有：醯胺基的存在。換言之，處理例6以 及7的過濾膜的附著物，可被推測為例如：是以蛋白質等的有機物為主體的附著物。另一方面，處理例1~5的過濾膜的附著物的光譜，是顯示出具有：以頻率1050cm-1為中心之寬廣的峰值，表示係有：磷酸鈣的存在。換言之，處理例1~5的過濾膜的附著物，可被推測為是以無機物為主體的附著物。因此，處理例6以及7的過濾膜的附著物不易被酸性水溶解，因此，處理例6以及7的過濾膜被認為是：使用酸性水的話，將會不容易清洗，而處理例1~5的過濾膜的附著物比較容易被酸性水所溶解，因此被認為是：使用酸性水的話，可以比較容易清洗。 Further, with respect to the above treatment examples 1 to 7, the surface of the filtration membrane after the high-durability drainage filtration treatment which had been performed for 30 minutes was measured using a Fourier transform infrared spectrophotometer (FT-IR), and was measured by the attenuation total reflection method. The spectrum measured by the same measurement for the new filter membrane, and the composition of the deposit of each filter membrane is derived from the difference between the two spectra. Deposit spectrum (difference spectrum) and the filter membrane 6 Example 7 The process is shown to have: there near 1650cm -1 broad peak centered at a frequency of 3300cm -1 1540cm -1 and a frequency in the frequency Has a peak, indicating the presence of a guanamine group. In other words, the deposits of the filtration membranes of the treatment examples 6 and 7 can be estimated to be, for example, an adherent mainly composed of an organic substance such as protein. On the other hand, the spectrum of the deposit of the filtration membranes of the treatment examples 1 to 5 showed a broad peak centered on the frequency of 1050 cm -1 , indicating the presence of calcium phosphate. In other words, the deposits of the filtration membranes of the treatment examples 1 to 5 can be presumed to be adhering substances mainly composed of inorganic substances. Therefore, the deposits of the filtration membranes of Treatment Examples 6 and 7 are not easily dissolved by acidic water. Therefore, the filtration membranes of Treatment Examples 6 and 7 are considered to be difficult to clean when acidic water is used, and Treatment Examples 1 to 5 The deposit of the filter membrane is relatively easily dissolved by acidic water, and therefore it is considered that it is relatively easy to clean using acidic water.
為了證實本發明的效果，乃將上述高硬度的河川水先經過砂礫間接觸處理後的水，藉由日量為100m3的急速過濾裝置，進行了實證試驗。處理例8，是以聚合氯化鋁作為凝集劑，並且是以對原水為10質量ppm的濃度比例添加到上述高硬度排水內。pH值是6.8。將其以使用了粗密性較之5C濾紙(保留粒子徑為1μm)更低之有效直徑為0.5mm的石英砂之急速過濾裝置進行了過濾。(石英砂，是以有效直徑為0.4~0.7mm為宜，更好的有效直徑是0.5~0.6mm。) In order to confirm the effect of the present invention, the above-mentioned high-hardness river water was first subjected to a contact treatment between the gravel, and an empirical test was conducted by a rapid filtration device having a daily amount of 100 m 3 . In the treatment example 8, polyaluminum chloride was used as a coagulant, and it was added to the high-hardness drainage in a concentration ratio of 10 ppm by mass to the raw water. The pH is 6.8. This was filtered by a rapid filtration apparatus using quartz sand having an effective diameter of 0.5 mm lower than that of 5C filter paper (retained particle diameter of 1 μm). (Quartz sand is suitable for an effective diameter of 0.4 to 0.7 mm, and a better effective diameter is 0.5 to 0.6 mm.)
將所獲得的過濾水，以5psi的壓力，利用直徑為47mm、平均細孔徑為0.1μm的精密過濾膜進行膜過濾，每5分鐘就進行測定過濾水的量，並且計算出時間經過與流束變化之間的關係。此外，進行15分鐘的膜過濾所獲得之過濾水的合計量是525mL。 The obtained filtered water was subjected to membrane filtration using a precision filtration membrane having a diameter of 47 mm and an average pore diameter of 0.1 μm at a pressure of 5 psi, and the amount of filtered water was measured every 5 minutes, and the passage of time and the flow were calculated. The relationship between changes. Further, the total amount of the filtered water obtained by performing membrane filtration for 15 minutes was 525 mL.
第4圖係顯示：上述處理例8、以及作為比較例之未添加凝集劑且是利用濾紙進行過濾後的隨著時間經過之流束的變化。上述處理例8，初期的流束是41LMH/kPa(L/m2/H/kPa)、3分鐘後的流束是17LMH/kPa(L/m2/H/kPa)、5分鐘後的流束是14LMH/kPa(L/m2/H/kPa)、10分鐘後的流束是10LMH/kPa(L/m2/H/kPa)、15分鐘後的流束是8LMH/kPa(L/m2/H/kPa)。作為比較例之未添加凝集劑無且是利用濾紙進行過濾的例子，初期的流束是19LMH/kPa(L/m2/H/kPa)、3分鐘後的流束是6LMH/kPa(L/m2/H/kPa)、5分鐘後的流束是5LMH/kPa(L/m2/H/kPa)、10分鐘後的流束是4LMH/kPa(L/m2/H/kPa)、15分鐘後的流束是3LMH/kPa(L/m2/H/kPa)。上述處理例8，係可確保較之未添加凝集劑且以濾紙進行過濾的比較例之兩倍以上的流束。由此結果可以證實，藉由：實用裝置規模的凝集劑添加工序、以及以急速過濾的粗過濾工序來進行處理，可以有效改善膜過濾工序的過濾性。 Fig. 4 is a view showing the change of the flow of the above-mentioned treatment example 8 and the comparative example, in which the agglutinating agent was not added and filtered by the filter paper. In the above treatment example 8, the initial flow was 41 LMH/kPa (L/m 2 /H/kPa), and the flow after 3 minutes was 17 LMH/kPa (L/m 2 /H/kPa), and the flow after 5 minutes. The bundle was 14 LMH/kPa (L/m 2 /H/kPa), the flow after 10 minutes was 10 LMH/kPa (L/m 2 /H/kPa), and the flow after 15 minutes was 8 LMH/kPa (L/ m 2 /H/kPa). As a comparative example, an example in which no aggregating agent was added and filtered by a filter paper was used, and the initial flow was 19 LMH/kPa (L/m 2 /H/kPa), and the flow after 3 minutes was 6 LMH/kPa (L/ m 2 /H/kPa), the flow after 5 minutes is 5 LMH/kPa (L/m 2 /H/kPa), and the flow after 10 minutes is 4 LMH/kPa (L/m 2 /H/kPa). The stream after 15 minutes was 3 LMH/kPa (L/m 2 /H/kPa). In the above treatment example 8, it is possible to ensure a flow of more than twice that of the comparative example in which the aggregating agent is not added and filtered by the filter paper. From this result, it was confirmed that the filtration property of the membrane filtration step can be effectively improved by performing the treatment in the aggregating agent addition step on the practical device scale and the coarse filtration step in the rapid filtration.
1‧‧‧凝集槽 1‧‧‧ agglutination tank
2‧‧‧凝集劑添加裝置 2‧‧‧ agglutinating agent adding device
3‧‧‧過濾泵浦 3‧‧‧Filter pump
4‧‧‧過濾塔 4‧‧‧Filter tower
5‧‧‧膜過濾單元 5‧‧‧ membrane filtration unit
6‧‧‧清洗水槽 6‧‧‧cleaning sink
7‧‧‧清洗用泵浦 7‧‧‧cleaning pump
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