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印染廢水深度處理技術(shù)及回用的現(xiàn)狀和發(fā)展
毛艷梅 奚旦立 楊曉波
(東華大學(xué)環(huán)境科學(xué)與工程學(xué)院上海20051)
【摘 要】 根據(jù)印染廢水深度處理及回用的現(xiàn)狀，介紹了若干深度處理方案，并對其祝缺點(diǎn)進(jìn)行了評述;再從環(huán)境效益和經(jīng)濟(jì)效益雙贏的目標(biāo)出發(fā)，提出重視推廣綜合治理、不斷優(yōu)化回用方案、繼續(xù)開發(fā)膜集成技術(shù)是印染廢水回用的研究發(fā)展方向。
[關(guān)鍵詞] 印染廢水;深度處理;回用;膜技術(shù)
[中圖分類號]Tu992.3
0 前言
印染廢水一直以排放量大、處理難度高成為廢水治理工藝研究的重點(diǎn)。特別由于近年來化纖織物的發(fā)展和印染后整理技術(shù)的進(jìn)步，使PvA漿料、新型助劑等難生化降解有機(jī)物大量進(jìn)人印染廢水，更是給處理增加了難度;原有的生物處理系統(tǒng)大都由原來的70%COD去除率下降到50%左
右，甚至更低。由于水資源的日漸短缺和污染嚴(yán)重，印染行業(yè)的廢水處理引起政府的高度重視。我國印染廢水處理普遍采用物化處理+生化處理工藝，但處理效果并不十分穩(wěn)定，一般很難達(dá)到一級排放標(biāo)準(zhǔn)。為了能夠使廢水達(dá)標(biāo)排放，人們在不同工藝單元的組合、新工藝的開發(fā)和參數(shù)優(yōu)化方面都進(jìn)行了廣泛的研究，取得了不少進(jìn)展，為實(shí)現(xiàn)印染廢水深度處理和回用奠定了基礎(chǔ)。
1． 印染廢水回用處理技術(shù)的現(xiàn)狀
一直以來由于印染廢水本身難處理的特性，人們對印染廢水深度處理回用方面沒有引起足夠的重視。加人WTO后，隨著我國紡織印染行業(yè)的勢頭逐步看好，紡織印染行業(yè)用水的需求量不斷增大，而供給量卻相對減少;隨著排放標(biāo)準(zhǔn)的日趨嚴(yán)格和水費(fèi)的不斷上漲，人們將目光投向印染廢水深度處理和回用上。由于印染工藝本身的復(fù)雜性和工藝用水水質(zhì)要求的差異，目前國家對印染廢水的回用水質(zhì)標(biāo)準(zhǔn)還沒有統(tǒng)一的數(shù)據(jù)。近年來人們對印染廢水深度處理的工藝從技術(shù)和經(jīng)濟(jì)的可行性上都進(jìn)行了大量探索、分析和實(shí)踐，取得了可喜的環(huán)境效益和經(jīng)濟(jì)效益。目前出現(xiàn)的印染廢水深度處理組合方案主要有以下幾種:
1.1 印染廢水。生化出水*混凝*氣浮。砂濾*活性炭吸附*回用該方 案 完 全是物化技術(shù)的組合，何文杰等用此方案深度處理某毛紡廠經(jīng)生物接觸氧化法處理后的出水(水質(zhì)變化見表1)。經(jīng)接觸氧化池的出水已經(jīng)能夠達(dá)標(biāo)排放，但廢水中殘留的染料通常以膠體狀態(tài)存在，該方案能夠較有針對性地去除膠體物質(zhì)，使出水達(dá)到回用要求。Giovanni的研究也得出了相似的結(jié)論。
表1 水質(zhì)變化表
測定項目
生物接觸氧化出水
氣浮
活性碳吸附
總?cè)コВ?）
回用要求
COD（mg/L）
88
44
16.5
81.3
-
BOD（mg/L）
14.7
10.8
9.3
34
-
色度
71
3
1
98.6
5-10
碳度
-
2
1.1
-
＜4
PH
6.5
6.5
6.5
-
6.5-8
分別用氣浮后和吸附后的兩種出水作為回用水進(jìn)行染布試驗。實(shí)驗結(jié)果表明用回用水染布已達(dá)到一級品出廠標(biāo)準(zhǔn)。經(jīng)回用后，該毛紡廠每年節(jié)約新鮮水36萬m3，節(jié)約資金2400萬元。該方案操作流程簡便，適用于目前印染廢水已經(jīng)達(dá)標(biāo)排放的企業(yè)。
1.2 廢水處理站出水*生物陶粒一臭氧脫色升雙層濾料過濾。陽離子交換樹脂軟化。出水該方案是較為典型的各種處理方法的組合，充分發(fā)揮各組合單元的優(yōu)勢。李武全等用此方案對北京第二毛紡織廠的印染廢水(加人部分生活污水混合)的二沉池出水進(jìn)行深度處理(處理效果見表2)，并研究了各單元不同的組合順序?qū)λ|(zhì)處理效果的影響。實(shí)驗發(fā)現(xiàn)臭氧出水中的剩余臭氧可能會破壞交換樹脂結(jié)構(gòu)，使其失去交換能力。因此在工程中需要增加清水池待臭氧分解完畢后再進(jìn)入交換樹脂?；赜脤?shí)驗表明其工藝出水可以回用于洗毛和染色。該方案提示我們在進(jìn)行不同處理方法組合時不僅要看到其優(yōu)勢的方面，也要注意其相互制約、乃至有所破壞的方面，避免不利因素的影響。
1.3 印染廢水。混凝沉淀*內(nèi)循環(huán)厭氧-HCR/生物活性炭一接觸氧化。纖維球過濾賈洪 斌 等 采用了比較新型的生物復(fù)合處理工藝，即將HCR法與生物活性炭法相結(jié)合，使反應(yīng)器中氧利用率提高、抗沖擊負(fù)荷能力增強(qiáng)，有效解決了傳統(tǒng)好氧生物處理的不足之處。該工藝占地面積較小，且纖維球具有過濾速度快、效果好的優(yōu)點(diǎn)，使廢水能穩(wěn)定達(dá)到回用要求(水質(zhì)變化見表3)。回用水經(jīng)回用生產(chǎn)性實(shí)驗，發(fā)現(xiàn)水洗后的布樣色光、深度與自來水洗后的一致，說明采用回用水皂洗是可行的。該工藝對于目前采用傳統(tǒng)好氧工藝處理效果不理想的印染企業(yè)，在工藝改進(jìn)方面是一個很好的參考。
1.4 二級處理廠出水*電化學(xué)處理、化學(xué)絮凝。離子交換一爭回用電化學(xué)法，結(jié)合化學(xué)絮凝和離子交換法對印染廢水進(jìn)行深度處理研究。實(shí)驗表明添加少量的H202(約200mg/L)在電解池中可使電化學(xué)處理效率提高一倍。該方案的優(yōu)點(diǎn)是出水水質(zhì)好，可以回用到印染所有工序中(見表4);不足之處在于實(shí)驗發(fā)現(xiàn)pH為3時電化學(xué)效果最好，因此在進(jìn)行電化學(xué)處理前要調(diào)pH值，另外該方案對離子交換樹脂的依賴性較大(為了降低鐵離子濃度和電導(dǎo)率)，因此離子再生頻率升高不可避免。
1.5 印染廢水一調(diào)pH【加酸)葉鐵碳過濾升中和(加堿)-SBR--"回用鐵碳 過 濾 系統(tǒng)是用廢鐵屑(主要成分是鐵和碳)經(jīng)預(yù)處理和活化后作為填料，其工作原理是電化學(xué)反應(yīng)的氧化還原、鐵屑對絮體的電附集和對反應(yīng)的催化作用、電池反應(yīng)產(chǎn)物的混凝、新生絮體的吸附和床層的過濾等作用的綜合效應(yīng)。林金畫采用該方案對印染廢水進(jìn)行處理，出水達(dá)到一級排放標(biāo)(GB4287-92)(見表5)。出水回用于漂染的漂洗生產(chǎn)工序，8年來系統(tǒng)未出現(xiàn)過堵塞現(xiàn)象。該工藝優(yōu)點(diǎn)是以廢治廢，運(yùn)行穩(wěn)定;不足之處是pH必須來回調(diào)節(jié)。
1.6 二沉池出水斗一級砂濾-C102氧化什二級過濾。活性炭?；赜糜莩?偉 對 印染廠經(jīng)二級處理后的出水采用C102氧化，對廢水色度、COD的去除效果進(jìn)行了研究(見表6)。實(shí)驗結(jié)果表明:濃度為40m妙 C102對紫色等13種顏色的印染排放廢水進(jìn)行30min的氧化反應(yīng)，出水基本滿足了印染廢水的回用要求;再用活性炭對C102氧化出水進(jìn)行后處理去除余氯，進(jìn)一步提高回用水質(zhì)，擴(kuò)大回用水的應(yīng)用范圍。該工藝操作簡便，特別在色度去除上效果較好，值得進(jìn)一步研究和推廣。
2 印染廢水回用的發(fā)展方向
2.1重視推廣綜合治理
企業(yè)在選 擇印染廢水的深度處理工藝時，應(yīng)本著清潔生產(chǎn)的理念，結(jié)合自身情況，從源頭預(yù)防開始，盡量以廢治廢、綜合治理，進(jìn)一步削減和降低污染物的排放。是偉元對印染廢水進(jìn)行綜合治理，包括改進(jìn)生產(chǎn)工藝設(shè)計、設(shè)備的選型、篩選染化藥劑、殘漿殘液的集中處理、冷凝水基本回用，用鍋爐水膜除塵作預(yù)處理，部分水經(jīng)三級處理直接回用等等。馬志毅和胡穎華都用印染廢水與煙道氣及粉煤灰接觸，既滿足了除塵的目的，又節(jié)約了新鮮水用量，同時提高了印染廢水的處理效果。胡穎華還將處理后的廢水回用于染色和印花，與自來水相比色牢度基本無差別。
2.2不斷優(yōu)化回用方案
回用方案的優(yōu)化既包括水質(zhì)優(yōu)化，也包括水量優(yōu)化。水質(zhì)優(yōu)化即不同工藝單元的有效組合或是不同處理技術(shù)的集成，都是為了揚(yáng)長避短，使水質(zhì)達(dá)到回用要求。由于回用水質(zhì)要求差異較大，廢水回用方式有兩種，一是回用水全部按照需求最嚴(yán)格的水質(zhì)要求處理，二是先按照水量要求最大的水質(zhì)要求處理，個別有更高要求的小水量水再進(jìn)行適當(dāng)?shù)难a(bǔ)充處理。水量優(yōu)化即企業(yè)應(yīng)根據(jù)自身情況選擇一種較為經(jīng)濟(jì)的回用方式。實(shí)踐證明，上述多種組合方案處理后的回用水用于水質(zhì)要求相對較低、且用水量較大的雜用水，部分冷卻水及印染前工序用水(如退漿、煮練、氧漂、絲光等)都是完全可行的。若要用于水質(zhì)要求較高的后工序(如打底、皂洗等)，就要保證更加嚴(yán)格的深度處理，并可考慮將新鮮水與回用水定量配比混合使用。
2.3 繼續(xù)開發(fā)膜集成技術(shù)
隨著技術(shù)的進(jìn)步，膜分離技術(shù)的不斷開發(fā)是未來廢水深度處理的重要方向。越來越多的研究表明將不同的膜分離技術(shù)(如微濾、超濾、納濾等)相結(jié)合或是膜分離技術(shù)與其它技術(shù)(如催化氧化技術(shù)、電化學(xué)法等)相結(jié)合是印染廢水深度處理的一個研究方向。目前正在優(yōu)化和應(yīng)用的集成技術(shù)有MFIUF/RO集成系統(tǒng)、膜生物反應(yīng)器(MBR)+RO,抗污染反滲透復(fù)合膜等，另外還有離子交換、紫外線消毒等方法集成需要進(jìn)一步開發(fā)和研究。杜啟云等用膜集成技術(shù)處理鄂爾多斯羊絨集團(tuán)公司廢水。該系統(tǒng)用水膜除塵技術(shù)使廢水脫脂、脫色，超濾除菌除濁、反滲透脫鹽等過程使熱電廠煙道氣達(dá)標(biāo)排放，工業(yè)廢水得到深度處理，變成軟水供熱電廠和生產(chǎn)車間回用。該系統(tǒng)日處理生產(chǎn)廢水1500m'，水回收率70%用混凝一陶瓷膜一納濾膜技術(shù)對印染廢水的二次出水進(jìn)行處理。試驗發(fā)現(xiàn):用聚合鋁作為混凝劑可防止廢水中的懸浮固體和膠體顆粒對陶瓷膜的污染，使陶瓷膜的化學(xué)清洗周期延長為一周一次;陶瓷膜保護(hù)納濾膜，可不添加任何化學(xué)物也能連續(xù)運(yùn)行。研究結(jié)果表明水質(zhì)完全符合回用標(biāo)準(zhǔn)。有資料報道，美國棉花公司用Fenton試劑一UF/NF技術(shù)處理活性染料印染廢水，廢水經(jīng)Fenton試劑氧化脫色，再經(jīng)OF/NF分別得到濃縮液和淡水，試驗表明淡水用于漂白、染色、淋洗等，對織物的色澤和質(zhì)量無任何不利影響;用濃縮液染色還需進(jìn)一步研究。
3 結(jié)論
若要切實(shí)達(dá)到經(jīng)濟(jì)效益和環(huán)境效益雙贏的目的，企業(yè)必須同等重視印染廢水的污染預(yù)防和治理，并在保證產(chǎn)品質(zhì)量不受影響的前提下努力做到廢水深度處理回用以及廢物料的回收再利用，這樣既節(jié)約水資源和原料，又能有效減輕印染廢水對環(huán)境的污染。因此得出以下結(jié)論:
3.1隨著環(huán)境保護(hù)力度的加大，印染企業(yè)應(yīng)該越來越重視清潔生產(chǎn)。低污染和環(huán)保原料的使用以
及生產(chǎn)工藝的改進(jìn)可以減少廢水及有毒有害污染物的產(chǎn)生，從而降低印染廢水處理與深度處理的難度，有利于印染廢水的回用。
3.2 目前印染廢水的回用主要是以達(dá)標(biāo)排放為前提，因此在繼續(xù)開發(fā)和研究新的低成本的深度處理技術(shù)的同時，一方面要研究不同深度處理技術(shù)的集成;另一方面要將傳統(tǒng)工藝與新技術(shù)相結(jié)合進(jìn)行工藝改進(jìn)和優(yōu)化，使工藝和技術(shù)更加成熟，這樣既提高處理效果，又降低處理成本，是今后印染廢水回用技術(shù)的研究發(fā)展方向。
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Present situation and development that the technique reached back use are handle to the printing and dyeing liquid waste depth
Xi Danli Mao Yanmei is Yang Xiaobo
(Eastern China university environmental science together with project academy Shanghai 20051 )
【Abstract 】 On the basis of the printing and dyeing liquid waste depth handle reaches back the present situation of use ，Introduce several depth handle schemes ，moreover to such wishes that the defect has been underway the commentary ; twin target departs triumphhing again through environment beneficial result and the economic results ，Propose to value spreaing the comprehensive regulation 、continuously optimizing back employs the scheme 、the integrated technique of membrane is opened up in the contiuation is that printing and dyeing liquid waste gos back the use research development orientation 。
[ keyword ] printing and dyeing liquid waste ; The depth handle ; Going back use ; Membrane technique
[ middle figure class number ] Tu992.3
0 Foreword
Print to dye the waste water has been toing exhaust to have great capacity, handles the difficulty the high becoming the point that waste water manage craft research.Special because of turning the development of the thing of with print to tidy up the technical advance after dying in recent years, making the syrup of PvA anticipated, new help an etc. difficult living to turn to decline to solve organic matter large quantity enter the person prints to dye the waste water, also give to handles to increase the difficulty; the original living creature handles the system be done away with by original 70% COD mostly the rate descends to 50% , even much lower.Because the resources of water is missing gradually with contaminative serious, print the liquid waste processing that dye the profession cause the governmental valuing highly.The our country prints to dye the widespread adoption in liquid waste processing thing turns to handle+ living to turn to handle craft, but handle result and not quite stability, can hardly attain generally a class exhaustion standard.For enabling the waste water amount to the mark exhausts, people all proceeded the extensive research in the aspects of the development of the combination, new craft of the different craft unit ising excellent to turn with the parameter, making not a few progresses, for realizes to print to dye the waste water treatment.
1. Print to dye the waste water return to technical present condition in reason in use
Always since then because of printing to dye the waste water oneself the difficult processed characteristic, people to print to dye the waste water depth handles back to did not cause to value enoughly with the aspect.After adding the person the WTO, along with the our country spin and weave to print the power head that dye the profession think ° to be good gradually, spinning and weave to print to dye the profession use the aqueous demand to enlarge continuously, but supply the however opposite decrease in deal; along with the exhaustion standard is a strict soaring with water rate continuously gradually, people throw the vision to print to dye the waste water depth handles with return to use the top.Because printing the complexity that dye the craft oneself to use the difference that water fluid matter request with the craft, current nation to print to dye the waste water return to return to have no the united data with the fluid matter standard.In recent years people to print the craft that dye the waste water depth handles to proceeded with economic possibility top all from the technique large quantity investigates, analysis with practice, obtain can pleased environment performance with economic performance.Appear now of printing and dying the waste water depth handles the combination project has primarily below several kinds:
1.1 Print to dye the waste water.Living to turn a water .Sand the live adsorbs returns to use should the square case over and all is a water that thing turn the technical combination, why text hero etc. handles with this project depth some hair factory after living creature contact oxidize method handles.( fluid matter variety see the table 1)Wasing oxidized by contact a water of the pond has caned reach the mark exhausts, but the dyestuff remained in the waste water usually exsits with the gum appearance, that project can than aim at the sex ground do away with the gum material, using the water attain back to use the request.The Giovanni research also gets alike conclusion. Use the spirit to return after floating behind with two kinds of a waters conduct and actions that adsorb to proceed to dye cloth to experiment with the water respectively.The experiment result express to use back to dye cloth with the water already to a class article a factory standard.After return to use year of the hair's spins factory economizes the fresh water 24 economy funds 2400 ten thousand dollars.That project operation process is simple being applicable to print to dye the waste water to have reached the business enterprise that mark exhaust now.
1.2 The liquid waste processing stands a water living creature grain a the ozone takes off the color rises a layer anticipates the percolation.The cation commutation resin softens.A water that project is advantage that more typical and every kind of combination that handles method, develop each combination unit well.Lee's is identically equal to use this project to Peking the second hair textile mill prints to dye the waste water( add the living dirty water of part of person mixs with) of two sink the pond a water proceed the depth handles( handle the result see the table 2), and studies the different combination in each unit sequence to handles to the fluid matter the influence of the result.The experiment discovers the ozone an aquatic surplus ozone may break the commutation resin construction, making its lose the commutation ability.Therefore at need to increase in the engineering the clear water pond need the ozone resolves to complete behind again enter the commutation resin.Returning to express with the experiment its craft a water cans return to used for washing the hair with dye.That project hints us in the aspects of proceeding differently handling method combination hour not only seeing its advantage of, also noticing its make mutually roughly, is to have the destructive aspect, avoid the influence of the disadvantageous factor.
1.3 Print to dye the waste water.The precipitates the inside circulate live in oxygenliving creature in a the contact oxidizes.The fiber ball filters Jiabinhing etc. Adopted the new living creature reunites to handle craft, will soon the method of HCR combine together with live the method of in living creature, making reactor inside the oxygen utilization increases, the anti- pounds at the burthen ability strengthens, solving effectively the not enough place that traditional good oxygen living creature handles.That craft covers the area smaller, and the fiber ball has the percolation speed quick, advantage that result like, can make waste water stabilized to attain back to use the request.( fluid matter variety see the table 3)Return to use the water after return to experiment with the production, discover cloth kind color light, depth that water wash in accordance with the running water wash behind of, explain it is viable that adoption return to wash with the soap of water.That craft prints traditional good oxygen in current adoption craft handles result not very much to dye the business enterprise, ising an in the aspects of craft improving good consulting.
1.4 It is second class to handles factory a water the electricity chemistry handles, chemistry .Ion exchange a the return to use to give or get an electric shock the chemistry method with the Tak- H yun, combination chemistry with ion exchange method to print to dye the waste water proceed the depth handles research.The experiment express to increase a little amount H202( roughly 200 mgs/ L) to can make give or get an electric shock in electrolysis pond the chemistry handles the efficiency increases a times.The advantage of that project is a dependence that a water fluid matter is good, can return to use to print to dye all works preface inside( see the table 4); not enough be placed in to discovers pH as 3 hours electricity chemistry result in the experiment best, therefore at proceed to give or get an electric shock the chemistry before handling want to adjust the pH value, another that project is bigger( for lowering the iron ion density with electric conductivity rate) to ion exchange resin, the reborn frequency in for this reason ion go up and can't avoid.
1.5 Print to dye the waste water on adjusting thePH (adds sour) leaf the iron carbon filters to rise to moderate( add the alkali)- SBR-" return to use the carbon of iron to is a , new-born of that the catalyst function, battery that the electricity to uses the scrap iron scraps( the main composition is an iron with the carbon) after prepares to handle with activate be used as the filler, its work principle is give or get an electric shock chemical reaction oxidizes to restore, the scraps of iron to of attaches to gather with respond the outcome to the reaction adsorb over the system of to synthesize the effect with percolation etc. function of the bed layer.Wood the gold painting adopts that project to print to dye the waste water proceeds to handle, a water attains a the class exhausts the mark( GB4287-92).( see the table 5)That a water return to to used for the to dye to wash the production work preface,8 in the last years systems have never appeared to stop the phenomenon.The craft's advantage toes discard to cure to discard, circulating the stability; the not enough place is a pH and must regulate back and forth.
1.6 Two sink the pond a water a the class sand - c102 oxidizes the second class percolation in what .Live return to accept the with the worry to print to dye the factory was oxidized by second class a water adoption c102 handling behind away with to the waste water color degree the result proceeded the research . ( see the table 6)Experiment result enunciation: the density is a wonderful C102 to wait to the purple color 13 kinds of colors prints to dye to exhaust the waste water proceeds a 30 mins oxidizing the reaction, a water is basic to satisfied to print to dye the waste water of returning and using request; use again the live to oxidize to the C102 a the water handles to do away with the remaining after proceeding, further increases back to use the fluid matter, extend back to use the aqueous application.That craft the operation is simple, specially the result is better in color degree doing away with, deserving further research with expand.
2 Print the waste water that dye the development direction return to use
2.1 value the expansion synthesize to manage
Business enterprise at choose to choosethe depth that print dyes the waste water to handle Craft be in the light of the principle that sweep the production oneself circumstance from a prevention discard to cure to discard to manage to the best reduction with lower the pollutant exhausts.Is a the dollar of great to print to dye the waste water proceed to synthesize to manage the improvement produce the technological design equipments of choose the type, sieving dye concentration that turn the medicine a syrup liquid handles, the congealed water is basic to return to use, divideding by with the boiler water membrane the makes to prepare to handle, parts of waters through x-rated handles to return to use the etc. directly.The horse ambition use to print to dye with Hulihua all the waste water contacts smoke jet of gas and powder ash from stoves, since satisfied to divided by the purpose of the ,economizing the fresh the dosage of water again, increasing to print to dye at the same time the waste water handles result. Hulihua will still the waste water handling behind returns to used for the dyeing with the stamp-tax, comparing with running water the color prison a basic indiscrimination.
2.2 continuously excellent turn back to use the project
Return to use the project excellent to turn since include the fluid matter the excellent turning, also include the amount of water the excellent turning.The fluid matter is excellent to turn the valid combination of the namely different craft unit or different handles to gather technically, is all for the sake of the to grow to avoid short, make fluid matter attained back to use the request.Because returning to request the difference with the fluid matter bigger, the waste water return to have with the way two kinds of, on ising a small water to return to use the water all according to require with the most strict fluid matter request handles, two is first to request according to the amount of water biggest fluid matter request handles, individual have the higher requesting to measure the water proceeds again appropriate complement handles.The amount of water is excellent to turn namely the business enterprise should choose according to the oneself circumstance a kind of than return to use the way economicly.Practice the proof, above various combinations project return to used for with the water after handling the fluid matter request to be opposite and lower, and use the amount of water the bigger and miscellaneous using the water, the part cools off the water and prints to dye the ex- work makes appointment to post the water( if back the syrup and boil to practice, oxygen, silk light etc.) is all complete viable.If used for the fluid matter request the higher empress work preface( if beat the bottom, soap wash etc.), will guarantee the more strict depth handles, combining can consider the fresh water with return to go together with with the fixed amount of water the ratio mixs with usage.
2.3 Continue to develop the membrane gather technique
Along with the technical advance, the membrane separates the technical developping continuously is an important direction that future waste water depth handles.More and more