醫藥中間體生產廢水處理技術
引言
安(an)徽省(sheng)某藥(yao)業(ye)(ye)有(you)限公司是(shi)從事醫(yi)(yi)藥(yao)中(zhong)間(jian)(jian)體(ti)(ti)、動植物(wu)(wu)藥(yao)提取以(yi)(yi)及(ji)生物(wu)(wu)化(hua)(hua)學(xue)原(yuan)料藥(yao)的(de)技術研(yan)(yan)發(fa)、產(chan)品(pin)生產(chan)與銷售的(de)一(yi)家外商(shang)獨資企(qi)業(ye)(ye)。該企(qi)業(ye)(ye)在投產(chan)初期主要產(chan)品(pin)有(you)SP(舒必利:C15H23N3O4S),POTA(鄰芐基苯甲酸:C14H12O2),CP(氯丙嗪:C17H19CIN2S)以(yi)(yi)及(ji)REBA(瑞巴派特(te):C19H15CIN2O4)等(deng)醫(yi)(yi)藥(yao)中(zhong)間(jian)(jian)體(ti)(ti)。隨著市場需(xu)求不斷擴大(da),企(qi)業(ye)(ye)生產(chan)規模不斷擴大(da),逐步開展(zhan)了唑嘧胺中(zhong)間(jian)(jian)體(ti)(ti)、鹽酸依匹斯汀中(zhong)間(jian)(jian)體(ti)(ti)、格(ge)列美脲中(zhong)間(jian)(jian)體(ti)(ti)等(deng)近(jin)30類中(zhong)間(jian)(jian)體(ti)(ti)研(yan)(yan)發(fa)生產(chan)。醫(yi)(yi)藥(yao)中(zhong)間(jian)(jian)體(ti)(ti)生產(chan)過程中(zhong)產(chan)生的(de)廢(fei)水(shui)具(ju)(ju)有(you)排放量大(da)、成分復雜、有(you)機物(wu)(wu)濃(nong)度高(gao)、可生化(hua)(hua)性差等(deng)特(te)點,導(dao)致處理(li)(li)的(de)難度比較大(da)[1-3]。生化(hua)(hua)處理(li)(li)技術具(ju)(ju)有(you)運行費(fei)用低、投資省(sheng)、效(xiao)率高(gao)等(deng)優點[4],被廣泛應用于醫(yi)(yi)藥(yao)中(zhong)間(jian)(jian)體(ti)(ti)廢(fei)水(shui)的(de)處理(li)(li)中(zhong)[5-6]。本設計采用“預處理(li)(li)-UASB-二級生物(wu)(wu)接(jie)觸(chu)氧化(hua)(hua)”為主體(ti)(ti)的(de)廢(fei)水(shui)處理(li)(li)工藝,廢(fei)水(shui)處理(li)(li)系統投入運行以(yi)(yi)來效(xiao)果(guo)良好,且出(chu)水(shui)水(shui)質穩(wen)定達(da)標。
1廢水(shui)(shui)(shui)水(shui)(shui)(shui)質、水(shui)(shui)(shui)量(liang)及(ji)排放標準
醫藥中間(jian)體生產廢(fei)水(shui)由(you)工藝(yi)廢(fei)水(shui)和生活污(wu)水(shui)2部分組(zu)成,綜合廢(fei)水(shui)水(shui)質(zhi)指標均為平均值,排放標準(zhun)(zhun)執行當地園區(qu)污(wu)水(shui)處理廠的(de)接管標準(zhun)(zhun)。廢(fei)水(shui)水(shui)質(zhi)及接管標準(zhun)(zhun)見表1。廢(fei)水(shui)產生量約(yue)為260m3/d,設計處理量為300m3/d。
2廢水(shui)處理工藝設計
2.1工(gong)藝流程
首先通(tong)(tong)過預處理調節廢水(shui)(shui)(shui)的(de)(de)(de)pH值、去除大(da)顆粒SS,然后(hou)通(tong)(tong)過曝氣調節池調節水(shui)(shui)(shui)量水(shui)(shui)(shui)質,調節均勻(yun)的(de)(de)(de)廢水(shui)(shui)(shui)通(tong)(tong)過水(shui)(shui)(shui)泵提入厭氧反應(ying)階(jie)(jie)段(duan),在厭氧菌的(de)(de)(de)作(zuo)用下,將難以(yi)降(jiang)解的(de)(de)(de)大(da)分子有(you)(you)機物(wu)分解為小分子有(you)(you)機物(wu),提高廢水(shui)(shui)(shui)的(de)(de)(de)可(ke)生(sheng)化(hua)性(xing),通(tong)(tong)過厭氧段(duan)的(de)(de)(de)降(jiang)解,具(ju)有(you)(you)良好可(ke)生(sheng)化(hua)性(xing)的(de)(de)(de)廢水(shui)(shui)(shui)進入接(jie)觸(chu)氧化(hua)階(jie)(jie)段(duan),通(tong)(tong)過好氧菌的(de)(de)(de)好氧硝化(hua)降(jiang)解,將廢水(shui)(shui)(shui)中的(de)(de)(de)污染物(wu)質轉化(hua)為無機物(wu),完成廢水(shui)(shui)(shui)的(de)(de)(de)處理。其工藝流程見圖1。
2.2主要工藝(yi)設計參數(shu)
(1)預處理設施(shi)
由于醫藥中(zhong)(zhong)(zhong)間體生產(chan)廢(fei)水受pH值影響較(jiao)大[3],且(qie)廢(fei)水中(zhong)(zhong)(zhong)SS濃度較(jiao)高,所以預處理階段的設(she)置是非常必要的。預處理設(she)施主(zhu)要包括中(zhong)(zhong)(zhong)和(he)(he)池、沉淀(dian)池和(he)(he)過濾池:中(zhong)(zhong)(zhong)和(he)(he)池有(you)效容(rong)積(ji)40m3(4.5m×4.5m×3.4m,有(you)效水深(shen)2m),地(di)下式磚混結構,表面做防腐處理,池內(nei)安裝(zhuang)UPVC氣(qi)動攪拌裝(zhuang)置;沉淀(dian)池有(you)效容(rong)積(ji)及池體尺(chi)寸與中(zhong)(zhong)(zhong)和(he)(he)池相同,池內(nei)安裝(zhuang)斜板填(tian)料;過濾池以活性(xing)炭作為(wei)(wei)濾料,池體尺(chi)寸為(wei)(wei)4.5m×4.5m×3.4m,有(you)效水深(shen)為(wei)(wei)2m,填(tian)料層高度為(wei)(wei)1m。
(2)曝(pu)氣(qi)調節池
由于生(sheng)產排水不(bu)均勻,故(gu)設1個調節池(chi)(chi)以(yi)調節水量(liang)水質(zhi),保證(zheng)后續(xu)處理(li)工(gong)段的穩(wen)定運行。曝氣調節池(chi)(chi)有(you)效容積440m3(14m×9m×5m,有(you)效水深3.5m),地下式鋼筋(jin)混凝土結構(gou);池(chi)(chi)內(nei)安裝(zhuang)穿孔(kong)管(guan),通過鼓風機向池(chi)(chi)內(nei)提(ti)供空氣;池(chi)(chi)內(nei)安裝(zhuang)2臺提(ti)升泵,將廢水提(ti)升到厭氧處理(li)階段。
(3)厭氧處理設施
UASB池(chi)(chi)(chi)具(ju)有(you)較高(gao)的(de)有(you)機負荷,能夠有(you)效(xiao)的(de)降低廢(fei)水(shui)(shui)(shui)中(zhong)污(wu)染物質的(de)濃度,提高(gao)廢(fei)水(shui)(shui)(shui)的(de)可(ke)生(sheng)化(hua)性(xing)。UASB池(chi)(chi)(chi)有(you)效(xiao)容積為(wei)310m3(Φ6m×12m,有(you)效(xiao)水(shui)(shui)(shui)深(shen)(shen)11m),采用地(di)上8.5m,地(di)下(xia)3.5m的(de)鋼混結(jie)構,池(chi)(chi)(chi)內(nei)上部安裝多面球填(tian)料,下(xia)部安裝2m的(de)軟性(xing)填(tian)料,提高(gao)微生(sheng)物與廢(fei)水(shui)(shui)(shui)的(de)接觸面積。UASB池(chi)(chi)(chi)出水(shui)(shui)(shui)進(jin)入水(shui)(shui)(shui)解酸化(hua)池(chi)(chi)(chi),降解一些大分子有(you)機物質,進(jin)一步提高(gao)廢(fei)水(shui)(shui)(shui)的(de)可(ke)生(sheng)化(hua)性(xing),有(you)利于(yu)后續好(hao)氧階段處理。水(shui)(shui)(shui)解酸化(hua)池(chi)(chi)(chi)有(you)效(xiao)容積為(wei)240m3(9m×5.5m×5.2m,有(you)效(xiao)水(shui)(shui)(shui)深(shen)(shen)4.8m),池(chi)(chi)(chi)底設置2個泥(ni)(ni)斗,并安裝2臺污(wu)泥(ni)(ni)回流泵(beng),將污(wu)泥(ni)(ni)回流到UASB池(chi)(chi)(chi)內(nei)。
(4)好氧處理設施
經水解處理后的廢水進入二(er)級(ji)接(jie)觸氧(yang)化(hua)(hua)處理設施,在(zai)好(hao)氧(yang)生(sheng)物膜的作用(yong)下,大部(bu)分(fen)的有(you)機(ji)污染物被去除。一級(ji)接(jie)觸氧(yang)化(hua)(hua)池(chi)(chi)有(you)效容積540m3(14m×8m×5.2m,有(you)效水深4.8m),控(kong)制CODCr有(you)機(ji)負(fu)荷為2.0kg/(m3·d);二(er)級(ji)接(jie)觸氧(yang)化(hua)(hua)池(chi)(chi)有(you)效容積290m3(14m×8m×5.2m,有(you)效水深4.6m),控(kong)制有(you)效負(fu)荷在(zai)0.5kg/(m3·d),池(chi)(chi)體為鋼(gang)混(hun)結(jie)構;接(jie)觸氧(yang)化(hua)(hua)池(chi)(chi)池(chi)(chi)底安(an)裝(zhuang)微孔曝(pu)氣裝(zhuang)置,通過(guo)鼓風(feng)機(ji)提供氧(yang)氣,池(chi)(chi)中(zhong)安(an)裝(zhuang)3.5m的軟性(xing)填(tian)料。2級(ji)接(jie)觸氧(yang)化(hua)(hua)池(chi)(chi)中(zhong)間設置1座中(zhong)間池(chi)(chi),用(yong)于污泥(ni)回(hui)流(liu),池(chi)(chi)中(zhong)安(an)裝(zhuang)2臺污泥(ni)回(hui)流(liu)泵。
(5)后(hou)處理(li)設施(shi)
廢水(shui)(shui)經過2級接觸氧化處理后,進入斜(xie)(xie)管沉(chen)淀(dian)池(chi)(chi),將隨(sui)水(shui)(shui)流帶出的微(wei)生物沉(chen)淀(dian)下來(lai),降低出水(shui)(shui)的SS含量。斜(xie)(xie)管沉(chen)淀(dian)池(chi)(chi)有效容積為45m3(7m×2m×3.5m,有效水(shui)(shui)深3.2m),池(chi)(chi)體為鋼混結構,池(chi)(chi)底(di)設(she)置1個泥(ni)斗,安裝1臺污(wu)泥(ni)泵,將剩(sheng)余污(wu)泥(ni)打入污(wu)泥(ni)濃縮池(chi)(chi)。
(6)污泥處理(li)設施
剩余(yu)污(wu)泥(ni)(ni)含水量很高,經過(guo)污(wu)泥(ni)(ni)濃(nong)縮池(chi)進(jin)一(yi)步濃(nong)縮之后,用(yong)污(wu)泥(ni)(ni)泵(beng)打入污(wu)泥(ni)(ni)干(gan)化(hua)池(chi)進(jin)行干(gan)化(hua)處理。污(wu)泥(ni)(ni)濃(nong)縮池(chi)有(you)(you)效(xiao)容積為50m3(4m×4m×3.5m,有(you)(you)效(xiao)深度3.2m),地上(shang)式(shi)鋼混(hun)結構(gou),濃(nong)縮液回流至(zhi)調節(jie)池(chi);污(wu)泥(ni)(ni)干(gan)化(hua)池(chi)有(you)(you)效(xiao)容積20m3(6m×3m×1.5m),有(you)(you)效(xiao)干(gan)化(hua)面積為18m2,地上(shang)式(shi)磚混(hun)結構(gou),池(chi)底設置砂濾(lv)層,滲濾(lv)液回流至(zhi)調節(jie)池(chi)。
3調試及運行(xing)效果
該工(gong)(gong)程(cheng)調(diao)試過(guo)(guo)程(cheng)中(zhong)(zhong)(zhong)所需污泥(ni)(ni)取自污水(shui)(shui)(shui)處理廠污泥(ni)(ni)脫水(shui)(shui)(shui)間(jian),投加(jia)質量濃度(du)(du)為3000mg/L。馴化(hua)過(guo)(guo)程(cheng)采用(yong)(yong)階梯式(shi)馴化(hua)法,池(chi)中(zhong)(zhong)(zhong)溫度(du)(du)控(kong)制在18~24℃,pH值控(kong)制在6~8,ρ(DO)在4~8mg/L,HRT為48h。進(jin)(jin)水(shui)(shui)(shui)中(zhong)(zhong)(zhong)添(tian)加(jia)一定量的工(gong)(gong)業葡萄糖、尿素(su)和(he)磷(lin)(lin)酸二氫鉀補充碳源、氮源和(he)磷(lin)(lin)源,進(jin)(jin)水(shui)(shui)(shui)中(zhong)(zhong)(zhong)ρ(COD)∶ρ(N)∶ρ(P)=200∶5∶1;每(mei)日進(jin)(jin)水(shui)(shui)(shui)中(zhong)(zhong)(zhong)添(tian)加(jia)一定比例的廢(fei)水(shui)(shui)(shui),使得進(jin)(jin)水(shui)(shui)(shui)中(zhong)(zhong)(zhong)廢(fei)水(shui)(shui)(shui)的濃度(du)(du)隨時(shi)(shi)間(jian)不(bu)斷(duan)(duan)增加(jia),同時(shi)(shi)不(bu)斷(duan)(duan)減少營(ying)養源的使用(yong)(yong)量,直到進(jin)(jin)水(shui)(shui)(shui)全部(bu)為廢(fei)水(shui)(shui)(shui),并且污泥(ni)(ni)對COD的去(qu)除(chu)率達(da)到穩(wen)定,馴化(hua)完成(cheng)。
階(jie)梯式馴(xun)化(hua)(hua)法(fa)(fa)(fa)是采用逐(zhu)步提高污(wu)泥馴(xun)化(hua)(hua)過(guo)程(cheng)中的(de)(de)(de)廢水(shui)(shui)水(shui)(shui)量(liang)(liang)(liang),同(tong)時減(jian)少營(ying)養物(wu)質的(de)(de)(de)投加量(liang)(liang)(liang),直至進水(shui)(shui)全部為廢水(shui)(shui)的(de)(de)(de)馴(xun)化(hua)(hua)方(fang)(fang)法(fa)(fa)(fa)。與(yu)傳(chuan)統(tong)的(de)(de)(de)全負荷馴(xun)化(hua)(hua)方(fang)(fang)法(fa)(fa)(fa)相比,該馴(xun)化(hua)(hua)方(fang)(fang)法(fa)(fa)(fa)可(ke)以(yi)使(shi)活性(xing)污(wu)泥中的(de)(de)(de)微生(sheng)物(wu)盡快的(de)(de)(de)適應(ying)馴(xun)化(hua)(hua)環境(jing),有利于處(chu)理(li)(li)醫藥中間(jian)體生(sheng)產廢水(shui)(shui)的(de)(de)(de)優(you)勢菌種(zhong)的(de)(de)(de)培(pei)養,優(you)勢菌種(zhong)的(de)(de)(de)成長可(ke)以(yi)顯著的(de)(de)(de)減(jian)少馴(xun)化(hua)(hua)所需要(yao)的(de)(de)(de)時間(jian),同(tong)時有利于節(jie)約馴(xun)化(hua)(hua)過(guo)程(cheng)中消耗的(de)(de)(de)營(ying)養源。經過(guo)1個月左右的(de)(de)(de)培(pei)養馴(xun)化(hua)(hua),污(wu)水(shui)(shui)處(chu)理(li)(li)系(xi)統(tong)中的(de)(de)(de)活性(xing)污(wu)泥就實(shi)現了穩定增長,并(bing)能(neng)夠大幅(fu)降解生(sheng)產廢水(shui)(shui)中的(de)(de)(de)污(wu)染物(wu)質。1個月后開(kai)展系(xi)統(tong)聯動調試(shi),將系(xi)統(tong)的(de)(de)(de)運行(xing)(xing)負荷提高到80%,測(ce)試(shi)系(xi)統(tong)各工段的(de)(de)(de)設備、工藝運行(xing)(xing)情況。通過(guo)不(bu)斷(duan)(duan)調整生(sheng)物(wu)接觸氧化(hua)(hua)工段所需風量(liang)(liang)(liang)、污(wu)泥回流量(liang)(liang)(liang)及剩余污(wu)泥量(liang)(liang)(liang),UASB系(xi)統(tong)內部的(de)(de)(de)污(wu)水(shui)(shui)回流量(liang)(liang)(liang),并(bing)不(bu)斷(duan)(duan)優(you)化(hua)(hua)預處(chu)理(li)(li)工段的(de)(de)(de)運行(xing)(xing)參數,使(shi)系(xi)統(tong)達到最佳的(de)(de)(de)運行(xing)(xing)狀態。
系統經(jing)過(guo)(guo)2個月調(diao)試后,各項測試指標均(jun)達到污水(shui)處(chu)理廠的接(jie)管(guan)(guan)標準。運(yun)行結果表明(ming),該系統運(yun)行穩定(ding),抗沖擊負荷能力強。環保部門(men)抽檢(jian)及企業自(zi)檢(jian)結果顯示,廢水(shui)各項指標均(jun)穩定(ding)達標。近期運(yun)行數據見(jian)表2。由表2可見(jian),廢水(shui)經(jing)過(guo)(guo)“預(yu)處(chu)理-UASB-二級接(jie)觸氧化”工藝處(chu)理后,平均(jun)去除效率(lv)分別為CODCr96.3%,BOD592.1%,NH3-N93.6%,SS89.7%,出(chu)水(shui)監測指標均(jun)優于接(jie)管(guan)(guan)標準。
4結論
(1)“預處(chu)(chu)理-UASB-二(er)級接觸氧化(hua)”工藝(yi)能有效處(chu)(chu)理高濃度,水(shui)(shui)量、水(shui)(shui)質變化(hua)較大的(de)醫藥(yao)中間(jian)體生產(chan)廢水(shui)(shui),CODCr,BOD5,NH3-N,SS等去除(chu)效果穩定,達標率(lv)高。
(2)該(gai)工藝(yi)各段優勢菌(jun)性(xing)能突出,能針(zhen)對廢水中不同的(de)有(you)機污染(ran)物發揮作用,該(gai)工藝(yi)具有(you)耐沖擊負荷強、污染(ran)物質(zhi)去除(chu)效率高、投資少(shao)、運(yun)行(xing)費(fei)用低、污泥產生量少(shao)等(deng)優點。

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