煤氣化廢水處理技術及其應用進展
摘要:根據目前國內外應(ying)(ying)用(yong)較多的Lurgi碎煤加壓氣(qi)(qi)(qi)(qi)化(hua)技(ji)術(shu)(shu)、Shell干粉(fen)煤氣(qi)(qi)(qi)(qi)化(hua)技(ji)術(shu)(shu)和Texaco水(shui)煤漿氣(qi)(qi)(qi)(qi)化(hua)煤氣(qi)(qi)(qi)(qi)化(hua)技(ji)術(shu)(shu),總結了(le)上(shang)述3種煤氣(qi)(qi)(qi)(qi)化(hua)廢(fei)水(shui)的水(shui)質,綜述了(le)煤氣(qi)(qi)(qi)(qi)化(hua)廢(fei)水(shui)的預處(chu)(chu)理技(ji)術(shu)(shu)、生化(hua)處(chu)(chu)理技(ji)術(shu)(shu)、深度(du)處(chu)(chu)理技(ji)術(shu)(shu)及回用(yong)(或(huo)近零排放)技(ji)術(shu)(shu),列舉了(le)上(shang)述技(ji)術(shu)(shu)在實際(ji)中(zhong)的應(ying)(ying)用(yong),指出了(le)煤氣(qi)(qi)(qi)(qi)化(hua)廢(fei)水(shui)處(chu)(chu)理技(ji)術(shu)(shu)和回用(yong)技(ji)術(shu)(shu)的現存問(wen)題及未來發(fa)展方向(xiang)。
關鍵詞:煤(mei)氣化(hua)廢水;預(yu)處理;生化(hua)處理;深(shen)度處理;回用
雖然(ran)(ran)我國(guo)的(de)(de)能源(yuan)結(jie)構調整取得了(le)顯著效果,但煤(mei)(mei)(mei)(mei)(mei)在(zai)(zai)我國(guo)的(de)(de)能源(yuan)消(xiao)費中仍處(chu)于主導地(di)(di)位。發(fa)(fa)展以(yi)煤(mei)(mei)(mei)(mei)(mei)為(wei)原料的(de)(de)化(hua)(hua)(hua)(hua)工(gong)產(chan)(chan)業,可(ke)以(yi)依靠我國(guo)豐富的(de)(de)煤(mei)(mei)(mei)(mei)(mei)炭(tan)(tan)資(zi)源(yuan),保障我國(guo)的(de)(de)基本化(hua)(hua)(hua)(hua)學品供給和(he)(he)能源(yuan)安全,具有十分重要(yao)的(de)(de)意義。煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)產(chan)(chan)業可(ke)分為(wei)傳(chuan)統(tong)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)和(he)(he)新(xin)型(xing)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)2 大(da)(da)類(lei)。目前,傳(chuan)統(tong)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)產(chan)(chan)品已經存在(zai)(zai)結(jie)構性產(chan)(chan)能過剩的(de)(de)現(xian)象,以(yi)煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)為(wei)龍(long)頭的(de)(de)新(xin)型(xing)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)項(xiang)目,如煤(mei)(mei)(mei)(mei)(mei)制天然(ran)(ran)氣(qi)(qi)(qi)、煤(mei)(mei)(mei)(mei)(mei)制油(you)、煤(mei)(mei)(mei)(mei)(mei)制烯烴、煤(mei)(mei)(mei)(mei)(mei)制乙二(er)醇等,作為(wei)潔凈、高(gao)效利用(yong)煤(mei)(mei)(mei)(mei)(mei)炭(tan)(tan)的(de)(de)先進工(gong)業技(ji)(ji)術正在(zai)(zai)逐漸替(ti)代傳(chuan)統(tong)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)在(zai)(zai)我國(guo)迅速發(fa)(fa)展[1-3]。但是,新(xin)型(xing)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)項(xiang)目仍是一項(xiang)耗水(shui)(shui)(shui)量(liang)(liang)高(gao)、廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)量(liang)(liang)高(gao)、污染物排放量(liang)(liang)大(da)(da)的(de)(de)產(chan)(chan)業,而我國(guo)的(de)(de)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)項(xiang)目多建(jian)設(she)在(zai)(zai)內蒙古(gu)、新(xin)疆(jiang)、陜西、山西和(he)(he)寧(ning)夏等煤(mei)(mei)(mei)(mei)(mei)炭(tan)(tan)資(zi)源(yuan)豐富但水(shui)(shui)(shui)資(zi)源(yuan)短缺的(de)(de)地(di)(di)區,煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)的(de)(de)快速發(fa)(fa)展引發(fa)(fa)了(le)一系列水(shui)(shui)(shui)資(zi)源(yuan)、水(shui)(shui)(shui)環境的(de)(de)問(wen)題。因此,發(fa)(fa)展高(gao)效、穩定(ding)的(de)(de)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)處(chu)理技(ji)(ji)術,開(kai)發(fa)(fa)最大(da)(da)程度的(de)(de)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)回(hui)用(yong)技(ji)(ji)術已經成(cheng)為(wei)以(yi)煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)為(wei)核(he)心(xin)的(de)(de)新(xin)型(xing)煤(mei)(mei)(mei)(mei)(mei)化(hua)(hua)(hua)(hua)工(gong)項(xiang)目可(ke)持(chi)續發(fa)(fa)展的(de)(de)關(guan)鍵問(wen)題之一[4]。針對不同的(de)(de)煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)技(ji)(ji)術產(chan)(chan)生的(de)(de)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui),本文中對其水(shui)(shui)(shui)質進行了(le)總結(jie),綜(zong)述了(le)煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)的(de)(de)處(chu)理技(ji)(ji)術和(he)(he)回(hui)用(yong)技(ji)(ji)術,并列舉了(le)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)處(chu)理和(he)(he)回(hui)用(yong)技(ji)(ji)術在(zai)(zai)實際煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)中的(de)(de)應用(yong),針對應用(yong)中發(fa)(fa)現(xian)的(de)(de)問(wen)題提出了(le)煤(mei)(mei)(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui)(shui)(shui)處(chu)理和(he)(he)回(hui)用(yong)技(ji)(ji)術的(de)(de)未來發(fa)(fa)展方向,為(wei)進一步發(fa)(fa)展提供支撐。
1 煤氣化技術及其氣化廢水概述
不(bu)(bu)同的(de)(de)(de)(de)煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)技術(shu)適用(yong)(yong)的(de)(de)(de)(de)煤(mei)(mei)(mei)種不(bu)(bu)同,對(dui)應的(de)(de)(de)(de)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)廢水(shui)水(shui)質(zhi)也有所不(bu)(bu)同。根(gen)據(ju)固體和氣(qi)(qi)(qi)體間的(de)(de)(de)(de)相對(dui)運(yun)動(dong)方式,煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)技術(shu)可分為固定床(chuang)煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)、流化(hua)(hua)(hua)(hua)床(chuang)煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)、氣(qi)(qi)(qi)流床(chuang)煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)3 種,目前,國內外應用(yong)(yong)較多的(de)(de)(de)(de)是固定床(chuang)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)技術(shu)中的(de)(de)(de)(de)Lurgi 碎煤(mei)(mei)(mei)加壓氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)、氣(qi)(qi)(qi)流床(chuang)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)技術(shu)中的(de)(de)(de)(de)Shell 干粉(fen)煤(mei)(mei)(mei)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)和Texaco 水(shui)煤(mei)(mei)(mei)漿(jiang)氣(qi)(qi)(qi)化(hua)(hua)(hua)(hua)[5-6]。
Lurgi 碎煤(mei)加壓(ya)氣(qi)(qi)化(hua)(hua)工藝多用于生(sheng)產(chan)天然(ran)氣(qi)(qi),Lurgi 碎煤(mei)加壓(ya)氣(qi)(qi)化(hua)(hua)廢(fei)(fei)水中的污染(ran)成分(fen)(fen)較(jiao)為復雜,酚(fen)(fen)(fen)類(lei)物(wu)質、COD、氨(an)氮等指標數值均(jun)較(jiao)高(gao),酚(fen)(fen)(fen)氨(an)回(hui)(hui)收(shou)前(qian)廢(fei)(fei)水中COD 濃度(du)通常(chang)在20 000 mg/L 以(yi)上;Shell 粉(fen)煤(mei)氣(qi)(qi)化(hua)(hua)產(chan)水量(liang)小,不(bu)含有酚(fen)(fen)(fen)類(lei)、油類(lei)等污染(ran)物(wu),水質比較(jiao)潔凈;Texaco 水煤(mei)漿氣(qi)(qi)化(hua)(hua)廢(fei)(fei)水不(bu)含油類(lei),酚(fen)(fen)(fen)類(lei)物(wu)質較(jiao)少,廢(fei)(fei)水也較(jiao)為潔凈;酚(fen)(fen)(fen)氨(an)回(hui)(hui)收(shou)后的碎煤(mei)加壓(ya)氣(qi)(qi)化(hua)(hua)廢(fei)(fei)水、粉(fen)煤(mei)氣(qi)(qi)化(hua)(hua)廢(fei)(fei)水和水煤(mei)漿氣(qi)(qi)化(hua)(hua)廢(fei)(fei)水主要成分(fen)(fen)見表1[7]。
表1[7]。
2 煤氣化廢水處理技術
2.1 預處理技術
預處(chu)(chu)理(li)由(you)于(yu)氣(qi)化(hua)(hua)工藝(yi)(yi)的(de)(de)不同而差別(bie)較大。對(dui)于(yu)Texaco 水(shui)煤(mei)漿氣(qi)化(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui),預處(chu)(chu)理(li)多(duo)采用(yong)“化(hua)(hua)學軟化(hua)(hua)+沉(chen)淀”的(de)(de)組合工藝(yi)(yi)以去除廢(fei)(fei)(fei)(fei)水(shui)中的(de)(de)懸浮物、二氧(yang)化(hua)(hua)硅和硬度;對(dui)于(yu)Shell 干粉煤(mei)氣(qi)化(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui),預處(chu)(chu)理(li)多(duo)采用(yong)漂水(shui)破氰工藝(yi)(yi);對(dui)于(yu)Lurgi 碎煤(mei)加壓氣(qi)化(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui),多(duo)采用(yong)“浮動收油(you)+隔油(you)+氣(qi)浮”組合工藝(yi)(yi)進(jin)行脫塵除油(you)后,進(jin)行酚(fen)氨回收[8]。
通常(chang)采用汽提法進行脫(tuo)(tuo)(tuo)(tuo)氨并去除廢水中(zhong)的酸(suan)(suan)性(xing)氣體,酚(fen)(fen)回(hui)收則以溶(rong)劑萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)為(wei)主,目前(qian)在工(gong)(gong)(gong)(gong)(gong)業中(zhong)使用的脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)萃(cui)取(qu)劑主要有二異丙醚(mi)(DIPE)和甲(jia)基異丁(ding)基甲(jia)酮(MIBK)2 種。應用較為(wei)廣(guang)泛的酚(fen)(fen)氨回(hui)收工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)主要有4 種:LurgiPhenosolvanCLL 工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)(酸(suan)(suan)化(hua)后萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)再(zai)(zai)(zai)脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)脫(tuo)(tuo)(tuo)(tuo)氨工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi))、脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)后脫(tuo)(tuo)(tuo)(tuo)氨雙塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)、脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)脫(tuo)(tuo)(tuo)(tuo)氨再(zai)(zai)(zai)萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)單(dan)塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)和雙塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)[9]。其(qi)中(zhong),LurgiPhenosolvanCLL 工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)在國內工(gong)(gong)(gong)(gong)(gong)程(cheng)應用案(an)例較少;賽鼎公司研發的脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)后脫(tuo)(tuo)(tuo)(tuo)氨雙塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)正逐(zhu)漸被取(qu)代;華南(nan)理工(gong)(gong)(gong)(gong)(gong)大學化(hua)工(gong)(gong)(gong)(gong)(gong)系統工(gong)(gong)(gong)(gong)(gong)程(cheng)研究中(zhong)心(xin)研發的脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)脫(tuo)(tuo)(tuo)(tuo)氨再(zai)(zai)(zai)萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)單(dan)塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)和雙塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)是(shi)國內主要采用的酚(fen)(fen)氨回(hui)收工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi),雙塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)的能(neng)耗要比(bi)單(dan)塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)的能(neng)耗高,目前(qian),脫(tuo)(tuo)(tuo)(tuo)酸(suan)(suan)脫(tuo)(tuo)(tuo)(tuo)氨再(zai)(zai)(zai)萃(cui)取(qu)脫(tuo)(tuo)(tuo)(tuo)酚(fen)(fen)單(dan)塔(ta)(ta)工(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)(yi)(yi)在中(zhong)煤哈(ha)爾濱煤化(hua)工(gong)(gong)(gong)(gong)(gong)有限公司和中(zhong)煤鄂爾多(duo)斯圖克化(hua)肥(fei)廠穩定運行[3-4]。
2.2 生化處理技術
煤氣(qi)化廢水(shui)經預處(chu)(chu)理(li)(li)(li)后進入(ru)生(sheng)化處(chu)(chu)理(li)(li)(li)單元,生(sheng)化處(chu)(chu)理(li)(li)(li)技術通常分為好(hao)氧生(sheng)物處(chu)(chu)理(li)(li)(li)技術、厭氧生(sheng)物處(chu)(chu)理(li)(li)(li)技術、厭氧-好(hao)氧組(zu)合(he)處(chu)(chu)理(li)(li)(li)技術。煤氣(qi)化廢水(shui)的水(shui)量大、成分復雜(za),目前國(guo)內應用較為廣泛的生(sheng)物處(chu)(chu)理(li)(li)(li)技術為厭氧-好(hao)氧組(zu)合(he)處(chu)(chu)理(li)(li)(li)技術。
在(zai)國內,厭(yan)(yan)氧(yang)(yang)(yang)(yang)/好氧(yang)(yang)(yang)(yang)(A/O)工(gong)(gong)(gong)(gong)藝(yi)(yi)是煤氣化(hua)(hua)(hua)廢水(shui)(shui)(shui)生(sheng)化(hua)(hua)(hua)處理(li)中(zhong)(zhong)應(ying)用(yong)最(zui)為(wei)廣泛的(de)(de)工(gong)(gong)(gong)(gong)藝(yi)(yi),根(gen)據(ju)來水(shui)(shui)(shui)水(shui)(shui)(shui)質(zhi)的(de)(de)不同(tong),在(zai)A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)的(de)(de)基(ji)礎上(shang)又衍生(sheng)出了A/A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)、A/A/O/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)、A/O/A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)等。A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)與其他(ta)工(gong)(gong)(gong)(gong)藝(yi)(yi)的(de)(de)耦(ou)合也被廣泛研究(jiu),Wang 等[10]利用(yong)A/A/O-膜生(sheng)物反應(ying)器(MBR)組(zu)合工(gong)(gong)(gong)(gong)藝(yi)(yi)處理(li)Lurgi 碎煤加壓氣化(hua)(hua)(hua)廢水(shui)(shui)(shui);徐鵬(peng)等[11]采用(yong)外(wai)循(xun)環厭(yan)(yan)氧(yang)(yang)(yang)(yang)(EC 厭(yan)(yan)氧(yang)(yang)(yang)(yang))-改良(liang)(liang)AO-MBR 工(gong)(gong)(gong)(gong)藝(yi)(yi)處理(li)新疆某煤化(hua)(hua)(hua)工(gong)(gong)(gong)(gong)項(xiang)目廢水(shui)(shui)(shui);徐春(chun)艷[12]利用(yong)生(sheng)物增(zeng)濃(nong)(nong)-改良(liang)(liang)A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)處理(li)煤制氣廢水(shui)(shui)(shui),廢水(shui)(shui)(shui)中(zhong)(zhong)的(de)(de)COD、總氮、氨氮去除率分別可以達(da)到99%、80%、95%以上(shang)。在(zai)工(gong)(gong)(gong)(gong)業(ye)上(shang),外(wai)循(xun)環厭(yan)(yan)氧(yang)(yang)(yang)(yang)(EC 厭(yan)(yan)氧(yang)(yang)(yang)(yang))-改良(liang)(liang)AO-MBR 工(gong)(gong)(gong)(gong)藝(yi)(yi)、EC 厭(yan)(yan)氧(yang)(yang)(yang)(yang)-生(sheng)物增(zeng)濃(nong)(nong)池-改良(liang)(liang)A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)、升流式厭(yan)(yan)氧(yang)(yang)(yang)(yang)污(wu)(wu)泥(ni)(ni)床(chuang)(UASB)-A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)、O-A/O-MBR 工(gong)(gong)(gong)(gong)藝(yi)(yi)、A-載體流動床(chuang)生(sheng)物膜法(CBR)-O 工(gong)(gong)(gong)(gong)藝(yi)(yi)、水(shui)(shui)(shui)解酸(suan)化(hua)(hua)(hua)-A/O工(gong)(gong)(gong)(gong)藝(yi)(yi)都有所應(ying)用(yong)。此外(wai),在(zai)A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)的(de)(de)基(ji)礎上(shang),通(tong)過投加填料而(er)(er)組(zu)成的(de)(de)A/O-生(sheng)物膜工(gong)(gong)(gong)(gong)藝(yi)(yi)也被關注(zhu),趙(zhao)維電等[13]通(tong)過在(zai)O 池投加聚(ju)氨酯(zhi)填料而(er)(er)增(zeng)加了生(sheng)化(hua)(hua)(hua)單元的(de)(de)抗沖擊性(xing)(xing);滕濟(ji)林等[14]向A/A/O 工(gong)(gong)(gong)(gong)藝(yi)(yi)的(de)(de)O 池投加粉末活性(xing)(xing)焦形(xing)成生(sheng)物膜-懸浮污(wu)(wu)泥(ni)(ni)復合系統,并將(jiang)剩(sheng)(sheng)余污(wu)(wu)泥(ni)(ni)回流至系統前段對(dui)原水(shui)(shui)(shui)進行預處理(li),在(zai)提(ti)高O池活性(xing)(xing)污(wu)(wu)泥(ni)(ni)濃(nong)(nong)度的(de)(de)同(tong)時,含焦剩(sheng)(sheng)余污(wu)(wu)泥(ni)(ni)對(dui)原水(shui)(shui)(shui)也進行了吸附預處理(li)。
在煤氣(qi)化廢(fei)水(shui)的生化處理中,序(xu)批式活性污泥(SBR)工藝(yi)的應(ying)用(yong)也較為廣泛。對(dui)于(yu)(yu)Lurgi 碎煤加(jia)壓氣(qi)化廢(fei)水(shui),水(shui)解酸化-SBR-O 等耦合(he)工藝(yi)也在實際中有所應(ying)用(yong)。Tabassum 等[15]將(jiang)厭氧SBR-好氧SBR 用(yong)于(yu)(yu)煤氣(qi)化廢(fei)水(shui)中,發(fa)現總(zong)氮(dan)、總(zong)酚(fen)、揮發(fa)酚(fen)、氨(an)氮(dan)的去除率分(fen)別為65%、80%、99.5%、99.4%。趙茜[16]于(yu)(yu)實驗(yan)室構建了PACT-SBNR 組(zu)合(he)工藝(yi),將(jiang)活性炭(tan)-活性污泥工藝(yi)(PACT)和SBR 工藝(yi)耦合(he),構建了煤氣(qi)化廢(fei)水(shui)的短(duan)程脫(tuo)氮(dan)體系。
很(hen)多研究人員(yuan)采用移動床或(huo)生物接觸(chu)氧化(hua)工(gong)藝(yi)(yi)處理煤氣(qi)化(hua)廢(fei)(fei)水(shui)(shui),取得了不(bu)錯的(de)效果。Hui 等[17]利用移動床生物膜反應器(MBBR)去除(chu)煤氣(qi)化(hua)廢(fei)(fei)水(shui)(shui)中的(de)酚(fen)(fen)類(lei)、硫(liu)氰酸鹽和氨氮。于(yu)廣欣等[18]采用膨(peng)脹顆粒污泥(ni)床(EGSB)-接觸(chu)氧化(hua)工(gong)藝(yi)(yi)處理碎煤加壓(ya)氣(qi)化(hua)廢(fei)(fei)水(shui)(shui),實驗(yan)表明,當EGSB 水(shui)(shui)力(li)停(ting)留時(shi)間為(wei)48 h,接觸(chu)氧化(hua)停(ting)留時(shi)間為(wei)64 h 時(shi),COD 去除(chu)率(lv)達70%以(yi)上(shang),總(zong)酚(fen)(fen)去除(chu)率(lv)為(wei)80%左右,揮(hui)發酚(fen)(fen)全部去除(chu)。中煤龍化(hua)哈爾濱(bin)煤化(hua)工(gong)的(de)Lurgi 碎煤加壓(ya)氣(qi)化(hua)廢(fei)(fei)水(shui)(shui)則(ze)采用生物接觸(chu)氧化(hua)工(gong)藝(yi)(yi)進行COD 和氨氮的(de)去除(chu)[19]。
2.3 深度處理技術
由于煤(mei)氣化(hua)廢水中(zhong),尤(you)其是固(gu)定床煤(mei)氣化(hua)廢水中(zhong),難降解(jie)有機物多(duo)(duo)、毒性大(da)、可生化(hua)性差(cha),因此,生化(hua)單元(yuan)的出(chu)水通常需要(yao)進一(yi)步深度(du)處理(li)才(cai)能保證其穩定達標排放。近年來研(yan)究較多(duo)(duo)的深度(du)處理(li)技術主(zhu)要(yao)包括混凝(ning)沉淀技術、吸附技術、高級(ji)氧化(hua)技術、生物技術,而在實際工業應用上,基(ji)本采用上述技術的組合。
吸(xi)附技術是(shi)利(li)用吸(xi)附劑將廢(fei)(fei)(fei)水(shui)中的污(wu)染物富集(ji)在吸(xi)附劑上的一種方法。常用的吸(xi)附劑包括活性(xing)(xing)炭(tan)(tan)(tan)、活性(xing)(xing)焦、樹(shu)脂(zhi)等。蔣文新等[20]考(kao)察了不同原材料的活性(xing)(xing)炭(tan)(tan)(tan)對煤化(hua)工(gong)生化(hua)出(chu)水(shui)的吸(xi)附效果,并比較了混(hun)凝沉淀(dian)(dian)、活性(xing)(xing)炭(tan)(tan)(tan)吸(xi)附以及混(hun)凝沉淀(dian)(dian)+活性(xing)(xing)炭(tan)(tan)(tan)吸(xi)附工(gong)藝(yi)的處(chu)理效果。Agarwal 等[21]采(cai)用FeCl3 負載的改(gai)性(xing)(xing)活性(xing)(xing)炭(tan)(tan)(tan)處(chu)理含苯(ben)酚(fen)和氰(qing)化(hua)物的廢(fei)(fei)(fei)水(shui)。大唐克旗煤制天然氣項目(mu)采(cai)用活性(xing)(xing)焦深度(du)(du)處(chu)理煤氣化(hua)廢(fei)(fei)(fei)水(shui),吸(xi)附飽和的活性(xing)(xing)焦則進行(xing)燃燒(shao)處(chu)理。在煤化(hua)工(gong)廢(fei)(fei)(fei)水(shui)中應用的樹(shu)脂(zhi)分為離(li)子交換(huan)樹(shu)脂(zhi)和大孔樹(shu)脂(zhi)2 種,其(qi)中離(li)子交換(huan)樹(shu)脂(zhi)在深度(du)(du)處(chu)理中通常用于除(chu)硬,而大孔樹(shu)脂(zhi)主要是(shi)進行(xing)COD 的去除(chu)。
吸(xi)附技術是將煤(mei)化(hua)(hua)(hua)(hua)(hua)(hua)工廢(fei)(fei)(fei)(fei)水(shui)(shui)中的(de)(de)(de)污染物(wu)(wu)轉移,而非破壞。高(gao)(gao)級氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術作為一種將有(you)機(ji)(ji)物(wu)(wu)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)成CO2、H2O 和(he)無機(ji)(ji)鹽(yan)的(de)(de)(de)技術,在(zai)煤(mei)氣化(hua)(hua)(hua)(hua)(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui)(shui)處理(li)(li)中得到廣(guang)泛的(de)(de)(de)研究,目前,在(zai)煤(mei)氣化(hua)(hua)(hua)(hua)(hua)(hua)深度處理(li)(li)領域中,應用(yong)最多的(de)(de)(de)高(gao)(gao)級氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術是臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術,該技術在(zai)新疆、寧夏(xia)、鄂爾多斯(si)等煤(mei)氣化(hua)(hua)(hua)(hua)(hua)(hua)項目中都有(you)所使用(yong)。為了(le)提高(gao)(gao)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)的(de)(de)(de)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)能力(li)和(he)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)效率,在(zai)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術的(de)(de)(de)基礎上開發(fa)出了(le)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術。Zhuang 等[22]利用(yong)剩余(yu)污泥制備活性炭(SBAC)并負載金屬(shu)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)物(wu)(wu),研制成催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji),并考察了(le)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)技術對(dui)(dui)Lurgi 碎煤(mei)加壓(ya)氣化(hua)(hua)(hua)(hua)(hua)(hua)廢(fei)(fei)(fei)(fei)水(shui)(shui)的(de)(de)(de)二沉池出水(shui)(shui)的(de)(de)(de)處理(li)(li)效果,實(shi)(shi)驗結果表(biao)明(ming),該催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji)可以顯著提高(gao)(gao)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)對(dui)(dui)有(you)機(ji)(ji)污染物(wu)(wu)的(de)(de)(de)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)去(qu)除效果。杜松等[23]采用(yong)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)鋁粉(fen)末為原(yuan)料制備了(le)MgO-Al2O3 催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji),并利用(yong)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)處理(li)(li)煤(mei)化(hua)(hua)(hua)(hua)(hua)(hua)工高(gao)(gao)含鹽(yan)廢(fei)(fei)(fei)(fei)水(shui)(shui),實(shi)(shi)驗表(biao)明(ming),臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)單獨氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)和(he)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)對(dui)(dui)COD 的(de)(de)(de)去(qu)除率分(fen)別達到45%和(he)61%,后者對(dui)(dui)COD 的(de)(de)(de)去(qu)除效果更(geng)(geng)好。何軼杰[24]制備了(le)摻(chan)雜型MnO2RGO(還原(yuan)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)石墨烯(xi))/Al2O3 催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)劑(ji),建立微氣泡體系(xi)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)工藝(yi),并用(yong)于煤(mei)化(hua)(hua)(hua)(hua)(hua)(hua)工廢(fei)(fei)(fei)(fei)水(shui)(shui)的(de)(de)(de)深度處理(li)(li)中,實(shi)(shi)驗表(biao)明(ming),處理(li)(li)后COD 的(de)(de)(de)去(qu)除率在(zai)51%以上,TOC 去(qu)除率達到62%。章麗萍等[25]以甲醇制烯(xi)烴(MTO)裝置(zhi)廢(fei)(fei)(fei)(fei)水(shui)(shui)中的(de)(de)(de)苯(ben)(ben)乙烯(xi)為研究對(dui)(dui)象,采用(yong)單獨臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)、臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)、單獨紫外、紫外+過硫(liu)酸(suan)鈉4 種技術進行處理(li)(li),研究表(biao)明(ming),相較于其他3 種技術,臭(chou)(chou)(chou)氧(yang)(yang)(yang)(yang)(yang)(yang)催(cui)化(hua)(hua)(hua)(hua)(hua)(hua)氧(yang)(yang)(yang)(yang)(yang)(yang)化(hua)(hua)(hua)(hua)(hua)(hua)對(dui)(dui)煤(mei)化(hua)(hua)(hua)(hua)(hua)(hua)工廢(fei)(fei)(fei)(fei)水(shui)(shui)中苯(ben)(ben)乙烯(xi)的(de)(de)(de)去(qu)除更(geng)(geng)具優勢。
在廢水(shui)(shui)深度(du)處理領(ling)域(yu)中(zhong),工(gong)(gong)(gong)業(ye)上最常用(yong)(yong)的(de)(de)生(sheng)(sheng)物(wu)技術是曝氣生(sheng)(sheng)物(wu)濾池(BAF),此外,MBBR 也有較多研究。Zhuang 等[26]利(li)用(yong)(yong)缺氧移動床(chuang)生(sheng)(sheng)物(wu)反應器(qi)(ANMBBR)和(he)BAF 構建了短程生(sheng)(sheng)物(wu)脫(tuo)氮工(gong)(gong)(gong)藝用(yong)(yong)于(yu)煤氣化(hua)廢水(shui)(shui)的(de)(de)深度(du)處理,實驗發現,ANMBBR 可以(yi)(yi)提高廢水(shui)(shui)可生(sheng)(sheng)化(hua)性并減輕毒性,使得(de)ANMBBR-BAF 工(gong)(gong)(gong)藝在毒性較高的(de)(de)情況下仍能保(bao)證(zheng)較高的(de)(de)氨氮和(he)總氮的(de)(de)去處效果(guo)。張國(guo)梁[27]采用(yong)(yong)A/O-MBR 工(gong)(gong)(gong)藝對(dui)某煤化(hua)工(gong)(gong)(gong)企業(ye)的(de)(de)廢水(shui)(shui)處理設(she)施(shi)進行(xing)(xing)了改造,工(gong)(gong)(gong)程運(yun)行(xing)(xing)結(jie)果(guo)表明,改造后的(de)(de)工(gong)(gong)(gong)藝對(dui)COD、NH3-N、SS 和(he)濁度(du)的(de)(de)平均去除率達到(dao)了80%、95%、90%和(he)95%以(yi)(yi)上,滿足企業(ye)對(dui)中(zhong)水(shui)(shui)回(hui)用(yong)(yong)的(de)(de)進水(shui)(shui)要求(qiu)。公彥欣中(zhong)試采用(yong)(yong)A/O-MBR-RO 組合(he)工(gong)(gong)(gong)藝處理煤制(zhi)烯烴廢水(shui)(shui),出水(shui)(shui)水(shui)(shui)質完全滿足《工(gong)(gong)(gong)業(ye)循環冷卻水(shui)(shui)處理設(she)計(ji)規(gui)范》(GB 50050—2007)中(zhong)的(de)(de)再生(sheng)(sheng)水(shui)(shui)水(shui)(shui)質指標的(de)(de)要求(qiu)[28]。
2.4 中水回用以及零排放
我國與生態環保相關(guan)的(de)(de)(de)法(fa)規(gui)不(bu)斷(duan)完善,相關(guan)標(biao)準也不(bu)斷(duan)提(ti)(ti)高(gao),目前,除了(le)(le)對(dui)煤(mei)化工(gong)廢(fei)水(shui)(shui)(shui)的(de)(de)(de)污染物排放(fang)濃度(du)提(ti)(ti)出(chu)要(yao)求(qiu),也對(dui)其排放(fang)水(shui)(shui)(shui)量或者回用水(shui)(shui)(shui)量提(ti)(ti)出(chu)了(le)(le)要(yao)求(qiu),對(dui)新建的(de)(de)(de)煤(mei)化工(gong)項目,更是要(yao)求(qiu)廢(fei)水(shui)(shui)(shui)實現近零(ling)排放(fang)(即實現最大(da)程(cheng)度(du)的(de)(de)(de)水(shui)(shui)(shui)回用)。由于煤(mei)化工(gong)廢(fei)水(shui)(shui)(shui)中的(de)(de)(de)鹽(yan)度(du)較高(gao),為了(le)(le)避免管路和(he)設備的(de)(de)(de)結垢(gou)、腐蝕等問題(ti),經過(guo)預處理(li)、生化處理(li)和(he)深度(du)處理(li)后的(de)(de)(de)煤(mei)化工(gong)廢(fei)水(shui)(shui)(shui)通常要(yao)進(jin)行脫(tuo)鹽(yan)處理(li)才能(neng)進(jin)一步(bu)回用。脫(tuo)鹽(yan)處理(li)分為含鹽(yan)水(shui)(shui)(shui)處理(li)、濃鹽(yan)水(shui)(shui)(shui)處理(li)和(he)蒸(zheng)發結晶。
含(han)鹽(yan)廢(fei)水(shui)處(chu)(chu)(chu)理(li)工(gong)(gong)(gong)藝(yi)(yi)工(gong)(gong)(gong)業(ye)(ye)上基本(ben)采(cai)用雙膜工(gong)(gong)(gong)藝(yi)(yi)(超濾+反(fan)滲透),經處(chu)(chu)(chu)理(li)后(hou)的(de)產水(shui)回用,濃水(shui)的(de)TDS 達到(dao)15 000~60 000 mg/L。為了減(jian)少(shao)蒸發(fa)(fa)結(jie)晶(jing)單元(yuan)(yuan)的(de)處(chu)(chu)(chu)理(li)量,雙膜工(gong)(gong)(gong)藝(yi)(yi)出水(shui)進入(ru)濃鹽(yan)水(shui)處(chu)(chu)(chu)理(li)單元(yuan)(yuan)進一步濃縮,濃鹽(yan)水(shui)處(chu)(chu)(chu)理(li)工(gong)(gong)(gong)藝(yi)(yi)選擇(ze)較為多樣,包(bao)括高效反(fan)滲透工(gong)(gong)(gong)藝(yi)(yi)(HERO)、振動膜反(fan)滲透工(gong)(gong)(gong)藝(yi)(yi)(VSEPRO)、超級膜濃縮工(gong)(gong)(gong)藝(yi)(yi)(SCRM)、機械蒸汽(qi)再(zai)壓縮工(gong)(gong)(gong)藝(yi)(yi)(MVR)、電(dian)滲析工(gong)(gong)(gong)藝(yi)(yi)、碟管式反(fan)滲透工(gong)(gong)(gong)藝(yi)(yi)(DTRO)、正滲透工(gong)(gong)(gong)藝(yi)(yi)等[3,29-30]。濃鹽(yan)水(shui)處(chu)(chu)(chu)理(li)單元(yuan)(yuan)的(de)出水(shui)進入(ru)蒸發(fa)(fa)結(jie)晶(jing)單元(yuan)(yuan)進行固化處(chu)(chu)(chu)理(li),目(mu)前(qian)工(gong)(gong)(gong)業(ye)(ye)界(jie)常用的(de)蒸發(fa)(fa)結(jie)晶(jing)技(ji)術(shu)主要有(you)MVR 技(ji)術(shu)和多效蒸發(fa)(fa)(MEE)技(ji)術(shu)。
3 結論和展望
(1)煤(mei)(mei)氣(qi)(qi)(qi)(qi)化(hua)廢水(shui)(shui)(shui)因(yin)生產工(gong)(gong)藝(yi)、操(cao)(cao)作條件和煤(mei)(mei)種的(de)不同,污染物(wu)構成差異很大,但是,相比于對(dui)煤(mei)(mei)種要求不高的(de)Lurgi 碎煤(mei)(mei)加(jia)壓氣(qi)(qi)(qi)(qi)化(hua)工(gong)(gong)藝(yi),Shell 干粉煤(mei)(mei)氣(qi)(qi)(qi)(qi)化(hua)工(gong)(gong)藝(yi)和Texaco 水(shui)(shui)(shui)煤(mei)(mei)漿氣(qi)(qi)(qi)(qi)化(hua)工(gong)(gong)藝(yi)對(dui)煤(mei)(mei)種還(huan)是具(ju)有一定范圍性要求,同時,煤(mei)(mei)化(hua)工(gong)(gong)廢水(shui)(shui)(shui)處(chu)理各個(ge)單元(yuan)的(de)技術類型眾(zhong)多。因(yin)此,煤(mei)(mei)化(hua)工(gong)(gong)廢水(shui)(shui)(shui)的(de)處(chu)理,既需(xu)要研究者根(gen)據(ju)煤(mei)(mei)氣(qi)(qi)(qi)(qi)化(hua)工(gong)(gong)藝(yi)和操(cao)(cao)作條件對(dui)水(shui)(shui)(shui)質特(te)征進行(xing)系統總結,也需(xu)要根(gen)據(ju)規模(mo)、水(shui)(shui)(shui)質特(te)點進行(xing)具(ju)體判(pan)斷,進而選擇合(he)適(shi)的(de)處(chu)理技術。
(2)隨(sui)著環保標準的不斷提高,煤化(hua)工(gong)廢水處(chu)(chu)理(li)(li)流(liu)程從“預處(chu)(chu)理(li)(li)-生化(hua)處(chu)(chu)理(li)(li)”增加至“預處(chu)(chu)理(li)(li)-生化(hua)處(chu)(chu)理(li)(li)-深度處(chu)(chu)理(li)(li)-含鹽(yan)水處(chu)(chu)理(li)(li)-濃鹽(yan)水處(chu)(chu)理(li)(li)-蒸(zheng)發結晶”。對于煤化(hua)工(gong)廢水的處(chu)(chu)理(li)(li)方案,研究者既要考慮(lv)各(ge)個單元的穩定性和(he)高效性,又要統籌考慮(lv)各(ge)個單元銜接的合理(li)(li)性和(he)彼此(ci)的適應性。
(3)煤(mei)(mei)化(hua)(hua)(hua)工廢(fei)水(shui)(shui)處理系(xi)統(tong)存在(zai)投資(zi)大、流(liu)程(cheng)長、運行成本高(gao)、零排放產生(sheng)的(de)(de)(de)雜鹽處理費用(yong)高(gao)等問(wen)題。因此(ci),多種技(ji)術(shu)(shu)的(de)(de)(de)一體化(hua)(hua)(hua)研(yan)(yan)究,高(gao)效、低(di)成本技(ji)術(shu)(shu)研(yan)(yan)究,煤(mei)(mei)化(hua)(hua)(hua)工廢(fei)水(shui)(shui)系(xi)統(tong)的(de)(de)(de)整(zheng)體優(you)(you)化(hua)(hua)(hua),煤(mei)(mei)化(hua)(hua)(hua)工廢(fei)水(shui)(shui)系(xi)統(tong)過(guo)程(cheng)控制(zhi)的(de)(de)(de)優(you)(you)化(hua)(hua)(hua),濃鹽水(shui)(shui)的(de)(de)(de)分質資(zi)源(yuan)化(hua)(hua)(hua)技(ji)術(shu)(shu)研(yan)(yan)究以(yi)及現有(you)分鹽技(ji)術(shu)(shu)的(de)(de)(de)適(shi)應(ying)性研(yan)(yan)究,都是煤(mei)(mei)化(hua)(hua)(hua)工廢(fei)水(shui)(shui)處理的(de)(de)(de)發展(zhan)方向。

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