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Nu trong nhn benzen c mt vi nhm th th s ng phng ca nhm nitro s b n ng khng gian. Bng cc kt qu nghin cu cu trc ngi ta chng minh c khuynh hng ng phng vi vng thm ca nhm nitro v nh hng ca nhm th, v tr th n khuynh hng ny [23]. Chng hn, pdinitrobenzen c tnh ng phng, m-dinitrobenzen nhm nitro khng nm trong mt phng cha vng benzen, o-dinitrobenzen tnh ng phng b lch mnh nht c th gc quay ca nhm nitro tng i so vi vng benzen ti 900 [23]. Tnh ng phng c th chng minh c bng ph hp th phn t. Nu lch ng phng cng nhiu, tc l lin hp cng yu th tn s dao ng bt i xng cng ln. Dao ng ny c trng cho bn ca lin kt N O trong nhm nitro. i vi hp cht nitroparafin do khng c s lin hp nn tn s ny cao hn trong hp cht nitro thm. Tnh cht ng phng b ph v c nh hng rt ln n kh nng phn ng ca cc hp cht nitro thm.
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
1.1.1.2. Tnh cht vt l Hp cht nitro vng thm c bn nhit cao. Trong cc hp cht nitro, nhm nitro lin kt trc tip vi nguyn t cacbon, lin kt kh bn v quyt nh bn nhit cao ca chng, ngay c i vi cc hp cht polynitro. a s nhng hp cht nitro khng c kh nng t phn hy v t bng chy. Chng bn vi nhit (v d 2,4,6-trinitrotoluen un nng thm ch 1500C cng khng b phn hy). Cc polynitro thm u l cc cht rn t nhy vi cc tc dng c hc, tnh cht n tng khi s nhm nitro trong phn t tng. 1.1.1.3. Tnh cht ha hc Tnh cht ha hc ca cc hp cht nitro do s c mt ca cc nhm nitro quyt nh. Ngi ta chia ra thnh: phn ng nhm nitro v phn ng vng thm. - Phn ng nhm nitro Cu to ca nhm -NO2:
(+)
O O
(-)
hoc
(+)
O O
(1/2-) (1/2-)
Gc lin kt ONO dao ng t 125-134 o, di lin kt N-O t 1,17-1,30 A o, ph thuc vo cu to ca gc hidrocacbon [7,9]. + Phn ng kh: Khi cho tc dng hidro mi sinh vi hp cht nitro, nhm nitro b kh thnh nhm amino: ArNO2 + 6H ArNH2 + 2H2O Qu trnh kh hp cht nitro tri qua mt s giai on trung gian. Trong mi trng axit, phn ng xy ra mnh lit, lc u to ra hp cht nitrozo, sau n dn xut hidroxylamin v nu kh tip s n amin: ArNO2 ArNO ArNH(OH) ArNH2 Trong mi trng kim, phn ng xy ra yu hn v sn phm cui cng l dn xut hidroxylamin b ngng t thnh hp cht azoxy. ArNO + ArNH(OH) Ar N = N Ar + H2O
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
O Trong mt s trng hp khi kh trong mi trng kim, phn ng tin hnh theo cch ring. V d, nu kh hp cht nitro c nhm metyl v tr para vi nhm nitro th mt hoc hai nguyn t hydro ca nhm metyl b tch ra v to thnh dn xut dibenzyl hoc stilben.
O2N CH - CH2 2 CH= CH NO 2 NO 2
H3C
NO2
O2N
Phn ng ny c gi tr trong cng nghip sn xut thuc nhum. + Tc dng vi axit sunfuric Phn ng c trng th hai ca hp cht nitro l tc dng vi axit sunfuric nh mt baz. Cc hp cht nitro thm to vi axit sunfuric, c bit l oleum, nhng sn phm ion dng mui c mu, v d:
[C H - N
6 5
OH] HSO 4 O
Trong axit sunfuric 100%, nitrobenzen b ion ha ti 40%. Mu vng c c l do cu trc ion ca vng quinoid:
+ + N O OH
+ Phn ng th nhm nitro linh ng ca nhm nitro trong cc hp cht nitro thm ph thuc vo v tr ca n so vi cc nhm th khc, trong trng hp nm v tr meta so vi nhm th nhn in t khc hoc nm trong v tr octo, para so vi nhm th cho in t. S c mt ca nhiu nhm th trong vng thm lm cho nhm nitro linh ng hn, cc nhm thay th nhm nitro thng l nhm cho in t nh - NH 2, NH2-NH2, Cl,...
Cl O2N Cl NO2
Cl O2N Cl NH2
- HNO2 5
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
+ Phn ng ng vng Nhm nitro c th tham gia vo s hnh thnh d vng cha nit vi cc nhm chc cha hidro linh ng ni phn t hoc ngoi phn t mt s cht nh: anilin, 2 nitro, 2axetic diphenyl,...
NaOH, HCl - (CO2 + H2O) NO2 CH2COOH N=C
- Phn ng vng thm Ngoi nhng phn ng chung ca nhm nitro th cc hp cht nitro thm cn tham gia cc phn ng nhn thm nh benzen, tuy nhin s c mt ca nhm nitro lin kt vi vng thm gy nh hng ng k n cc nguyn t hidro hoc cc nhm th trong vng, nh hng ny do hiu ng ht in t -I v -C ca nhm nitro quyt nh. Do cc hiu ng ny, nn cc v tr octo v para ca nhm NO 2 b dng hn v tr meta. V vy phn ng th i nhn s u tin vo v tr octo v para (kh nng th yu hn khi khng c nhm th nitro), cn phn ng th i in t u tin vo v tr meta (s c mt ca nhm nitro lm tng kh nng phn ng th v tr ny). - Phn ng nhm metyl ca hp cht nitro thm Cc nhm nitro lm tng ng k kh nng phn ng vi cc tc nhn i nhn nhm metyl trong dn xut nitro ca toluen, do tng kh nng chuyn dch m my in t khi nhm metyl bi tc ng ca hiu ng cm ng v hiu ng siu lin hp ca nhm metyl i vi vng thm. V th, nhm metyl trong nitrotoluen phn ng vi benzandehit d hn trong toluen to ra dn xut stylben. Mono-, di-, trinitrotoluen phn ng vi p-nitrozodimetylannilin, nhng vi toluen th khng xy ra. Nhm metyl ca 2,4-dinitrotoluen khi c mt ca iot phn
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
ng vi N-oxit ca pyridin cho 2,4-dinitrobenzen cn vi pyridin cho 2,4-dinitro benzylpyridiniodua. nh sng mt tri v tia t ngoi lm tng kh nng phn ng ca cc hp cht nitro v gy ra phn ng oxy ha ni phn t nhm metyl thnh ru nh oxy ca nhm nitro v tr octo.
- nh hng ca nhm nitro n tnh cht ca cc nhm th khc Nhm nitro lm tng kh nng phn ng ca cc nhm th khc trong vng thm. Nhm nitro lm tng ng k tnh axit ca phenol do hiu ng cm ng -I:
Hiu ng ny th hin r hng s phn ly (K) ca phenol v cc dn xut nitro ca n: Phenol 1,2.10-10 o-nitro phenol 6,8.10-8 m-nitro phenol 5,0.10-9 p-nitro phenol 7,0.10-8 2,4-dinitro phenol 5,6.10-4 2,6-dinitro phenol 1,0.10-4 1.1.1.4. c tnh ca cc hp cht nitro thm [7,9,10] Tt c cc hp cht nitro thm u c c tnh cao. Chng gy hi cho h thn kinh v ch yu vo mu ph v qu trnh cung cp oxy cho c th. Mt s hp cht nitro gy bnh vim da nh dinitro clo benzen. Mc gy c cho con ngi ca tng hp cht nitro khc nhau. Ni chung, c tnh gim khi tng s nhm nitro, nu cng s nhm nitro th khi trong phn t c mt nhm metyl (-CH 3) hoc sunfonic (-SO3H) mc c hi gim [22,23,26].
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Du hiu c trng khi ng c hp cht nitro thm l chng mt, au u. S nhim c thng qua da hoc qua ng h hp do s bay hi ca cc hp cht nitro. Phng tin s cu khi ng c l quinon v oxy. 1.1.1.5. iu ch v ng dng Cc hp cht nitro thm c iu ch bng cch nitro ha vi hn hp axit sunfuric - nitric v t khi sn phm k thut l cht tinh khit. Thng thng sn phm bao gm mt s ng phn vi lng nhiu hay t ph thuc vo iu kin nitro ha v qu trnh x l tip theo. Mt s ng phn c trong sn phm l nhng tp cht c hi (v d hp cht trinitro bt i xng). Mun sn phm n nh tnh cht cn tch cng tinh khit cng tt. Cc hp cht mononitro thm khng c tnh cht n do cn bng oxy m, song s c mt ca nhm nitro lm tng ng k tc phn hy nhit ca cc hp cht nitro thm. Hp cht nitro dy thm rt c ngha thc t, c dng ch yu lm cht n v c sn xut quy m cng nghip kh rng ln. Cc hp cht mononitro thm dng lm nguyn liu iu ch amin trong cng nghip phm mu. Trong cng nghip cht n chng c s dng nhiu dng sn phm trung gian sn xut cc cht n ph hoi. Mt s hp cht moninitro c dng c lp lm cht ph gia thun ha cho tng hp cht trinitro. Chng hn, mononitronaphtalen dng trong hp chy vi trinitrophenol. Cc hp cht dinitro thm c tnh n. Mt s hp cht ny c s dng lm cht n nhng khng dng c lp m thng phi hp vi nhng cht n khc do sc n yu v tip nhn n km. Cc hp cht trinitro thm c dng trc tip lm cht n. Trong cc hp cht tetra, penta, hexanitro cc nhm nitro lin kt km bn hn nhit cao, nhy hn vi tc dng c hc, chnh v l khng ng dng thc tin c. 1.1.2. Mt s hp cht nitro vng thm nghin cu
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Cng thc phn t: C7H6N2O4 DNT l cht hu c rt d b phn hy di tc dng ca nh sng mt tri v cc vi sinh vt. DNT trong mi trng khng kh v trong mi trng nc b phn hy di tc dng ca nh sng mt tri. Trong iu kin khng c oxy hoc nh sng mt tri, DNT b phn hy di tc dng ca cc vi sinh vt, chng s dng DNT nh l ngun nng lng v gii phng ra CO2 v nc [50]. Tnh cht vt l 2,4-dinitrotoluen l cht rn mu vng, mi thm nh. Khi lng phn t M=182.13 g.mol1. Mt s tnh cht l hc ca cc ng phn DNT nh sau: Bng 1.1. Mt s tnh cht l hc ca cc ng phn DNT ng phn 2,42,63,42,33,6 (2,5)3,50 Nhit ha rn, C 69,55 65,1 58,5 59,23 50,25 92 0 0 Nhit si, C Si p sut thng km theo s phn hy di 300 C Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. DNT k thut bao gm ch yu l cc ng phn 2,4- v 2,6- l cht tinh th mu vng, ha rn 50- 540C, cha mt lng tp cht dng du (hp chy ca cc ng phn DNT). T trng 710C l 1,32. DNT tan tt trong dung mi hu c hn 2,4,6-trinitrotoluen (TNT), nhng tan trong nc khng ng k. tan DNT trong axit H2SO4 tng khi nng axit tng: Bng 1.2. tan ca DNT k thut trong axit H2SO4 c nng khc nhau (g/100g axit) Nng H2SO4, % 20 40 50 Nhit 60 70 80 100
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
80,0 1,2 2,5 3,8 83,6 3,6 4,7 5,8 6,3 88,7 6,1 10,0 12,8 18,3 90,0 8,5 16,8 20,0 93,0 26,4 33,8 53,4 58,8 99,8 72,6 144 337 1121 Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. dng vi axit. CH3C6H3(NO2)2 + H2SO4 Tnh cht ha hc + Phn ng nhm metyl
tan ca DNT tng ln mnh nng axit H 2SO4 gn 100% do DNT tc [CH3C6H3(NO2)(NOOH)]+ + HSO4-
Trong DNT nhm nitro nh hng ng k n tnh cht ha hc ca nhm metyl. Nhm ny c kh nng th cc nguyn t hydro bng mt nhm th khc, chng hn, khi tc dng vi p-nitrozodimetylanilin.
+ Phn ng vi kim: Di tc dng ca kim, DNT to ra cc dn xut stylben, c bit khi c tc nhn oxy ha (oxy khng kh, NaOCl):
Khi tc dng dung dch KOH 10%, 2,4-DNT trong mi trng axeton to ra mu xanh da tri, ng phn 2,6 khng cho mu ny. + Phn ng vi Natrisunfit
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
+ Phn ng to phc cht DNT c kh nng to thnh phc phn t vi cc hidrocacbon thm v amin. Hp cht 3,5-DNT c kh nng to phc phn t cao nht cn cc dinitro khc th gim dn theo dy ng phn 2,4; 2,6; 3,4. iu ch Dinitrotoluen c iu ch bng cch nitro ha nitrotoluen (MNT) vi hn hp H2SO4 - HNO3 theo phng trnh: CH3C6H4(NO2) + HNO3 CH3C6H3(NO2)2 + H2O Nu nitro ha MNT k thut cha c ba ng phn s c DNT k thut gm 6 ng phn c thnh phn phn trm nh sau: Bng 1.3. Thnh phn phn trm ca cc ng phn DNT 2,4-DNT 75,6% 2,3-DNT 1,44% 2,6-DNT 19,7% 3,6-DNT 0,61% 3,4-DNT 2,57% 3,5-DNT 0,08% Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. Khi nitro ha tng ng phn MNT, t l phn trm ca ng phn DNT thu c nh sau:
11
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
ng dng DNT l mt cht n nhng yu. trng thi tinh th v kch n bng kp s 8, DNT n cho dn n bom ch l 210ml, nhng kh nng tip nhn n km nn khng s dng c lp. C th dng mt lng nh DNT lm cht do ha khi ch to thuc phng nitroglyxerin. Gn y DNT (ch yu ng phn 2,6-) c dng nhiu sn xut tolulendizoxynat cho cng nghip cht do xp. DNT c s dng sn xut polyurethane do (loi nha tng hp dng ch to sn) c s dng trong cc ngnh cng nghip ging m v ni tht. DNT cng c s dng sn xut n dc v cht n v lm thuc nhum. N cng c s dng trong cc ti kh ca xe t. c tnh ca 2,4-dinitrotoluen [45,47] DNT c th xm nhp vo c th qua h h hp hoc tip xc qua da. Khi DNT vo trong c th, n c phn b trong mu v trong nc tiu [45]. - Cc biu hin nhim c cp tnh DNT: + Cc nghin cu trn ng vt cho thy khi nhim c cp tnh DNT s c nh hng n mu, gan, thn v h thn kinh trung ng [45]. - Cc biu hin nhim c mn tnh DNT: + DNT nh hng n h thn kinh trung ng dn n ming c v kim loi kh chu, suy nhc c th, au u, chn n, hoa mt, chng mt, bun nn, mt ng, au nga t chi ca ngi tip xc. + Tc dng vo mu, gy xanh xao thiu mu i vi cc cng nhn tip xc vi DNT nng ln [45].
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
+ Biu hin nhim c mn tnh trn ch v chut bch th nghim khi n phi DNT l suy nhc c th, co git, mt kh nng iu ha c th v mt cm gic [45,47]. - nh hng n kh nng sinh sn: + Nhng ngi cng nhn nhim c mn tnh vi DNT c th b gim ng k kh nng sinh tinh trng v hnh thi ca tinh trng nam gii v tng t l sy thai n gii [45]. + Trn ng vt n phi DNT dn n gim kh nng sinh sn, c th l gim kh nng sinh tinh trng, teo tinh hon v thoi ha ng sinh tinh chut c v teo bung trng v s hot ng khng bnh thng ca c quan sinh sn chut ci th nghim [45,47]. 1.1.2.2. 2,4-dinitrophenol (DNP) 2,4-dinitrophenol cn c tn gi khc l - dinitrophenol hay 1-hydroxy2,4-dinitrobenzen, c cng thc cu to:
Cng thc phn t: C6H4N2O5 Tnh cht vt l Dinitrophenol l tinh th rn mu vng nht nhng n thng c tm thy dng dung dch. Khi lng phn t M=184,11 g.mol 1. Nhit ha rn 120C, t trng so vi nc l 1,68, t trng so vi khng kh l 6,36. tan ca 2,4dinitrophenol trong nc l 0,14g/100ml 540C. Tnh cht ha hc V trong phn t 2,4-dinitrophenol c cha nhm -OH lin kt trc tip vi
Csp 2
kt hydro.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Do s lin hp gia electron n ca oxy v electron ca vng thm, lin kt O - H ca 2,4-dinitrophenol d phn ly, song lin kt C - O li km phn cc, bn vng hn v kh tham gia phn ng. Ngoi ra cng do hiu ng lin hp ca -OH m vng benzen tr nn giu mt electron hn v c kh nng phn ng cao hn benzen. Trong phn t DNP c s lin hp p - ca cp electron p ca nguyn t oxi vi cc electron ca vng benzen lm cho lin kt O-H phn cc hn so vi lin kt O-H ca ancol. Do , DNP c tnh axit mnh hn ancol; tuy nhin vn yu hn nhiu axit cacboxilic v ngay c axit cacbonic CO 2.H2O. Tuy nhin DNP cng th hin tnh axit yu. N c kh nng tc dng vi kim loi kim gii phng hiro, ngoi ra cn tc dng vi dung dch kim to mui phenolat tan. DNP va mang tnh cht ha hc ca cc hp cht phenol li va mang tnh cht ha hc ca cc hp cht nitro vng thm. iu ch iu ch 2,4-dinitrophenol t dinitrochlorobenzen [48].
ng dng 2,4-dinitrophenol c s dng trong sn xut thuc nhum, cht bo qun g, v nh mt loi thuc tr su. Trong khong thi gian u nhng nm 30 ca th k XX, 2,4-dinitrophenol c s dng nh l mt loi thuc gim cn, nhng n nm 1938 n b cm s dng [44].
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
c tnh ca dinitrophenol [44,46] - Biu hin nhim c cp tnh: Nguyn nhn: 2,4-dinitrophenol hp th vo c th qua con ng tiu ha. Khi vo c th c th c phn b trong mu, nc tiu, v cc m ca ngi. Biu hin ca nhim c cp tnh 2,4-dinitrophenol ngi l bun nn, nn ma, m hi, chng mt, nhc u, v gim cn. Nu con ngi hp th 2,4dinitrophenol liu lng ln ngoi cc biu hin cp tnh trn s c thm triu chng tng t l chuyn ha c bn v cc triu chng khc. - Biu hin nhim c mn tnh: Cc biu hin nhim c mn tnh 2,4-dinitrophenol qua con ng tiu ha ngi l thng tn da, gim cn, gy ra cc nh hng ln ty xng, h thn kinh trung ng v h thng tim mch. Cc nghin cu ph n ung 2,4-dinitrophenol nh l mt loi thuc gim cn cho thy n c th nh hng n kh nng sinh sn, nhng cc thng tin ny cha c tnh thuyt phc cao. Mt nghin cu trn ng vt cho thy 2,4-dinitrophenol lm tng t l cht non v tng t l t vong khi con ca ng vt. - Nguy c gy ung th: Khng c thng tin v kh nng gy ung th ca 2,4-dinitrophenol trn ngi. Mt nghin cu cho thy 2,4-dinitrophenol khng thc y s pht trin khi u chut. 1.2.3. Styphnic axit (TNR) Styphnic axit cn c cc tn gi khc l: 2,4,6-trinitrorezoxin; 2,4,6trinitro-1,3-benzenediol. Styphnic axit c cng thc cu to:
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
OH O2N NO2
Cng thc phn t: C6H(NO2)3(OH)2 , M = 245,1 g.mol1 Tnh cht vt l Styphnic axit c nhit nng chy: t0nc = 175,50C Tinh th mu vng, nhum lng th kh tt. Trong 100ml nc ho tan 0,641g (140C) v 1,136g (620C). Theo Aubertein v Emeury ho tan ca axit styphnic nh sau: Bng 1.4. tan ca Styphnic axit trong nc ho tan trong 100ml H2O, g t = 15 C t0= 200C t0= 250C Styphnic axit 0,45 0,55 - 0,58 0,68 - 0,69 Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. Cht ho tan
0 0
NO2 OH
ha tan trong axit nitric vi nng khc nhau 250C Bng 1.5. tan ca Styphnic axit trong axit nitric HNO3 % trng lng 0 10,67 41,49 ho tan/100g axit, g 0,53 0,034 0,125 Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. 55,90 0,32 69,57 1,37
ha tan trong axit sunfuric vi nng khc nhau 250C. Bng 1.6. tan ca Styphnic axit trong axit sunfuric H2SO4 % trng lng 0 6 20 50 ho tan/100g axit, g 0,65 0,07 0,01 0,10 Ngun: Ho hc v bn ca vt liu n, NXB QND, 2002. ho tan ca styphnic axit trong HNO3 v H2SO4 l rt thp. 82 0,13 92 0,13
ho tan ca styphnic axit trong hn hp axit (gm HNO 3 (10%), H2SO4 (72%) v H2O (18%)) nhit phng thp di 0,005 %, cn nhit 35 - 40 0C thp di 0,01%, nhit 800C thp di 0,1%.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Styphnic axit l cht ht m mnh, khi tip xc vi kh quyn c m 60% nhit 20 - 250C, trong vng 30 - 100 gi n ht mt lng nc bng 2 - 3% trng lng bn thn. Styphnic axit d tan trong glycol diaxetat, c 100g dung mi 25 0C ho tan khong 13g styphnic axit. Tnh cht ha hc Phn t styphnic axit c cha hai nhm -OH (polyphenol) cng c phn ng tng t nh cc hp cht thm c cha 1 nhm -OH (monophenol). Song ty iu kin phn ng c th ch c mt hay hai nhm hydroxyl tham gia. Mt khc trong phn t styphnic axit cn cha 3 nhm -NO 2 ( v tr ortho v para). Nhm -NO2 v tr para c hiu ng - C v - I s lm tng tnh axit (ni chung nhm th v tr para th hin y hiu ng lin hp ca n). Cn nhm th v tr ortho thng gy ra mt hiu ng c bit lm tng tnh axit gi l hiu ng ortho. V vy styphnic axit l mt axit tng i mnh c th ho tan c st v km [20]. Trong phn t styphnic axit c 2 nhm -OH l nhm th hot ng ho lm tng kh nng phn ng ca vng benzen, cn 3 nhm -NO 2 li l nhm th phn hot ho c ngha l vng benzen trong phn t styphnic axit s kh b oxy ho hn. Styphnic axit ging nh cc thnh phn khc cng loi c th to thnh cc hp cht cng vi cc hydrocacbon thm [40]. iu ch iu ch styphnic axit t Resorcinol [42].
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
2,4-dinitrosoresorcinol (II)
Styphnic axit l hp cht hu c dng ch to thuc gi n, s dng trong cng nghip sn xut v kh, n. c tnh ca TNR Hin nay cha c ti liu no cp c th n nh hng ca styphnic axit i vi mi trng. Tuy nhin, styphnic axit vn nm trong danh mc 429 cht nguy hi cn phi x l. 1.2. NGUN NHIM CC HP CHT NITRO VNG THM TRONG NC V HIN TRNG CNG NGH X L NC THI NHIM CC HP CHT NITRO VNG THM 1.2.1. Ngun nhim cc hp cht nitro vng thm trong nc Hng nm, cc c s sn xut thuc phng, thuc n quc phng pht sinh mt lng nc thi vi tr lng kh ln. Loi nc thi ny thng cha cc thnh phn c tnh c hi cao vi mi trng v d gy chy n nh cc hp cht nitro thm, cc loi thuc nh 2,4,6-trinitrotoluen (TNT); 2,4-dinitrotoluen (DNT); nitroglyxerin (NG), dinitrophenol (DNP), hexogen, octogen; cc cht gi n nh styphnat ch, azotua ch, phuminat thu ngn, styphnic axit (TNR), cc ph gia n nh v cc loi ho cht, dung mi c hi khc s dng trong cng ngh x l b mt, bo qun v kh, trang thit b k thut [29]. Trong cc c s sn xut thuc phng, thuc n c cc dy chuyn cng ngh sn xut s dng ho cht nh: - Sn xut, gia cng thuc phng - Cng ngh sn xut thuc gi n - Cng ngh thu hi thuc n t n cp 5 - Cng ngh sn xut thuc n cng nghip AD1, nh tng v.v... Ngun nc thi ca cc dy chuyn cng ngh ny c cha nhiu hp cht hu c k trn c c tnh cao, trong :
18
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Nc thi ca cc dy chuyn sn xut, gia cng thuc phng thng cha cc tc nhn c hi: axit, kim cao, cc thnh phn thuc phng l cc ho cht c hi nh: NG, nitroxenlulo (NC), cc hp cht nitro thm, cc thnh phn an nh, dung mi hu c, v.v... Nc thi ca cc dy chuyn x n thu hi thuc n t n cp 5 c cha hm lng cao TNT v cc cht c hi khc. Nc thi ca dy chuyn sn xut thuc n cng nghip nh AD1, nh tng c cha hm lng cao TNT, cc hp cht nitrat, nitrit, v.v... Nc thi dy chuyn sn xut thuc gi n cha cn ca cc cht c tnh nhy n cao nh phuminat thu ngn, styphnat ch, azotua ch, cc hp cht nitro hu c c hi, cc kim loi nng nh ch, thu ngn,v.v... Bng 1.7. Hm lng cc hp cht nitro thm trong nc thi mt s c s cng nghip quc phng STT 1 2 3 Mu nc thi Dy chuyn sn xut DNT Dy chuyn sn xut thuc phng ng Dy chuyn sn xut thuc Cht nhim dinitrotoluen (DNT) nitroglyxerin (NG) Hm lng (mg/l) 106,7 212 910
nitroxenlulo (NC) phng hnh l Ngun: Thuyt minh d n x l cht thi cng nghip, 2009
1.2.2. Hin trng cng ngh x l nc thi nhim cc hp cht nitro thm c hi Cc cht nitro thm c hi l thnh phn ch yu ca cc c s sn xut thuc phng, thuc n, v vy hin nay c nhiu phng php v cc dy chuyn cng ngh x l cc cht ny. 1.2.2.1. Phng php ho hc Phng php ny da vo phn ng ho hc chuyn ho hp cht nitro thm thnh cc hp cht tan hon ton, khng nhy n, khng c so vi cht ban u. Mt trong nhng tc nhn ho hc c s dng l: NaHSO 3, Na2S hoc hn hp: HNO3, NaNO2, Na2S,...
19
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Phng php ny c s dng x l styphnic axit v styphnat ch bng hn hp axit nitric c (HNO3) vi natrinitrit (NaNO2) phn hy chng. Cn styphnat ch c thu gom trong b cha, sau dng hn hp HNO 3 c v NaNO2 ph hy, Pb2+ c tch bng kt ta vi Na2S. Phng php x l ny rt c hi vi mi trng do trong qu trnh phn hy sinh ra mt lng ln NO x gy nhim khng kh, ng thi mt lng ln NO 3-, NO2-, v Pb2+ thi ra cng gy nhim mi trng nc. Phng php ha hc cng c s dng phn hy TNT. TNT l hp cht bn, kh nng phn ng ha hc thp. x l TNT ng ch hn c l natri hydrosunfit (NaHSO3 15%) v natri metadisunfit (Na2S2O5), v chng c th phn hy TNT thnh sn phm khng nhy n v tan trong nc. Tuy nhin, nc thi sau khi x l vn cn mu v tc nhn gy c hi l DNT. Hn ch ca phng php ny l phi thc hin phn ng nhit cao 87 0 C, do kh trin khai p dng trong thc t [10,22]. Phn ng ca TNT vi clo (Cl 2) trong cc thp chuyn dng cng c s dng lm mt mu nc thi c cha TNT. Mt s c s sn xut thuc n cng nghip cng th nghim dng hp cht clo (Ca(OCl)2, NaOCl) lm mt mu nc thi cha TNT. Tuy nhin, trong iu kin cng nghip th vic x l nc thi cha hp cht nitro ch da vo mt cng on l dng OCl - phn hy th cn gp mt s tr ngi, nh phi dng lng d ng k OCl - mi phn hy ht cc hp cht nitro thm, c ngha l bng gii php ny s d to ra lng clo d trong dung dch sau x l [24]. Ngoi ra c th kh TNT bng bt st kim loi ha tr khng. Kt qu kh cho thy TNT b chuyn ha v amin, phn ng din ra qua nhiu giai on, to thnh cc sn phm trung gian RNO, RNHOH v sn phm cui cng l RNH 2 nh sau [28]: RNO2 + Fe 0 + 2H + RNO + Fe 0 + 2 H + RNHOH + Fe 0 + 2 H + RNO + Fe 2+ + H2O RNHOH + Fe 2+ RNH2 + Fe 2+ + H2O
20
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Nhn chung phng php ha hc c th chuyn ha c TNT thnh cc sn phm khng n nhng to ra cc hp cht trung gian m c tnh ca chng cha c nghin cu k. Theo J.G. Sims v cng s [36], sn phm trung gian trong qu trnh kh v oxi ha TNT c th thu c l 2-Hydroxylamino-dinitrotoluen (2HDNT), 4-Hydroxylamin-dinitrotoluen (4-HDNT), 2-Amino-dinitrotoluen (2-ADNT), 4Amino-dinitrotoluen (4-ADNT), 2,6-Diamino-nitrotoluen (2,6-DANT), 4,6-Diaminonitrotoluen (4,6-DANT), 2,4,6-Trinitrobenzen ancol, 2,4,6-Trinitro benzoic Cc hp cht hydroxylamin, trinitrobenzyl ancol v mono-amin c c tnh xp x hoc ln hn so vi TNT, tuy nhin hp cht dng diamin nh 2,4-DANT c c tnh gp nhiu ln TNT. Gi tr LC50 ca TNT v mt s sn phm trung gian nh sau: TNT (3,62 mg/l); 2-ADNT (3,83 mg/l); 4-ADNT (9,17 mg/l); DANT (1,69 mg/l) [22,36]. V vy, phng php phn hy ha hc mi ch dng phn hy lng nh cht thi cha TNT, cha p ng c yu cu v sinh mi trng v x l trit lng ln ngun nhim TNT v cc hp cht nitro thm cc c s sn xut quc phng. 1.2.2.2. Phng php chuyn ha bng nng lng UV Hp cht nitro thm c th b chuyn ha thnh cc sn phm: CO 2, HNO3, H2O bng nng lng UV. Phng php ny thng c kt hp vi cc tc nhn oxy ho khc nh ozon, H2O2,... Vit Nam hin nay c ti lun vn thc s ca Nguyn Vn Cht nghin cu kh nng phn hu TNT trong nc bng bc x UV [3]. Phng php ny da trn c s tnh cht quang ng phn ha ca TNT. Di tc dng ca nh sng mt tri, cc ng phn ca TNT b sm mu v thay i tnh cht (ch yu l nhit ha rn). Phng php s dng tia cc tm l k thut phn hu TNT bao gm s kt hp n UV p sut thp vi cc cht oxi ho l ozon hoc hydroperoxit v n UV p sut trung bnh vi hydroperoxit [3]. Sn phm ph ca qu trnh l trinitrobenzen (TNB), mt cht c c tnh cn cao hn c TNT (hnh 1.1). Khi x l bng phng php UV th 70% thi gian l phn hu TNB [3].
21
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Qu tr nh kh
NO 2 CH3 NO 2 NO 2 CH 3
NO 2 NO 2
CH 3
NO 2 NO 2
CH 3
NO 2
NO CH2 OH
O
O
N N
NHOH H2O
NH2
NO2
NO2
NO2
CH 3
NO2
CH 3
NO 2
H C
NO2 NO2
CH 3 N N
NO2 NO2
CH 3
O H2
Qu tr nh oxiho
NO 2
O NO 2
NO2 NO 2
HO C
NO2
NO2
NO2
NO2 NO 2
CO2 NO 2
NO2
Hnh 1.1. Mt s sn phm ph ca qu trnh phn hy TNT bng UV Quy trnh, cng ngh x l nc thi cha TNT bng phng php ny tuy n gin, nhanh v trit nhng i hi k thut v thit b phc tp. Ngoi ra kh nng truyn qua ca tia UV trong nc c b hn ch lm tng ng k thi gian x l do m gi thnh ca phng php ny kh cao [3,22]. iu kin trong nc cho n nay mi ch c mt vi cng trnh nghin cu cp n cng ngh ny vi mc th nghim phng th nghim. 1.2.2.3. Phng php ozon ho Dng ozon chuyn ha cc cht hu c (c bit l cc hp cht nitro thm) c c tnh trong nc thi l mt phng php mi cha c p dng rng ri [27]. Ozon l mt tc nhn oxy ho ng hng u v l mt cht cng hp cc mnh dn ti nhiu ng dng c hiu. Trong cng ngh ho hc n gi vai tr ti u trong cc qu trnh oxy ho hoc cng hp. c bit l kh nng phn ng vi cc lin kt i trong phn t nitro thm. Trong qu trnh phn ng vi cc lin kt i trong phn t nitro thm s xy ra hin tng ph vng v to thnh cc axit bo, cc axit ny v sau s c chuyn ho thnh cc sn phm trao i trung gian.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Phng php ozon ho nc thi cha hp cht nitro thm, ngoi sn phm cui cng khng gy nhim m trong qu trnh x l cc cht hu c khc trong nc thi cng b oxy ho. Nc thi sau x l c ch s COD gim ng k, ch s BOD gn nh khng cn, lng oxy ho tan trong nc s tng ln [27]. Cng vi qu trnh chuyn ha cc cht hu c, nc thi sau x l s gim ng k v mu, mi v c. Phng php ozn c nghin cu x l TNR. Phng php ny da trn kh nng oxi ha mnh ca ozn, c bit l kh nng phn ng ca n vi cc lin kt i trong phn t cc hp cht nitro thm trong c TNR [21]. Trong qu trnh phn ng, sau khi lin kt vi ni i trong phn t TNR s xy ra hin tng ph v vng v oxi ha n sn phm CO 2, H2O, HNO3. u im ca phng php ny l sn phm cui khng c hi, cc cht hu c c mt cng b oxi ha. Chnh v vy nc thi sau khi x l c cc ch s COD, BOD gim ng k. Thm vo lng oxi ho tan trong nc s tng ln. Cng vi qu trnh phn hy cc cht hu c, nc thi sau khi x l s gim ng k v c mu, mi v c [21,27]. Tuy c nhiu u im nh vy nhng cho n nay phng php ny vn cha c trin khai ng dng rng ri trong thc tin bi nhiu kh khn lin quan n thit b to ozn cng sut ln. Cc thit b pht ozn mi ch c s dng ch yu kh trng nc sinh hot v kh mi khng kh. 1.2.2.4. Phng php in ha [26] Chuyn ha hp cht nitro thm bng phng php in ho v thc cht l ngi ta thay th tc nhn oxy ho - kh ho hc bng tc nhn oxy ho - kh in ho chuyn ha hp cht nitro thm. Cc hp cht nitro thm tng i bn vng, kh x l ha hc v sinh ha. Trong khi cc hp cht amin, polyamin li d dng b oxi ha v phn hy trong mi trng kim. Do x l nc thi c cha cc hp cht nitro thm (TNT, TNR), cch thch hp nht l chuyn ha cc nhm nitro thm thnh cc nhm
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
amin bng s kh in ha trn catt v oxi ha cc sn phm thu c trn ant n CO2, H2O [26]. Gii php ny da trn c s phn ng phn hu in ha ca cc cht nh TNT, DNT, TNR,... n cc sn phm t hoc khng c vi mi trng trong cc thit b in phn c v khng c mng ngn. Kt qu nghin cu v th nghim gii php ny quy m phng th nghim cho thy kh nng phn hu in ha ca TNR nhanh v v c ha hon ton, cn TNT, DNT, RDX,... th tc phn hu chm hn. B in phn c cu to vi catot l thp khng g, ant l cc tm graphit. iu kin in phn: dung dch c pH=4, mt dng 0,5 - 2A/dm 2, nng NaCl = 3g/l, thi gian in phn l 45 pht. Sau khi in phn nc thi c iu chnh v pH = 6 - 8 v thi vo mi trng [26].
iu chnh pH
3
5 6
Hnh 1.2. S dy chuyn cng ngh x l nc thi cha TNR bng phng php in ho
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
u im ca phng php in phn l k thut thc hin khng phc tp, c kh nng phn hu trit v nhanh cht nhim. c bit l ngun nc thi nhim cc nguyn liu sn xut cht gi n nh TNR, styphnat ch,... rt kh x l bng cc phng php khc. Tuy nhin vn cn mt s hn ch nh lng kh thi c cha clo sinh ra trong qu trnh in phn. Dy chuyn in phn p dng b gii hn mc th cng, bn t ng nhng cng p ng c nhu cu bc thit x l ngun nc thi nhim cc cht gi n ny. 1.2.2.5. Hp ph bng than hot tnh Phng php hp ph c dng loi cc cht bn ho tan trong nc vi hm lng rt nh m phng php x l sinh hc cng cc phng php khc khng loi b c. Thng thng y l cc hp cht ho tan c c tnh cao hoc cc cht c mi, v v mu rt kh chu. Cc cht hp ph thng dng l: than hot tnh, t st hot tnh, silicagen, oxit nhm, mt s cht tng hp hoc cht thi trong sn xut nh x tro, x mt st,.v.v. Trong s ny than hot tnh c dng ph bin nht. Than hot tnh c hai dng l: dng bt v dng ht u c dng hp ph. Than hot tnh dng bt c kch thc t 15 - 20m, thng c s dng cc h thng khng c tnh lin tc, x l theo m, kh nng ti s dng thp. Trong h thng x l theo m, c s tip xc ca ton b th tch cht lng cn x l vi than hot tnh th cn phi c s khuy trn v n mang li tc dng tt cho vic chuyn khi din ra mt cch d dng hn [30]. Than hot tnh dng ht c kch thc t 0,3 - 3 mm, thng c s dng trong cc h thng x l lin tc, kh nng ti s dng than cao. Trong h thng lin tc a s s dng than hot tnh dng ht (GAC), chng c c nh trong ct hp ph. S hp ph din ra khi cho cht cn c x l i qua ct hp ph. Kch thc ca than ht dng x l cht hu c nm trong khong 0,4 - 1,7 mm, cao ca tng than thng ln hn 70 cm. Cc cht hu c, kim loi nng v cc cht mu d b than hp ph. Lng cht hp ph ty thuc vo kh nng hp ph ca tng cht v hm lng cht bn c trong nc.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Cc nghin cu ch ra rng, c 3 quy lut m t qu trnh hp ph ca than hot tnh hay c s dng nht l Freundlich, Langmuir v BET (Brunauer, Emmett, Teller) [1, 2, 30, 33]. - Phng trnh ng nhit Freundlich: Qu trnh hp ph ng nhit Freundlich m t trng thi cn bng trn b mt khng ng nht v tha nhn kh nng n lp. Freundlich cho rng:
a = K F .C
1 n
(1.1)
Trong :
Nu xc nh c gi tr K v 1/n th c th tnh c lng than cn thit x l mt th tch dung dch cht nhim bit nng thng qua cng thc sau:
m=
( C0 C ) .V
a
(1.2)
Trong :
m: khi lng than (g) V: th tch nc cn x l (l) a: lng cht b hp ph/mt n v than hot tnh hay dung lng
hp ph (mg/g) C0: nng cht hu c ban u (mg/l) C: nng cht hp ph trng thi cn bng (mg/l) - Phng trnh ng nhit Langmuir Qu trnh hp ph ng nhit Langmuir m t b mt cht rn ng nht v nng lng. Langmuir cho rng, ti tt c cc im xy ra hp ph c mt cn bng v i lc v s hp ph ti mt im khng nh hng n hp ph ti 1 im cnh . Trong trng thi hp ph, cc phn t cht b hp ph ch to thnh n lp v khng tng tc vi nhau (ch tng tc ngang), cn bng hp ph mang tnh cht ng, tc hp ph bng tc gii hp. Phng trnh ng hc c Langmuir a ra nh sau:
26
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
a = am .
K L .c 1 + K Lc
(1.3)
Trong :
a: dung lng hp ph (mg/g) am: dung lng hp ph n lp (mg/g) KL: hng s c: nng ca cht b hp ph (mg/l)
- Phng trnh ng nhit BET - Brunnauer - Emmett - Teller Qu trnh hp ph ng nhit BET: cho rng c nhiu lp hp ph trn cht hp ph. Phng trnh ng hc ca qu trnh ny nh sau:
p 1 1 C 1 p . = + . po p a C .am C.a m p0
(1.4)
Trong : p, p0: p sut v p sut bo ha a, am: dung lng hp ph v dung lng hp ph n lp (mg/g) C: hng s c trng cho nhit hp ph, nhit trng ngng Phng php hp ph bng than hot tnh c th hp ph c 58-95% cc cht hu c v mu. Cc cht hu c c th b hp ph c tnh n l phenol, alkylbenzen, sulfonic axit, thuc nhum cc hp cht thm. c nhng ng dng dng than hot tnh hp ph thu ngn v nhng thuc nhum kh phn hy nhng khng kinh t. loi b cc ion kim loi v kim loi nng, cc cht hu c, v c c hi ngi ta hay dng than bn hp ph v nui bo ty trn mt h. i vi ngun nc thi cc c s quc phng, phng php hp ph c s dng loi b cc hp cht nitro thm trong nc thi nh TNT [25]. Trong s cc phng php x l nc thi th phng php hp ph c trin khai thnh cng quy m cng nghip, p dng mt s cc c s sn xut quc phng. Phng php ny da trn c s s dng than hot tnh hp ph tch cc hp cht nitro thm khi nc thi, cn than hot tnh hp ph c a i x l ring bng phng php thiu t. Tuy nhin, trong thc t x l hiu qu loi nc thi ny, ngi ta thng b sung v h thng x l cc cng on nh x l
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
c hc, x l ha hc v sinh hc. y l gii php cng ngh tng hp, khu hp ph gi vai tr trng tm trong gii php x l. 1.2.2.6. Phng php s dng thc vt T gia nhng nm 90 th k trc, cc nh khoa hc bt u ch n mt gii php cng ngh mi l s dng cy ci loi b, kim ch hoc lm gim mc c hi vi mi trng ca cc cht nhim. Cng ngh ny da trn s thu nhn v chuyn ha cc sn phm nhim bi thc vt. Gii php cng ngh ny c quan tm v la chn v gi thnh r, hiu sut phn hy cao, an ton vi mi trng hn so vi gii php s dng ha cht. Trn th gii, gii php cng ngh ny c nghin cu ng dng kh rng ri nhng Vit Nam chng thc s mi ch bt u c quan tm nghin cu trong thi gian gn y [9]. Kh nng hp thu v chuyn ho cc loi thuc n nh TNT, hecxogen (RDX), octogen (HMX) t mi trng nc bng thc vt c nhiu tc gi nghin cu [32,34,37,39,43]. Th d, cy dng lai, thc vt thy sinh Myriophyllum aquatium c kh nng hp thu cc thuc n TNT, RNX, HMX khi trng thy sinh [34,37]. HMX khng c vi cy dng lai ngay c trong iu kin bo ho (70% HMX c di chuyn v tch ly trong l v khng c cht trao i no khc trong sut 65 ngy tip xc. Cc bnh nui r chm ca cy da cn ( Catharanthus roseus) cng c kh nng thu nhn HMX v RDX [34]. Thc vt thy sinh vng m ly Myriophyllum aquatium c kh nng hp th v chuyn ho TNT. Cc sn phm chuyn ho ca n bao gm cc hp cht azoxy v amin. Qu trnh ny khng ch lm sch cht thi nguy hi vng nhim m cn c th tng cng s sinh trng ca cc qun th sng thy vc [32]. trong nc, c mt s nghin cu tng i chi tit v cng ngh s dng thc vt thy sinh cho x l TNT, RDX, HMX, NG trong nc b nhim, v la chn c mt s loi thc vt c kh nng s dng kh c cho nc b nhim TNT, NG, RDX, HMX nh thu trc, ci, c ln, c lc, rong ui ch [4,9]. 1.2.2.7. Phng php tng hp x l hp cht nitro thm
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
T nm 2001 m hnh cng ngh tng hp (s dng kt hp 3 gii php ho hc, ho l (hp ph) v sinh hc hiu kh) x l nc thi nhim TNT c trin khai p dng ti mt s nh my trong qun i. Cc dy chuyn thit b x l y hot ng theo phng thc bn t ng. T nm 2004 n nay, Phn vin Cng ngh mi v Bo v mi trng/Vin Khoa hc v Cng ngh qun s trin khai hng nghin cu mi l hin i ho dy chuyn thit b t ng ho cc cng on iu chnh pH mi trng phn ng v cp nguyn liu ng thi nghin cu kh nng p dng cc gii php CNSH mi (s dng thc vt bc cao) ng b ho dy chuyn cng ngh x l nc thi nhim TNT.
H thng x l vi sinh (8) B lng lc III (9)
H thng x l bn (14)
H thng lc c hc (1)
B gom (2)
B iu ho (3)
B lc I (4)
B hp ph (5)
B lng lc II (6)
Hnh 1.3. S khi h thng x l nc thi nhim TNT bng gii php cng ngh tng hp c mt s cng trnh nghin cu trong nc tng i chi tit v x l TNT (2,4,6-trinitrotoluen, mt dng thuc n nhn thm thuc nhm dn xut nitro ca toluene) trong nc thi ca ngnh cng nghip sn xut thuc phng, thuc n bng hp ph (than hot tnh) v cc bin php sinh hc (s dng thc vt thy
29
Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
sinh) trong nc v t b nhim. Nhng cho n nay, cha c cng trnh nghin cu no v gii php s dng hp ph (than hot tnh) v cc bin php sinh hc (s dng thc vt thy sinh) cho x l nc b nhim DNT, DNP v TNR. Hy vng cc kt qu thc nghim trong qu trnh thc hin kho lun ny s la chn c cc loi than hot tnh v cc loi thc vt thy sinh kt hp trong phng php x l nc thi cha DNT, DNP v TNR ca cc c s sn xut thuc phng, thuc n.
Chng 2. I TNG V PHNG PHP NGHIN CU 2.1. I TNG NGHIN CU - Nc thi b nhim DNT, DNP v TNR.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
- c im hp ph ca DNT, DNP v TNR trn than hot tnh v cc yu t nh hng n kh nng hp ph. - Kh nng x l DNT, DNP v TNR bng thy trc v bo ci - Quy trnh x l nc thi cha DNT, DNP v TNR bng than hot tnh kt hp vi s dng thc vt thy sinh. 2.2. THIT B V HA CHT 2.2.1. Thit b - H thng thit b sc k lng hiu nng cao (HPLC) Model HP 1100, s dng detector Diode Array do hng Aligent (M) sn xut, ti Phng th nghim Phn vin Cng ngh mi v Bo v mi trng/ Vin Khoa hc v Cng ngh qun s. - Cn phn tch in t Mettler do hng Toledo (Thy S) sn xut, nhy 10-4 gram. - My o pH HACH (M). - Cc vi snh hnh tr c ng knh trung bnh 22 cm, chiu cao 22 cm. - Cc loi chu nha c ng knh trung bnh 35cm. 2.2.2. Ha cht - Dinitrotoluen (DNT): tinh khit 98%, dng rn (Merck - c). - Dinitrophenol (DNP): tinh khit >99,5%, dng bt (Merck - c). - Styphnic axit (TNR): tinh khit 99,5%, dng bt (Merck - c). - Dung mi dng cho phn tch HPLC: axetonitryl (Merck - c). - t ph sa c phi kh t nhin, m trung bnh 50%. Cc loi than hot tnh - Than hot tnh AG (Lin bang Nga). - Than ty mu TM do Cng ty Trng Pht - Bc Giang sn xut. - Than hot tnh TQ sn xut ti nh my ho cht Qung ng - Trung Quc. Cc loi than hot tnh s dng l loi than hot tnh dng bt, kch thc ht trung bnh t 15 - 20 m.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Bng 2.1. Mt s thng s cu trc xp ca cc loi than hot tnh (tnh theo hp ph ng nhit benzene) Loi than Din tch b mt (m2/g) Th tch cc loi mao qun (cm3/g) Vtng 1,034 1,244 1,059 Vnh 0,305 0,360 0,271 Vtrung 0,097 0,133 0,123 Vln 0,632 0,752 0,665
- Cy thu trc: Mua ti cc vn trng cy cnh trn a bn Ty M - T Lim - H Ni, chiu cao trung bnh t 30 - 40cm, ng knh thn cy t 0,3 0,6cm, tnh trng pht trin tt. - Bo ci ly ao khu vc T Lim - H Ni, tnh trng pht trin tt. 2.3. PHNG PHP NGHIN CU 2.3.1. Thit k th nghim 2.3.1.1. Th nghim hp ph DNT, DNP v TNR bng cc loi than hot tnh nh hng ca thi gian ln hiu qu hp ph Ly 100 ml dung dch DNT, DNP v TNR c nng xc nh cho vo bnh tam gic 250 ml, cn khi lng than hot tnh (bao gm 03 loi, AG; TM; TQ) xc nh cho vo bnh v lc u. Ly mu phn tch cc thi im 5 - 10 - 15 - 20 pht, s dng giy lc lc ly phn dung dch phn tch. Xc nh c thi gian hp ph t cc i. nh hng ca khi lng than ln hiu qu hp ph Ly 100 ml dung dch DNT, DNP v TNR c nng xc nh vo bnh tam gic 250 ml, cn khi lng than hot tnh vi cc mc khc nhau cho vo bnh v lc u, sau thi gian hp ph la chn (thi gian hiu qu hp ph ca cc cht t cc i), lc v phn tch trn thit b HPLC. nh hng ca nhit , pH ln hiu qu hp ph Ly 100 ml dung dch DNT, DNP v TNR c nng xc nh vo bnh tam gic 250 ml, cn khi lng than hot tnh xc nh cho vo bnh v lc u. t
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
ch nhit 25, 30, 35, 40 v 500C. Sau thi gian la chn ly mu v phn tch trn thit b HPLC. Ly 100 ml dung dch DNT, DNP v TNR c nng xc nh vo bnh tam gic 250 ml, iu chnh pH cc mc t 3 n 10, cn khi lng than hot tnh xc nh cho vo bnh v lc u. Sau thi gian la chn ly mu v phn tch trn thit b HPLC. 2.3.1.2. Th nghim th kh nng hp thu v x l ca cc loi thc vt thy sinh i vi DNT, DNP v TNR - B th nghim trng cy thu trc: dng cc vi snh c m t trn, th nghim c thit k nh sau: i chng 1: b ch cha 2 lt cc dung dch DNT, DNP v TNR - th nghim v kh nng t phn hu ca DNT, DNP v TNR bng nh sng mt tri. i chng 2: b cha 4kg t v 2 lt dung dch DNT, DNP v TNR - th nghim kh nng t x l ca t v h vi sinh vt trong t i vi DNT, DNP v TNR. Cc b trng cy c t v dung dch DNT, DNP v TNR, lng t v dung dch DNT, DNP v TNR s dng l: 2lt dung dch/ b v 4 kg t/ b - th nghim kh nng x l DNT, DNP v TNR khi c mt thu trc. Mt cy trng trong cc b th nghim: 300 890g sinh khi cy/0,038m2/ 4 kg t. - B th nghim vi cc loi bo: s dng cc chu th bo vi dung dch DNT, DNP v TNR l 2lt dung dch/chu. Cc b i chng cng c t tng t nh trn. Mt bo trong cc chu th nghim: 60 120g bo/0,096m2. - tt c cc th nghim u xc nh khi lng thu trc v bo ban u. Th tch dung dch khng thay i trong sut qu trnh th nghim (nh du mc nc v dng nc my b sung vo sau mi ngy nu b hao ht v th tch). nh k ly mu nc hoc t xc nh hm lng cc cht nhim (DNT, DNP v TNR) bng phng php HPLC. 2.3.2. Phng php phn tch nng cht nghin cu Nng cht nghin cu c xc nh bng phng php HPLC.
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
Nguyn tc ca phng php HPLC l da trn s hp ph v gii hp ph chn lc ca cc hp cht trong ct sc k vi pha ng nht nh trong iu kin p sut cao. Nh ngi ta c th tch ring tng cu t ca hn hp v s dng Detector UV hoc Detector - Diode Array o ph hp th ca cc cu t. - iu kin o: + Ct Hypersil C18 ( 200 x 4 mm ) + T l pha ng Axetonitril : H2O = 65 : 35 (theo th tch ) + p sut: 280 bar. Cch tin hnh: + Sau khi t xong cc thng s cn thit, tin hnh ra bm, ra ct, i ng nn v p sut n nh khong 30 - 45 pht. + Dng micrxilanh ly 5 l dung dch phn tch a vo bung mu. My s t ng ghi cc thng s: thi gian lu (t R), chiu cao pic v tnh din tch cng nh thnh phn phn trm (%) ca tng cu t trong hn hp. - Nng DNT trong dung dch c xc nh bng phng php HPLC iu kin: + Tn hiu o: = 245 nm + Tc dng: 0,42 ml/pht + Th tch bm mu: 5,0l + Thi gian lu (tR), ng vi pic ca DNT l 9,0 pht + n v o: mg/l - Nng DNP trong dung dch c xc nh bng phng php HPLC iu kin: + Tn hiu o: = 365 nm + Tc dng: 0,35 ml/pht + Th tch bm mu: 5,0l + Thi gian lu (tR), ng vi pic ca DNP l 7,0 pht + n v o: mg/l - Nng TNR trong dung dch c xc nh bng phng php HPLC iu kin: + Tn hiu o: = 420 nm + Tc dng: 0,35 ml/pht
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
+ Th tch bm mu: 5,0l + Thi gian lu (tR), ng vi pic ca TNR l 4,5 pht + n v o: mg/l 2.3.3. Cc phng php x l s liu thc nghim 2.3.3.1. Xc nh dung lng hp ph ca than hot tnh i vi DNT, DNP v TNR
a=
( C0 Ct ) V [ mg / g ]
m
(2.1)
Trong : a l dung lng hp ph (mg/g); C0 l nng ban u cht b hp ph (mg/l); Ct l nng ca cht b hp ph cn li trong pha lng (mg/l); V l th tch dung dch (l); m l khi lng than hot tnh (g). 2.3.3.2. Xc nh tc x l DNT, DNP v TNR ca cc loi thc vt
VXL =
Trong :
( C0 Ct ) Vdd
mt
(mg/gsk/ngy)
(2.2)
VXL : tc x l, tnh bng mg/g sinh khi/ ngy; C0 : nng ban u cht cn x l (mg/l); Ct : nng ca cht cn x l sau t ngy x l (mg/l); m: khi lng sinh khi cy trng (gram) (c th tnh theo thn l v r); t: thi gian x l (ngy); Vdd: th tch dung dch DNT, DNP v TNR s dng ban u. 2.3.3.3. Xc nh hiu sut x l DNT, DNP v TNR ca cc loi thc vt
H tv =
( C 0 Ct ) 100
C0
( %)
(2.3)
Trong : Htv: hiu sut x l sau t ngy (%); C0: nng ban u cht cn x l (mg/l);
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Nghin cu kh nng x l nc thi cha mt s hp cht nitro vng thm bng phng php hp ph trn than hot tnh kt hp vi s dng thc vt thy sinh
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