I I M U T VN

G H :

Sn xut tinh bt khoai m l mt ngnh thc phm chnh ng m Cng nghip ch bin tinh bt khoai m l mt ngnh cng nng nghip lm theo thi v, s dng khoai m lm nguyn liu chnh. Tinh bt khoai m l mt trong cc ngun hm lng tinh bt cao nht, c khoai m ch n 30% hm lng tinh bt nhng hm lng protein, cacbonhydrate v cht bo thp l ngun th n ho uc sng on ngi v l ngun nguyn liu cho cc ngnh cng nghip ch bin thc phm. Th trng tinh bt ngy ng tng do nhu u s dng nguyn liu cho sn xut ngy ng tng a cc ngnh sn xut bnh ko, bt ngt ; c bit l nhu c u cho vic s dng sn xut nhin liu sch( nhin liu sinh hc). Hin nay n c ta, trong cc ngnh cng nghip trng im c t n c th tinh bt sn l mt ngnh kinh t ng c s ch trng v thu ht u t a cc nh sn xut. c bit l lnh vc s dng nguyn liu sn cho cc nh my sn xut Et nol ng ngy c m rng v phm vi v quy m. N to ra nhng li ch kinh t, li ch x hi to l n: to ng n vi lm ho ngi l o ng, ng g p ho ngn s h nh n c, n nh vn nguyn liu cho sn xut trong n , qu n nh th trng. Tuy nhin cng v i s pht trin ca nh my, lun km theo nhiu vn bc thit c n gii quyt. Trong vn n c thi nh my t ln hng u guyn do y l ngnh sn xut s dng n tng i l n, n c thi t qu trnh ch bin tinh bt sn gy nhim ngun tip nhn cht hu , dng thi phn hy sinh ra mi hi thi v mt s cht kh lm nh hng n mi trng khng kh. Nguy him hn khi n c thi c thi ra t qu trnh ln men tinh bt sn, nu khng c x l tr khi r mi trng s gy ra nhng tc hi to l n ho on ngi, mi trng v sinh vt, do cha mt hm lng tng i Xianua. p ng nhu c u thc t , hng t s i tm hiu cng ngh x l Xianua n c thi trong qu trnh sn xut tinh bt sn. trong

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MC TIU V NI DUNG THC HIN Mc Tiu Ca Ti nh thnh ph n tnh cht n c thi sn xut tinh bt m. l i nu trong n thi tinh t sn

Ni Dung Thc Hin Nghin cu s l thuyt Thu thp phng n x l n c thi ngnh sn xut tinh bt hu thp phng n x l i nu trong n hn ng ngh x l i nu thi

K HIU VIT TT BOD: Biochemical Oxygen Demand Nhu c uoxi sinh ho, mg/l CO : Chemi l Oxygen em n Nhu c u xi ho hc, m/l SS : Suspended Solid - Cht rn l lng, mg/l DO : Dissolved Oxygen Oxi ho tan, mgO2/l UASB: Upflow Anaerobic Susdge Blanket - X l ym kh ngc dng c l p n l lng FAO: T ch lng thc Th gi i TCVN: Tiu chun Vit Nam TBS: Tinh bt sn N N nh m 7 1. h 2. hm n trng 3. guyn n hnh 4. nh Chin 5. Kim n in

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I I NG

G H :

H N

TNG QUAN V NGNH SN

TINH B

I. Gii thiu chung [7] Tinh bt khoai m l thc phm ho hn 500 triu ngi trn Th Gi i (theo Cock,1985; Jackson & Jackson, 1990) n c trn Th Gi i sn xut v xut khu. Brazil sn xut khong 25 triu tn /nm igeri , Indonesi v hi n ng sn xut mt lng l n xut khu (CAIJ,1993). Chu Phi sn xut khong 85,2 triu tn nm 1997, Chu 48,6 triu tn v 32,4 triu tn do M La Tinh v Caribbean sn xut (FAO,1998). Nguyn liu ch bin Tinh bt khoai m t c m ti u to v thnh ph n nh s u: 1. Cu to c khoai m

Hnh 1.1. Cu to c khoai m Cu to ca khoai m. [7] C khoai m c dng hnh tr, vut h i u. h th c c ty thuc vo thnh ph n dinh dng c t v iu kin trng, di 0,1 1 m, ng knh 2 10 cm. Cu to gm 4 ph n chnh: l p v g, v ci, ph n tht c v ph n li. 2. Phn loi khoai m C nhiu cch phn loi kho i m kh nh u, nhng h yu l c phn ra t hai loi: kho i m ng v khoai m ngt. Vic phn loi ny ph thuc vo thnh ph n cyanohydrin c trong c m. Da vo thnh ph n Cyanohydryn c trong c m m ngi ta phn n ra lm 2 loi ho i m ng v khoai m ngt: ho i m ng ( nihot p lm t nihot ipr ohl): Hm lng HC hn 50mg /kg c ho i m ng c thnh ph n tinh bt cao, s dng ph bin lm nguyn liu cho cc ngnh cng nghip ch bin thc phm, cng nghip ho dc, cng nghip giy v nhiu ngnh cng nghip khc.

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Khoai m ngt ( nihot ipr h y nihot utilissim ohl): Hm lng HC nh hn 50mg/ kg . Khoai m ngt c dng lm thc phm ti v v ngt v d to thnh bt nho, d nghin nt h y nh nhuyn - Thnh ph n ha hc c kho i m: th y i tu thuc vo ging, tnh cht, dinh dng c t, iu kin pht trin ca cy v thi gian thu hoch. Bng 1.1: Thnh phn ho hc cy khoai m [7]

n n sn ut t n t sn t Nam v t Sn c s dng kh ph bin sn xut tinh bt, y l ngun nguyn liu cho nhiu ngnh cng nghip nh ng nghip dt, thc phm, may mc, bnh ko, sn xut ln men cn, sn xut acid hu , Bng 1.2. Din tch, nng sut v sn lng sn ca th gii t nm 1995 2008[12] 3. D n tc (tr u a) 16,43 16,25 16,05 16,56 16,56 16,86 17,17 17,31 Nm 1995 1996 1997 1998 1999 2000 2001 2002 Nn sut (tn/ a) 9,84 9,75 10,06 9,90 10,31 10,70 10,73 10,61 n ln (tr u tn) 161,79 158,51 161,60 164,10 170,92 177,89 184,36 183,82

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I I 17,59 18,51 18,69 20,50 18,39 21,94

I 2003 2004 2005 2006 2007 2008

G 10,79 10,94 10,87 10,90 12,16 12,87

G H :

H 189,99 202,64 203,34 224,00 223,75 238,45

Ngun: Trn Cng Khanh tng hp t FAOSTAT qua cc nm. Bng 1.3. Din tch, nng sut v sn lng sn ca Vit Nam giai on 1995 2008[12]

Nm 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008

D n tc (nghn ha) 164,30 275,60 254,40 235,50 226,80 234,90 250,00 329,90 371,70 370,00 425,50 474,80 496,80 557,40

Nn sut (tn/ a) 9,84 7,50 9,45 7,55 7,96 8,66 8,30 12,6 14,06 14,49 15,78 16,25 16,07 16,85

n ln ( tr u tn) 1,62 2,06 2,40 1,77 1,80 2,03 2,07 4,15 5,23 5,36 6,72 7,77 7,98 9,3

Ngun: Trn Cng Khanh tng hp t Nin gim thng k qua cc nm.

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Bng 1.4. Din tch, nng sut v sn lng ca cc vng sinh thi Vit Nam nm 2008 [12] TT 1 2 3 4 5 6 Vng sinh thi ng ng sng Hng rung du v min ni ph rung v uyn hi min Trung Ty Nguyn ng C n m ng ng sng Cu ong D n tc (1000 ha) 7,90 110,00 168,80 150,10 113,50 7,40 557,40 Nn sut (tn/ a) 12,92 12,07 16,64 15,70 23,74 14,43 16,87 n ln (1000 tn) 102,10 1.328,00 2.808,30 2.356,10 2.694,50 106,80 9.395,80

Ngun: Trn Cng Khanh tng hp t Nin gim thng k qua cc nm. Hnh 1.2 Gi tr kinh t ca c khoai m [7] C I U CN

THC

BT CNG NGHIP NGNH CNG

PHM
G I SC V T Thc phm trc tip Bt BT CNG

NGHIP
St lt Vin nn Bt bn

NGHIP
Giy Keo ,H Dt si G , vn p Cao su Giy

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c t CN-: c t trong khoai m tn ti d i dng CN-. Ty thuc vo ging v t trng m hm lng c t trong khoai m khong 0,001 0,04%. Cyanua l nguyn t gy tnh o i v i on ngi v thy sinh vt. Cyanua t do tn ti d i dng HCN hay CN- l dng c tnh nht trong n l HC Cy nu ngn n qu trnh chuyn ha cc ion vo da, ti mt, thn, nh hng n qu trnh phn ha t bo trong h th n kinh.. CN- gy tnh ho , ng vt hoang d, vt nui. 4. Mt s quy trnh cng ngh sn xut tinh bt [7] Mt s quy trnh cng ngh sn xut tinh bt khoai m trn th gi i
ng

Khoai m

Sy kh

Lng

Qut ht

n c Tinh bt m nghin p Lc Qut ht

Hnh 1.3: Quy trnh sn xut tinh bt ca Indonesia [7] Quy trnh ch bi n c k oa m sn xut tinh bt c thc hin n sau

C khoai m Ra c Bc v v ra Mi xt c , c nc P sy Gel ha, p vin, sy Sn phm dng vin ht (tapioca) Sn phm dng tinh bt

Lc, ra

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Quy trnh cng ngh sn ut t n

c cp

t ca Thi Lan [7]

K oa m t Nc thi

c cp

Ra s , tch tp cht Song chn rc, cng trnh x l s

c cp

Bc v g, ra sch

Bm n

Mi, nghin

P , my nn

c cp

Trch ly, chi c sut

B m

Lc

Nc thi

Dehydrate ha

Trm x l nc thi Khi thi

Sy kh

Sng, lc H th ng x l khi n ao, v k o

-X ra ngun ti p nhn -S dng li ti cy p: H u -K53

Thnh phm

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Quy trnh cng ngh sn xut c p dng theo cng ngh ca Thi Lan, quy trnh ng b khp kn, k thut tin tin mang tnh t ng ha cao, thc hin trch ly v hydrat ha sa bt nhiu l n lp i lp li, lm tng ht lng tinh bt v tng t l thu hi sn phm. Thi gian t khi nguyn liu nhp vo dy chuyn my m n khi sn phm ra khong 1 gi. Thao tc s dng v vn hnh my mc, thit b n gin, d thc hin. u im chnh ca cng ngh hi n: Cng on trch ly chit sut c thc hin qua nhiu gi i on, kt hp v i x l bt bng SO2 o quy trnh ng ngh ca Thi Lan cho t l thu hi h tinh bt o, lng tinh bt to ra theo b c th hn ch t i mc thp nht. II. n p n v tc n ca cc c t a c c tron nc t n t n t sn 13 n my c

1. Thnh phn cc cht c tron nc thi ca nh my ch bi n tinh bt sn c sn xut c s dng nhiu nht ng on ra v ly tm t h ng n c thi r mi trng thng chim 80- 90 % n c s dng. c thi sinh ra t dy chuyn sn xut tinh bt sn c cc thng s trng nh: pH thp, hm lng cht hu v v o, th hin qu hm lng cht rn l lng (SS), cc cht dinh dng cha N, P,K, cc ch s v nhu c u oxy sinh ho hc (BOD), nhu u oxy ho h (CO ), m u...v i nng rt o, vt nhiu l n so v i tiu chun mi trng c thi c sinh ra t ng on sn xut chnh sau y: - Bc v, mi c, p : cha mt hm lng l n cyanua, alcaloid, antoxian, protein, xenluloz , pe tin, ng v tinh bt y l ngun chnh gy nhim n c thi, thng d o ng trong khong 20-25m3/ tn nguyn liu, c cha SS, BOD, COD rt cao. - Lng trch ly: cha tinh bt, xenluloza, protein thc vt, lignin v y nu , do SS, BOD, COD rt cao, pH thp. - Ra my mc, thit b, v sinh nh xng: c cha d u my, SS, BOD. - c thi sinh hot (n c thi t nh bp, nh tm, nh v sinh) cha cc cht cn , SS, BOD, COD, cc cht dinh dng (N, P) v vi sinh vt - m hy trn ti nh my cun theo cc cht cn , rc, bi. goi r , trong qu trnh sn xut, HC ho t n trong n c r , thot khi dy chuyn sn xut ng g p ph n gy nhim mi trng to mu sm c n c thi. Bn cnh n c thi n c kh thi trong nh my sn xut tinh bt sn phi k n l cc hp cht SOx t qu t nh ty r dng n c SO2, dung dch NaHSO3, CO2 t qu t nh ln men, cc loi kh NH4, indon, scaton, H2S, CH4 t qu t nh ln men ym kh v hiu kh cc hp cht hu nh tinh t, ng, protein trong n c thi, thi. Cc cht thi rn nh v snh (v l p ngoi cng ca c sn), cc ph n s, thi rn cha nhiu xenluloz , lc t my lc, my ly tm.
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Kt qu phn t h n c thi ti mt s doanh nghip sn xut tinh bt sn Vit Nam (Bng 1.5). Bng 1.5. Cht lng nc thi ca t sn xut tinh bt sn [13] Kt qu phn tch nc thi ti mt s doanh nghip sn xut tinh bt sn Vit Nam

Ghi ch: * Cc thng s quy nh trong tiu chun, h x t h s lin qu n n dung tch ngun tip nhn v h s theo lu lng ngun thi, trong : A - Thi vo ngun tip nhn dng cho m h sinh hot. B - Ngun tip nhn khc, ngoi loi A. C - Ngun tip nhn quy nh. Bng trn cho thy cht lng n c thi t quy trnh sn xut tinh bt sn hon ton khng p ng c tiu chun mi trng. Ngoi tnh cht xit, n c thi n cha lng cht rn, cc cht hu , HC n c x l. Bn cnh , khong cch dao ng v cc ch tiu n c thi o hn nhiu l n so v i tiu chun cho php. Thnh ph n n c thi ph phuc vo quy m sn xut, tng m u t, trnh cng ngh v h thng thit b x l n c thi, quy trnh vn hnh v quan tr mi trng. V i hm lng O / CO nh ng trn, n c thi ngnh sn xut tinh bt sn c th c x l ym kh (UASB), hiu kh, h sinh hc, s dng ch phm vi sinh vt p ng cc tiu chun mi trng uy nhin, n c thi sn xut tinh bt sn cc quy m khc nhau, h u nh h t c tiu chun n c thi cng nghip ca Vit Nam.

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2. c ng ca cc cht c tron nc thi. - Biochemical Oxygen Demand (BOD) l nhu c u oxy sinh ho h x nh m nhim c n c cp, n c thi cng nghip v n c thi sinh hot - Chemical Oxygen Demand (COD) l nhu c u oxy ho h oxy ho cc cht hu v v ha trong n c thi cng nghip S nhim ca cc cht hu dn n suy gim nng xy ha t n ( O) n c. xy h tan gim s t ng nghim trng n h thy sinh, c bit l h vi sinh vt. Khi xy ra hin tng phn hy ym kh v i hm lng BOD qu cao s gy thi ngun n c v git cht h thy sinh, gy nhim khng kh xung quanh v pht tn trn phm vi rng theo chiu gi. - Cht rn l lng ( ) ng l t nhn gy nh hng tiu cc t i ti nguyn thy sinh ng thi gy mt cm quan, bi lng lng h, sng sui... - Axit hu xy nu hydri (HC ) l c t c trong v sn hi h o, trong c sn khng c HCN t do m dng lin kt glucozit gi l phazeolutanin c cng thc ha hc l C10H17NO6 u khi o, d i tc dng ca enzym xyanoaza hoc trong mi trng xit th phazeolutanin phn hy to thnh glucoza, axeton v axit xyanuahydric. Axit ny gy ton thn ho ngi. Xyanua dng lng trong dung dch l cht linh hot, khi vo th n kt hp v i enzym trong xitochrom lm c ch kh nng p xy cho hng c u o , qu n th b thiu xy. Nng HCN thp c th gy chng mt, ming ng, bun nn. Nng HCN cao gy cm gic bng bnh, kh th, da hng, co git, m man, bt tnh, hoa mt, ng t gin, au nhi vng tim, tim ngng p v gy t vong. Trong sn xut sn, HCN tn ti trong n c thi, c phn ng v i st to thnh st xyanua c mu xm. Nu khng tch nhanh HCN s nh hng t i mu ca tinh bt v mu c n c thi Hm lng c t HCN trong c sn 0,001- 0,04 % ch yu v. ng y nhydri trong n c thi ch bin c khoai m c th ln n 3- 5mg/l, trong khi ch v i hm lng d i 0,3 mg/l gy cht c hng lot. C m ti ng nh (v c v ) c cha mt lng cht c hi d i dng Glycoside linamarin C10H17O6N C10H17O6N + H2O C6H12O6 + (CH3)2CO + HCN Glucose Aceton Axt hyrocyanic c thi trong qu trnh sn xut thng cha nhiu tp cht h (t, ct, bn, v, x), mt s tinh bt n st qua lc, mt t ng ha tan, protein, lipit v enzim, nn rt d b ln men ru sinh ra mi hi chua, hi thi, trng ti lng BOD5 > 2000mg/l, ti lng CO > 4000mg/l c thi ca cc nh my sn xut tinh bt sn quy m l n c BOD 6.200 - 23.000 mg/ lt v khi lng n c thi kh l n 1.500m3/ ngy m u n c thi khng c x l trit , khng t tiu chun mi trng, s gy nhim nghim trng cho ngun n , t v khng kh.
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H NG NG N

G H :

N P NG P P L N N N B N [6]

A. P NG P P I. P NG P P C

hng php x l hc s dng nhm m h t h cht khng ho tan v mt ph n cc cht dng keo ra khi n c thi. Nhng cng trnh x l hc bao gm : 1. Song chn rc 2. B lng ct 3. B lng 4. B ln ng 5. B lng ngang 6. B lng ly tm 7. B vt du m Hiu qu ca Phng php x l c hc : C th loi b n 60% tp cht khng ho t n trong n c thi v gim BOD n 30% tng hiu sut cng tc ca cc cng trnh x l hc c th dng bin php lm thong s , thong gi ng t sinh hc, hiu qu x l c th t t i 75% theo hm lng cht l lng v 40-50 % theo BOD. Trong s cc cng trnh x l hc c th k n b t hoi, b lng hai v, b lng trong ngn phn hu l nhng cng trnh v lng v phn hu cn lng . II. P NG P P Bn cht ca qu trnh x l n c thi bng phng php ho l l p dng cc qu trnh vt l v ho h vo n c thi cht phn ng no gy t ng v i cc tp cht bn, bin i ho hc, to thnh cc cht kh d i dng cn hoc cht ho tan nhng khng c hi hoc gy nhim mi trng. Gi i on x l ho l c th l gi i on x l c lp hoc x l cng v i phng php hc, ho hc, sinh hc trong cng ngh x l n c thi hon chnh.

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Nhng phng php ho l thng c p dng x l n c thi l: keo t, ng t, tuyn ni, hp ph, tr o i ion, thm l ngc v siu lc 1. P n p p keo t v n t 2. Tuyn ni 3. Hp ph 4. P n p p trao i ion. 5. Cc qu trnh tch bng mng 6. P n p p n ho 7. P n php trch ly III. P NG P P C

C phng php ho hc dng trong x l n c thi gm c: trung ho, oxy ho v kh. Tt c phng php ny u dng cc tc nhn ho h nn l phng php t tin gi ta s dng phng php ho h kh cc cht ho tan v trong cc h thng cp n c khp kn i khi phng php ny dng x l s tr c x l sinh h h y s u ng on ny nh l mt phng php x l n c thi l n cui thi vo ngun . 1. P n p p trun o

2. P n p p o y o k 3. Kh trn nc thi IV. P NG P P N C

hng php x l sinh hc l s dng kh nng sng, hot ng ca vi sinh vt phn hu cc cht bn hu trong n c thi. Cc vi sinh vt s dng cc hp cht hu v mt s khong cht lm ngun dinh dng v to nng lng. Trong qu trnh dinh dng, chng nhn cc cht dinh dng xy dng t o, sinh trng v sinh sn v th sinh khi c hng tng ln. Qu trnh phn hy cc cht hu nh vi sinh vt gi l qu trnh oxy h sinh h hng php x l sinh hc c th thc hin trong iu kin hiu kh (v i s c mt ca oxy) ho trong iu kin k kh( khng c oxy).

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hng php x l sinh hc c th ng dng lm sch hon ton cc loi n c thi cha cht hu ho t n hoc phn tn nh. Do vy phng php ny thng c p dng sau khi loi b cc loi tp cht th ra khi n c thi hm lng cht hu o Qu trnh x l sinh hc gm cc bc Chuyn ho cc hp cht c ngun gc cacbon dng keo v dng ho tan thnh th kh v thnh cc v t bo vi sinh To ra cc bng cn sinh hc gm cc t bo vi sinh vt v cc cht keo v trong n c thi Loi cc bng cn ra khi n c thi bng qu trnh lng . 1. l nc t n p n p p s n c tron u k n t n n t h ht n hu dng keo v ho t n trong iu kin t nhin ngi t x l n thi trong o, h ( h sinh vt) h y trn t ( nh ng t i, nh ng l ) s n vt H sinh vt l o h ngun g t nhin ho nhn to, n gi l h oxy ho, h n nh n thi, x l n thi ng phng php sinh h rong h sinh vt din r qu trnh oxy ho sinh ho ht hu nh loi vi khun, to v loi thy sinh vt kh , tng t nh qu trnh lm s h ngun n mt i sinh vt s dng oxy sinh r t ru to trong qu trnh qu ng hp ng nh oxy t khng kh oxy ho ht hu , rong to li tiu th CO2, photph t v nitr t mon sinh r t s phn hu, oxy ho ht hu i vi sinh vt h hot ng nh thng n phi gi gi tr pH v nhit ti u hit khng thp hn 60C. heo n ht qu trnh sinh ho, ngi t hi h sinh vt r loi h hiu kh, h sinh vt tu tin (F ul tive) v h sinh vt ym kh - s n vt uk Qu trnh x l n thi xy r trong iu kin y oxy, oxy ung p qu mt thong v nh qu ng hp to ho h lm thong ng nh h thng thit p kh. su h sinh vt hiu kh khng l n t 0,5-1,5m. s n vt tu t n C su t 1 5 2 5m , trong h sinh vt ty tin, theo hiu su l p n th din r h i qu trnh : oxy ho hiu kh v ln men ym kh ht n hu rong h sinh vt tu tin vi khun v to qu n h tng h ng v i tr n i v i s huyn ho ht s n vt y m k C su trn 3m ,v i s th m gi hng trm hng loi vi khun k kh t u v k kh khng t u C vi sinh vt ny tin hnh hng h phn ng ho sinh h phn hu v in i hp ht hu ph tp thnh nhng ht n gin, d x
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l Hiu sut gim O trong h th ln n 70% uy nhin n thi s u khi r khi h vn O o nn loi h ny h h yu p dng ho x l n thi ng nghip rt m v dng lm h 1 trong t hp nhiu - n n t - n n lc Cnh ng t i l nhng khong t nh t , th tip nhn v x l n thi l trong iu kin ny din r d i t dng vi sinh vt, nh sng mt tri, khng kh v d i nh hng hot ng sng th vt, ht thi hp th v gi li trong t, s u loi vi khun sn trong t s phn hu hng thnh ht n gin y trng hp th. thi s u khi ngm vo t, mt ph n y trng s dng. h n n li hy vo h thng tiu n r sng ho sung ho n ngun 2. l nc t n p n p p s n c tron u k n n n to - B lc s n c l sinh h l ng trnh nhn to, trong n thi l qu vt liu rn b o mt l p mng vi sinh vt l sinh h gm ph n hnh nh s u: ph n h vt liu l , h thng phn phi n m o t i u ln ton mt , h thng thu v dn n s u khi l , h thng phn phi kh ho l Qu trinh oxy ho ht thi trong l sinh h din r ging nh trn nh ng l nhng v i ng l n hn nhiu. ng vi sinh vt s dng v x vi sinh vt ht theo n tri khi t h khi n thi lng t 2. m o qu trnh oxy ho sinh ho din r n nh, oxy p ho l ng in php thng gi t nhin ho thng gi nhn to t liu l l sinh h th l nh l sti , x vng gm, Gr nit - B lc s n c n t dng hnh vung, hnh h nht ho hnh trn trn mt ng, l sinh h nh git lm vi theo nguyn t s u: thi s u lng t 1 v thit phn phi, theo hu k t i u n trn ton mt l thi s u khi l hy vo h thng thu n v dn r khi . Oxy p ho h yu qu h thng l xung qu nh thnh . t liu l sinh h nh git thng l ht ui, ng knh trung bnh 20 30 mm i trng n thi thp (0,5 1,5 m3/m3 vt liu l /ng). Chiu o l p vt liu l l 1,5 2m Hiu qu x l n thi theo tiu hun O t 90% ng ho trm x l n thi ng sut d i 1000 m3/ng - B lc s n c cao t l sinh h o ti u to v qun l kh v i l sinh h nh git , n thi t i ln mt nh h thng phn phi phn l ti trng 10 20 m3 n thi / 1m2 mt /ng u trng hp O n thi qu l n ngi t tin hnh
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ph lo ng hng ng n thi lm s h. thit k ho trm x l d i 5000 m3/ng. - B u k n ot tn B erotank h hn hp n thi v n hot tnh, kh p lin t vo trn u v gi ho n trng thi l lng trong n thi v p oxy ho vi sinh vt oxy ho cc ht hu trong n thi hi trong , ht l lng ng v i tr l ht nhn ho vi khun tr, sinh sn v pht trin d n ln thnh ng n gi l n hot tnh i khun v vi sinh vt sng dng ht nn ( O ) v ht dinh dng ( , ) lm th n huyn ho hng thnh ht tr khng ho t n v thnh t o m i lng n hot tnh sinh r trong thi gi n lu li trong Aerot nk lng n thi n u i vo trong khng lm gim nh nh ht hu do phi s dng li mt ph n n hot tnh lng xung y lng t 2, ng h tu n hon n v Aerot nk m o nng vi sinh vt trong h n n hot tnh d v n n n ho ng trnh x l n n kh x l. Aerot nk hot ng phi h thng ung p kh y v lin t u tr n l s n c k k - B B Qu trnh x l sinh hc k kh Qu trnh phn hy k kh l qu trnh phn hy sinh hc cc cht hu trong n c thi trong iu kin khng oxy to ra sn phm cui cng l kh CH4 v CO2 (trng hp n c thi khng cha NO3- v SO42-).

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I I B. N

H N

G H : B N

H N B N [6]

I. quy tr n

l nc t [6]:

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I. Thuy t m n quy tr n x l nc thi c thi t quy trnh cng ngh c dn qua song chn r loi b tp cht th c k h th c l n, s u n c thi c dn qua b gn bt thu hi lng tinh bt st li s u ng on ly tm, lng tinh bt ny thng nh hn n c, ni ln c v t em bn cho lm th n gi s , n c thi c dn qua b lng ct, ti y nhng ht ct c kch th c l n hn 0,2 mm s c gi li trnh nh hng n h thng m cc cng trnh ph s u c thi c dn qua b xt h kh CN - v i thi gi n lu n c l hai ngy, sau khi ra b id h , n c thi c pha trn NaOH v cht dinh dng to mi trng thun li cho cng trnh x l sinh hc ph s u c thi tip t s ng UASB, pH thun li cho hot ng ca b UASB l 6,7 7,5. Ti b UASB, cc vi sinh vt dng k kh s phn hy cc cht hu trong n c thi, hiu sut x l ca b A tnh theo CO , O t 60- 80% thnh cc cht v dng n gin v kh Biogas (CO2, H2S, CH4, NH3) theo phn ng sau: Cht hu + vi sinh vt k kh CO2 + CH4 + H2S + sinh khi m i + Ph n CN n li tip t c phn hy b UASB. Sau b A c thi dn qua b Aeroten x l trit cc hp cht hu Ti b Aeroten din ra qu trnh sinh hc hiu kh duy tr t my thi kh. Ti y vi sinh vt dng hiu kh (bn hot tnh) s phn hy cc cht hu n li trong n c thi thnh cc cht v dng n gin nh: CO2, H2O heo phn ng sau: - S oxy ha tng hp COHNS + O2 + dinh dng CO2 + NH3 + C5H7NO2 + cc sn phm khc - Phn hy ni bo C5H7NO2 + 5O2 5 CO2 + NH3 + H2O + nng lng Qu trnh phn hy ca cc vi sinh vt ph thu vo iu kin sau: pH, nhit , cc cht dinh dng, nng bn v tnh cht ng nht c n c thi o n phi theo di cc thng s ny trong b Aerotank. Hiu qu x l COD trong b t t 90-95%. T b Aerotank n c thi dn sang b lng, ti y din ra qu trnh phn tch gia n c v bn hot tnh. Bn hot tnh lng xung y c thi n h sinh vt tr khi c x ra ngun tip nhn. Bn hot tnh y lng mt ph n m tu n hon v b Aerotank nhm duy tr hm lng vi sinh vt trong b n d m vo nn bn trng l lm gim th t h u m n ngn khuy trn ca my l p ng ti khuy trn cng polyme, ri i qu h thng ng ti p bn. Bn thi ra c dng bnh em i chn lp hoc s dng lm phn bn.

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C th nhim v ca tng thi t b: 1. Song chn rc Song chn rc c nhim v gi li cc tp cht th k h th c l n nh r , v kho i m Cc tp cht ny c th gy ra s c trong qu trnh vn hnh h thng nh lm tc ng ng hoc knh dn, o n ng ng, thit b, tng tr l dng chy nn lm tng tiu h o nng lng m Qu trnh ly rc - Dng co ly rc khi cc thanh chn. - Cho rc va co vo thit b cha rc - n ni r nhn vin v sinh mi trng n thu gom nh k hng ngy v ch n ni x l cht thi rn tp trung. - Chu k ly rc song chn rc ph thu vo lng rc. Vic ly rc phi tin hnh ng qui nh v rc ng qu lu khng nhng gy mi hi thi m n gy cn tr ng chy t song chn r n b lng 2. B gn bt: B gn bt c tc dng tch cc cn rn k h th c l n v gn li vng bt ni ln trn, bt s c v t bng phng php th ng v em n ho s hn nui lm th n gi s 3. B lng ct Loi b ct, cui v nhng mnh vn v kh phn hy trong n c thi. Nu ct khng c tch ra khi n c thi c th gy nh hng n cc cng trnh pha s u nh mi n thit b, nh nh lm h m, lng cn trong ng mng n n phi s dng b lng t m bo cho cc cng trnh x l tip theo t hiu qu tt hn v hot ng n nh hn B lng ct c tnh ton v i vn t ng chy trong l n cc ph n t hu nh khng lng v nh ct v tp cht rn v gi li trong b. Trong b lng t ng ng, ng chy theo h ng ngang v vn t c kim sot theo k h th c b, ca phn phi u vo v mng trn u ra. Vn tc chy thng g n bng 0.15-0.3m/s, thi gi n lu n c t 30 90s. Ct sau lng c ly ra khi b bng phng php th cng, thit b m thy lc hoc s dng cc thit b kh nh gu cp, m trc vt, m kh n n, m phn l Ct s u n sn phi t 4. B Axit Ha o lu lng, thnh ph n, tnh cht n c thi ca nh my sn xut tinh bt ty thuc vo dy chuyn sn xut nn thng d o ng nhiu trong mt ngy m n nh ch ng chy ng nh ht lng n u vo cho cc cng trnh x l pha sau, c n thit phi c mt b iu ha lu lng. Kh CNtrong n c thi kho i m v x l mt ph n n c thi. Ti b axt ha, COD gim t 10-30% v ph n l n cc cht hu
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phc tp nh protein ht o, ng chuyn h thnh xt ng thi h u ht CN- c kh ht trong b axt ha. c thi sn xut bt m c pH thp nn rt thch hp cho cc vi khun axt ha. Trong b axt ha xy ra 3 qu trnh sau: - Qu trnh thy phn: Qu trnh thy phn cc cht hu thng th kh chm. Tc thy phn c quy nh bi pH, kch c ca cht nn, hiu qu ca cht nn. - Qu trnh axt ha: S to thnh xt h c thc hin bi nhiu nhm vi sinh vt. Ph n l n l cc vi sinh vt ym kh, nhng mt s c th ty nghi tc l chng c th dng oxygen. S lng hng thng rt thp ch khong 1% trong tng s lng vi sinh vt. Sn phm ca qu trnh l cc axt bo d y hi, ru, axt lactc, CO2 - Qu trnh acetate ha: Cc axt s b chuyn tip v dng et te, n c v CO2 iu kin t nhin CN- c th phn hy c n thi gi n kh di in hnh l trong 5-7 ngy khong 30% CN- b phn hy. Ti b xt h hm lng CN- c kh nhanh hn rt nhiu, thi gi n 2 ngy l lng CN- s gim khong trn 50% v khong 30% COD b phn hy. Qu trnh kh COD Cht hu phc tp cht hu n gin CO2 + H2S + NH3 5. B UASB T b xt n c thi m k kh UASB. Nhim v ca qu trnh x l n c thi qua b UASB l nh vo s hot ng phn hy cc vi sinh vt k kh bin i cht hu thnh dng kh sinh hc. Chnh cc cht hu tn ti trong n c thi l cht dinh dng cho vi sinh vt. S pht trin ca vi sinh vt trong b hi thnh 3 gi i on: - Gi i on 1: Nhm vi sinh vt t nhin trong n c thi thy phn cht hu phc tp thnh cc cht hu n gin c trng lng nh nh: onos rit, mino xt to ra ngun th n v nng lng cho vi sinh hot ng. - Gi i on 2: Nhm vi khun to men axt bin i hp cht hu n gin thnh cc axt hu l xt etic, nhm vi khun ym kh to axt l nhm vi khun axt focmo. - Gi i on 3: Nhm vi khun to mtan chuyn ha hydro v axt acetic thnh kh metan v cacbonic. Nhm vi khun ny gi l Mtan focmo. Vai tr quan trng ca nhm vi khun Mtan focmo l tiu th hydro v xt eti Chng tng trng rt chm v qu trnh x l ym kh cht thi c thc hin kh mtan v cacbonic thot ra khi hn hp. Hiu qu x l COD l 60-80%. 6. B Aerotank. c thi sau khi qua cc cng trnh x l hc v sinh hc bc I nng ca cc cht bn vn cn kh cao v vy nu p dng b Aerotank c in thng thng x l
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s khng m bo tiu chun p dng v khng t hiu qu cao. Aerotank xo trn hon ton l mt gii php kh thng dng v phng php ny ho ph p nng BOD5 vo b l 1000 mg/l m hiu sut x l ca cng trnh vn m bo yu c u. 7. B lng II: Chn b lng t II kiu b lng ly tm c tit din mt ct hnh vung. Lng hn hp n c bn t b aerotank dn qua. Lng cht l lng cn trong n c sau khi qua b aerot nk v c bn hot tnh n nng nht nh ph n cui ca b m tu n hon li b aerotank v ph n d r ngoi B lng 2 s phn phi n c bng ng ng t tm b v thu n c ra bng mng thu t xung quanh b. Trong b c thit b gt cn quay quanh tr t tm b gt cn lng y v h thu cn. Bn h s n b nn bn. 8. H Thc Vt c thi sau khi qua b aerotank th hm lng nit, photpho cn rt l n hnh v vy ta s dng thm h thc vt v i cc loi thc vt nh lc bnh, o tyn c thi sau khi ra khi b hm lng nit v photpho s t tiu chun loi B. 9. B nn bn Tch b t n c do mt ph n bn hot tnh t b lng 2, b A vo, lm gim s b m ca bn, to iu kin thun li cho cc qu trnh x l bn ph n tip theo. u m: - Thi gian khi ng ngn, vic kim bn hot tnh khi ng d dng v sn c. - Hiu qu x l sinh hc cao. - C th tn dng lng tinh bt tht thot, tn dng lng kh CH4 lm nng lng. - Nng xy nu trong n c thi ch bin tinh bt khoai m d o ng trong khong 19 96 mg/L, v i gi tr trng d o ng trong khong 22 34 mg/L. Tuy nhin, kh may mn l cc hp cht xyanua ny rt d t phn hy o , khi vn hnh h thng A trong dy gi tr nng xy nu trong n c thi thng khng quan st thy bt k nh hng bt li no n h thng, v nng xy nu u ra lun thp hn 1 mg /L. N c m: - Chi ph vn hnh l n. - Din tch xy dng l n. - Vn hnh i hi k thut cao - duy tr s n nh ca qu trnh x l k kh, phi duy tr c trng thi cn bng ng ca qu trnh theo 4 ph n nu (Thy phn, acid ha, acetate ha v methane ha). Mun vy trong b x l phi m bo cc yu t sau:
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+ Nhit Nhit l yu t iu tit ng c qu trnh, c n duy tr trong khong 30350C. Nhit ti u ho qu trnh ny l 350C. + pH pH ti u ho qu trnh d o ng trong phm vi rt hp, t 6,5 n 7,5. S sai lch khi khong ny u khng tt cho pha methane ha. + Cht d n dng C n cht dinh dng theo t l CO : : = (4001000):7:1 vi sinh vt pht trin tt, nu thiu th b sung thm rong n c thi sinh hot thng c cha cc cht dinh dng ny nn khi kt hp x l n c thi sn xut v n c thi sinh hot thng khng c n b sung thm cc nguyn t dinh dng. + kim kim ti u n duy tr trong b l 15003000 mg CaCO3/l to kh nng m tt cho dung d h, ngn n s gim pH d i mc trung tnh. + Mu i (Na+, K+, Ca2+) h meth ne h v id h lipid u b c ch khi mn vt qu 0,2 M NaCl. S thy phn protein trong ng c ch mc 20 g/l NaCl. IC50 = 4700 7600 mg/l. + Lipid y l hp cht rt kh b phn hy bi vi sinh vt. N to mng trn VSV lm gim s hp th cc cht vo bn trong. Ngoi ra cn ko bn ni ln b mt, gim hiu qu ca qu trnh chuyn i methane. i v i LCFA, IC50 = 5001250 mg/l. + Kim loi nng Mt s kim loi nng (Cu, i, Zn) rt , c bit l khi chng tn ti dng ha tan. IC50 = 1075 mg Cu2+ tan/l. Trong h thng x l k kh, kim loi nng thng c loi b nh kt ta cng v i carbonate v sulfide. Ngoi ra c n m bo khng cha cc ha cht , khng hm lng qu mc cc hp cht hu kh - UASB c th gy ra qu trnh mtan ha khng hon ton; kt qu l pH gim, qu trnh sinh kh biogas gim v hiu qu x l CO ng gim. Gi tr pH u vo thp c th nh hng ng k n hot ng ca qu n th vi sinh vt trong h thng UASB, do qu trnh mtan ha ch xy ra v i pH ti u trong khong 6,5-7,5. nh hng ny ng c th xy ra ngay khi pH khng qu thp khong 6,10. Kt qu nghin cu ch ra rng v i gi tr pH 6,10, ng gy nh hng bt li trong qu trnh vn hnh h thng, kt qu l hiu qu x l COD v qu trnh sinh kh biogas gim mnh, ngay c khi vn hnh v i pH nh trn h ko di trong vng 4h.
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- Mc d h thng UASB cho hiu qu x l cht hu rt o, nhng hm lng CO u ra thp hn 300 mg/ vn khng th t n trong trng hp p dng cho n c thi ch bin tinh bt khoai m t c tiu chun x thi Vit m, n c thi sau x l bng h thng UASB c n phi phi c x l trit tr c khi x vo ngun tip nhn. - Kt qu nghin cu ch ra rng cc ion [ v i nng thp hn 64 mg/ khng lm gim c tnh ca xyanua (do hnh thnh thio-cyanate) m thay vo n lm tng thm c tnh ca n. Tuy nhin, s c mt Fe2+ s lm gim ng k c tnh ca xyanua c trong qu trnh thy phn ln trong qu trnh mtan ha do c s hnh thnh phc cht fero-cyanide. D vy, s gim c tnh ny ng khng th kch thch qu trnh phn hy xy nu nh nh hn C. CNG NGH THCH HP X NC THI TINH BT KHOAI M [1] Nhng cng ngh truyn thng n gin khng p ng c nhu c u x l v qun l n c thi phc v cho pht trin bn vng, in hnh l ngnh ch bin tinh bt khoai m ti Vit Nam. Da vo cc kt qu nghin cu t c qui m phng th nghim, cng ngh thch hp x l n c thi tinh bt kho i m xut nh hnh v d i y :

Hnh 1.4. Cng ngh thch hp x l nc thi ch bin tinh bt khoai m.[1]
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y l ng ngh x l v i nhiu u im nh khng i hi qu nhiu nng lng, c th ti sinh nng lng t ngun kh iog s thu c, gim thiu ng k nhu c u s dng t rng l n cho h thng h sinh hc. Mt khc, thc t ho thy rng h thng x l k kh cao ti thc s c hiu qu i v i nhng loi n c thi ch hm lng cht hu o uy nhin, s u h thng x l k kh bao gi ng n c x l trit tip theo ng l l do ti sao c n phi p dng qu trnh x l trit v i h thng bn hot tnh hiu kh v s u l h thng h sinh hc t nhin, gim thiu nng cht hu v ht dinh dng n mc thp nht, t tiu chun x thi n c thi cng nghip hin hnh ti Vit Nam (ngun loi ) Gi i on tin x l v i thit b AF cp n ph n trn c th c xem l s la chn khng bt buc, bi v kt qu thc nghim ho thy rt r rng khng xy ra bt k tc hi nghim trng no do cht rn l lng gy ra trong sut 300 ngy vn hnh h thng UASB v i hm lng cht rn l lng nh hn 1 800 mg/ Hin ti, mt h thng x l th im, cng sut 10 m /ng c thit k v lp t (b qua thit b UAF). H thng x l ny c khi ng v vn hnh vo gia thng 2 nm 2006 ti nh my tinh bt khoai m KMC, tnh nh h c. Sau 73 ngy vn hnh, h thng A ng c vn hnh v i ti trng hu trong khong 6,2 7,4 kgCOD/m ng, hiu qu x l t c kh tt Hm lng CO u vo gim t 3.020 3.660 mg/L gim cn 620 1.040 mg/L u ra, hiu qu x l CO d o ng trong khong 72 82%. Kt qu vn hnh cho thy lng kh sinh r d o ng trong khong 260 350 L kh biogas (> 60% mtan) cho 1kg COD b kh ng kh iog s o c sau khi cho ton b kh sinh r i qu dung dch kim loi b CO2 v H2S. Thnh ph n ca hn hp kh sinh r h c phn tch chnh xc. Vic ng dng thnh cng cng ngh x l ny c th gp ph n ng k n s pht trin bn vng cho ngnh ch bin tinh bt khoai m ti Vit Nam.
3 3

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L XYANUA TRONG N TINH BT SN I. TNG QUAN V XYANUA [9] 1. Tnh cht l hc

NH MY SN XUT

- Axit xyanhydric (hay nitrifocmic) c cng thc ho hc HCN, trng lng phn t 27. th khan l cht lng rt linh ng, t trng d=0,696. Nhit si 200C, ng c -140C, c mi hnh nhn, v rt ng, ho tan rt d trong n v ru, l mt cht axit yu c pK~9,4 Hi a HCN c t trng d=0,968. - Cc mui xyanua kim nh C , C l mui tinh th trng, d b phn hu trong khng kh bi hi n c, CO2, SO2..., Tan rt tt trong n , t t n trong ru, tan trong dung d h n ru. Dung d h n c ca cc mui ny c tnh kim mnh. - Mui xyanua ca cc kim loi kim th tan nhiu trong n c, xyanua ca cc kim loi kh t n t hn - Mui xyanua thu ngn Hg(CN)2 t n trong n nhng l ht in ly yu. - Xyanua trng thi t do CN rt c (gi hung l nhn ngn) nhng khi n lin kt bn trong phc, th d phc Fe[Fe(CN)6] th li khng c. V s phn ly ca phc qu nh nn trong dung dch nng khng gy c. - ixy n (C )2 l cht kh c khng mu, mi hnh nhn, tan tt trong H2O v ru, (CN)2 hnh thnh do nhit phn mt s mui xy nu nh Hg(C )2 hay oxy ho CuCN bng FeCl3. (CN)2 km bn, do b thu phn. 2. Tnh cht ho hc - Axit xyanhydric v cc xyanua b oxy ho bi oxy trong khng kh chuyn thnh xianat: 2CN - + O2 2CNO- dung dch long 1:5000 trong 5 thng HCN b phn hu ht HCN + 2H2O 2HCN + 2H2S + O2 HCOONH4 (ammonium foocmic) 2HCNS + 2H2O (axit sunfoxyanhydric)

- Cc mui xyanua kim loi kim b dioxyt cacbon trong khng kh phn hu to thnh HCN. 2NaCN + CO2 + H2O 2HCN + Na2CO3 V vy phi bo qun mui kim loi xy nu trong thng kn, ch mt.
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- Cc mui xy nu t n trong n c d to v i cc xyanua khng tan thnh cc ion phc. - Axit nitric tc dng v i cc cht hu nh xit m li , xitri , n loit, t nin ng to nn HC Qu t ngh vic to nn cc glucosit xyanhydric mt s thc vt. - C ldehyt, ng ng ph hu c HCN C7H13O6N

C6H12O6 + HCN

- Trong mt s cc cy ci, thc vt c cha cc dn xut hu a Axit xyanhydric, v d: hnh nhn ng, nhn qu mn, l tr nh o, r sn, mng tre na, nm, cc ht l v cnh loi u phaseolus lunatus. D u hnh nhn ng c cha amogdalis C20H27NO11 do tc dng ca men emulsin hay synaptase s b thu phn v gii phng HCN: C20H27NO11 + 2H2O C7H6O + 2C6H12O6 + HCN Trong d u hnh nhn ng c 1,5g d u th 0,24g HC ng HCN cha trong nm, su ht hnh nhn git cht mt em b. Trong ht u c cht phaseolumatin C10H17NO6 do tc dng ca men phaseosaponin s thu phn v gii phng HCN: C10H17NO6 + H2O 3.1. c tnh - Axit xyanhydric tc dng ln qu trnh h hp t bo bng cch lm t lit cc men st ca xyto erom oxydaza ho men vacbua (Warburg). Do thiu oxy nn mu trong tnh mch c m u thm v c nhng triu trng ngt. - Axit xy nhydri gy nh nh qu ng h hp, v i liu lng 0,3mg/1kg trng lng th th gy cht ngay. Nng t 0,12 - 0,15mg/l gy cht t 30 pht n 1 gi. Qu ng tiu ho: liu lng gy t vong l 1mg/1 kg trng lng th i v i cc mui nh C , C - Axit xyanhydric c th thm nhp vo th ri gy ng c bng cch thm qua cc vt thng ngoi d Nng cho php tip xc nhiu l n trong khng kh l 10ml/m3 hoc 11mg/m3 khng kh 200. C6H12O6 + CH3 - CO - CH3 + HCN 3. c tnh ca axit xyanhydric v cc xyanua tan.

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3.2. Triu trng lm sng - Ng c cp: Xy ra khi ht phi hay ung phi liu cao HCN. Ng c xy ra rt nhanh chng, cc trung tm hnh tu b t lit, ngi b nn bt tnh, co git v cng. S h hp b ngt qung v dng li, tim p rt nhanh v khng u, nn nhn cht sau 1 - 2 pht. - Ng c bn cp: Cc hin tng thng gp l chng mt, bun nn, u u, cc nim mc h hp b kch thch. Nn nhn s hi, lo lng nhng vn cn sng sut, s u xut hin ri lon th n kinh, co git, d n ng t, cng hm, hin tng ngt bt u, nn nhn cht sau 20 pht. Nu cp cu kp thi, nn nhn khng cht nhng tn thng tim, t lit b phn. - Ng thng din: Xy r i v i nhng ngi lm vi thng xuyn ni kh HCN bc ln. Cc hin tng r rt l u u, chng mt, nn v mt nhc. 3.3. Cch cp cu, u tr - Nu b ng c bng ng h hp: nh nhn ra khi vng nhim , ngi lm cp cu phi eo mt n phng. Tin hnh ngay h hp nhn to, cho th xy hoc ca ongen loi nhanh cht qu ng phi. Tim cc thuc tr tim nh Caphein campho, niketamit. Nu try tim, tim thng vo tim ubain. ng thi v i vic lm cc cp cu, v n hi, h hp t bo c n tin hnh: + im tnh mch glutation liu 0,01 + Tim cc cht to nn methemoglobin. C ng th iu tr bng cc cht to nn methemoglobin khc: + im tnh mch 5-10ml dung dch 2-3% n trinitrit s u tim tip vi l n na (liu khng qu 1-1,5g) + im tnh mch 50ml dung dch xanh metylen. Ngoi ra c th dng cc thuc chuyn HCN thnh cht khng nh tim n tri tiosunphat (20ml dung d h 25% vo tnh mch) c th t i 200ml. - Nu ng qu ng tiu ho th dng v i pomo phin gy nn. Ra d dy v i dung dch 2% KMnO4, hoc v i pehyrol v cp cu nh nu trn II. P NG P P P XYANUA NHIM [9] 1. P n p p nh tnh
h m th hin : 7 K53 27 p: H u -

NG

I I

G H :

pht hin xyanua ta dng cc phn ng sau - To thnh mu xanh beclin Fe2+ + 6CN 4Fe3+ + 2 [Fe(CN)6]4[Fe (CN)6]4Fe4[Fe(CN)6]2 xanh beclin

Ly vo ng nghim 1ml dung dch nghin cu c cha CN - , tip thm vi git NaOH, mt vi git mui st 2(FeSO4), un n ng hn hp, sau xit ho hn hp bng HCl v thm mt vi git dung dch Fe3+(Fe2(SO4)3.H2SO4). - Phn ng Chinha hay picrosodic: Ly mt ng giy lc, l n lt nhng vo dung dch bo ho axit picric, xong nhng vo dung dch 10% Na2CO3, p kh bng giy l v phi trong ti (giy c mu vng). Khi c HCN tc dng vo, giy chuyn sang m u vng cam r rt ca isopurprin. tng nhn bit sau khi chun b giy th trn, tip tc nhng mt n ng giy vo xit xeti 10% trung ho cacbonat (vng ny tr nn c tnh axit s khng nhy v i HCN). Khi c HCN tc dng ng giy c hai mu r rt. hng php ny pht hin HCN trong khng kh, trong kho tng sau khi phun thuc chng rp c cn HCN khng. 2. P n p p n lng x nh lng xyanua trong ngun n , t t dng phng php n gin v d thc hin nht l chun th t h chun th t h xy nu dng phng php chun iot hoc chun bc. 2.1. P n p p c un iot Phn ng chun CN - + I2 + H2O Khi ht CN - th I2 + tinh bt CNO- + 2I - + 2H+ mu xanh

Trung ho dung dch cha CN - bng natri hydrocacbonat bo ho, tt nht l dng thng vi gam NaHCO3 bt, chun dung dch bng dung dch I2 0,1 N cho t i khi xut hin mu xanh ca ch th h tinh bt v i I2. 1ml dung dch I2 0,1 Phn ng chun
h m th hin : 7 K53 28 p: H u -

tng ng v i 0,00135g HCN

2.2. P n p p c un bc nitrat

I I

H 2CN - + Ag+

G H : [Ag (CN)2] -

im cui chun xut hin kt ta do [Ag (CN)2] - + Ag+ 2AgCN Kim ho dung d h nh phn c cha CN - bng vi gam NaHCO3 bt, s u thm vi git Cl lm tng ch th v chun bng bc nitrat cho t i khi xut hin kt ta khng tan mu trng c. 1 ml dung dch AgNO3 0,1 tng ng v i 0,0054g HCN III. CNG NGH X L XYANUA 1. a c n cid ho l nc anua [8] s la c n c d a l NKt qu nghin cu kh CN- trong n c thi tinh t m trn

aci h a [8]

Hm lng C - trong n thi kho i m trung nh khong 5 25 mg/l. Tuy nhin trong mt s trng hp it (n thi hm lng ht hu o), do ngun nguyn liu n u l kho i m trng lu nm ho kho i m ng (g tilissim ) nn hm lng C trong n thi kho i m th ln n 75 mg/l Chnh hm lng CN o l mt trong nhng nguyn nhn gy nh hng tr tip n hot ng ng trnh x l sinh h s u ny rong ng ngh m o tnh n nh h thng n ng ngh kh C -. Trong iu kin t nhin, pH thp, CN- cng c th t phn hy nhng khng trit v i hi thi gian phn hy di. in hnh l sau 5 7 ngy ch 30% CN c phn hy. Ti aci ho, hm lng CN- c kh nhanh hn so v i tn tr t nhin ng thi tc kh CN- ph thu c vo hm lng CN- an u trong n c thi. Khi hm
h m th hin : 7 K53 29 p: H u -

I I

G H :

lng CN- nh hn 12 mg/l, ch cn 2-4 ngy khong 90-100% CN- c x l v khi hm lng CN- cao hn khong 16 35 mg/l cn khong 5 ngy m i c kh nng x l 70% CN-. Trong nc thi tinh bt m, CN- tn ti di dng linamarin, di tc dng ca enzim trong mi trng acid, linamarin b phn hy to thnh glucose, aceton v acid cyanhydric theo phn ng [8]:

Trong iu kin t nhin, linamarin di tc dng ca enzim s chuyn ho theo c ch: CN- + O2 + enzyme CNOCNO- + H2O NH3 + CO2 Hoc: HCN + 2H2O NH4COOH Ti b acid, di iu kin k kh s din ra cc phn ng sau: CN- + H2S HSCN + H+ HSCN + 2H2O NH3 + H2S + CO2 hn hung phn ng kh C u ho sn phm ph H3. i id h hm lng v CO x l kh o (10 30% CO x l) h thng hot ng hiu qu n thit k id h x l trit C - v gim ti trng ho ng trnh x l s u 2. c p n p p l xyanua Xyanua rt d b phn hu thnh nhng cht khng c bi cc tc nhn ho hc. V vy, bin php x l ho hc cht xy nu l n gin, r tin v d thc hin nht. Tuy nhin, ty tng trng hp c th ngi ta vn dng phng php x l khc nh u i y l mt s phng php x l:
h m th hin : 7 K53 30 p: H u -

I I

G H :

2.1. P n php oxy ho [9]: Xyanua d b oxy ho bi t nhn oxy ho thng thng nh lo, hydropeoxyt, focmandehyt, permanganat, axit peoximonosunfuric (H2SO5), persunfat v.v... Nguyn tc: oxi ha xyanua t do v phc ca n thnh hp cht t hn, yanat ho kh nit v oni Cht oxy ha c th l: n c Clo, H2O2, NaOCl, CaOCl2, KMnO4 u kin ti n hnh: oxi ho cc xyanua ph thuc vo: - Loi cht oxi ho s dng, nng xyanua t do v phc cht, pH ca dung dch. - Liu lng cht oxi ho quyt nh m sch c n c sau x l, nhng liu lng ny ph thuc vo nng xyanua v dng tn ti c hng trong n c thi, vo pH v bin ng pH trong qu trnh x l. Nng xyanua cng long cng tn nhiu cht oxi ho h vy m i oxi ho trit xy nu c.

Hnh 3.1. Thit b lm sch nc thi theo chu k, c h thng cn bng v iu chnh [9] 1- my trn n c thi v i cht phn ng, 2-thng phn ng, 3- n iu khin t 4-dng c o, 5- n ong, 6- m
h m th hin : 7 K53 31 p: H

ng,

u -

I I

G H :

cng ngh thit b lm s h n c thi xy nu c trnh by trn. C th vn hnh t ng, lin t h y gin on, th cng. Trn n c thi v i cht phn ng hay dung dch thi b bng khuy , my trnkhng dng kh n n khuy. 2.1.1 Oxy ho bng kh clo, n c giaven hay clorua vi. Tc nhn oxy ho y chnh l hypocloril OCl [9] :

Hnh 1.6.S cng ngh lm sch nc thi xyanua lin tc bng kh clo [9]. 1-b gom n c thi, 2-b cha kim , 3- n iu khin , b cha oxit, 5- thit b phn ng, 6- trn, 7- m c x l qua mt quy trnh h i gi i on Gi i on u tin l oxy ha xyanua thnh xyanat bng cch s dng t nhn oxy h nh Clo h y Natri hydroclorit trong mi trng kim (pH o) Gi i on h i l oxy h y n t (t c hi hn y nu ) thnh on dioxit v nit thng qu vic s dng nhiu hn Clo h y tri hydro lorit pH thp hn so v i gi i on u. - Phn ng ha hc din r trong gi i on u nh s u: CN- + OCl- C O- + C lC + OCl OC + Cl

2NaCN + Ca(OCl)2 2 2NaCN + Cl2 + 2

h m th hin : 7 K53

OC + C Cl2 OC + 2 Cl + H2O
p: H u -

OH 2

32

I I

G H :

Vic oxy ho xyanua thnh xyanat din r c l nh oxy nguyn t tch ra t cc cht oxy ho, ch khng phi oxy phn t tch ra . Lu : Khi dng clo lng ng phi lu rng khi ho t n lo vo n c s xy ra hin tng axit ho theo phn ng. Cl2 + H2O HCl + HOCl T l ngoi xit hipo lor n to thnh axit clohidric. V vy khi dung clo lng oxy ho xyanua phi thng xuyn cho thm kim trung ho axit clohidric t do, nu khng s to ra cloxiyan mt sn phm c ca qu trnh oxy h trc tip xyanua. 2CN- + Cl2 2ClC - Phn ng ha hc din r trong gi i on h i nh s u: tri xi n t ( OC ) t hn nhiu v d phn hu to nn sn phm khng c. Thc hin quy trnh tiu hu pH = 11-12. pH = 5 - 8 xyanat c th b oxy ho tip: 2NaOCN + 3NaOCl + H2O 2 2NaOCN + 3Cl2 + 6NaOH 2 HCO3 + N2 + 3NaCl HCO3 + N2 + 6NaCl + 2H2O

hng nu 8 < pH < 10 s xy ra phn ng ph bt li: NaCN + NaOCl + H2O C Cl + 2 v CNCl + 2NaOH + H2O OC + OH (xyanua clorua d Cl + 2H2O y hi v rt c)

Bi vy qu trnh tiu hu phi khng ch pH = 11,5 khng xy ra phn ng ph sinh ra CNCl. Sau khi phn hu ht (CN -, CNO-) c th h thp pH xung 5-8 phn hu trit CN- thnh nhng sn phm khng c. Cc tc nhn oxy ho ny ph hu CN - rt mnh v trit nhng k thut thc hin tng i ngt ngho. x l xyanua quy ra 1kg HCN c n dng 3,9 kg lng Clo m bo thng phi dng gp i, khuy trong b l n lin tc trong mt gi. Trong qu trnh trung ho xyanua c to ra hydroxit Ca(OH)2, Pb(OH)2, Fe(OH)3, gi pH t 7,59 kim tra. u m Cng ngh thit lp tt Cy n te l tng i t hi v tip t nit pH thp hn oxy h thnh r on dioxide v

h m th hin : 7 K53

33

p: H

u -

I I

G H :

N c m: h hypo lori l hi; o sn phm hi; hi ph t; Clo phn ng v i ht hu hnh thnh hp ht Clo; ngun hypo lori t 2.1.2. Oxy ho bng ClO2 [9] Clodioxyt c ch to ti ch bng tc dng ca mui NaClO2 v i Cl2 hay axit clohydric: 2NaClO2 + Cl2 5NaClO2 + 4HCl Oxy ho CN - n 2ClO2 + 2NaCl 4ClO2 + 5NaCl + 2H2O

n t hn 1,2 kg ClO2/1kg CN -

Ni chung vic oxy ho CN - bng tc nhn ClO phn t hoc Clodioxyt phi thc hin k nghim ngt khng gy c hi cho nhng ngi thao tc thc hin quy trnh. 2.1.3. Oxy ho bng ozon [2] Ozon : - Ozon l ht oxy ho - Ozon l hot tnh o
-

o v ho t n trong n

l n

- n trong mi trng xit hn so v i mi trng kim kh nng oxy ho rt - dng nhng oxy nguyn t hot tnh ho tp ht hu . nhn ny t c hi hn lo, thc hin n gin hn v oxy ho C cht khng c. - Gi i on 1: Ozon oxy h CN - + O3 tr tip xy nu to thnh y n te: OCN - + O2 trit thnh

- Gi i on 2: u s dng hm lng ozon d th y n te oxy h to nitrogen v r on te (ho i r orn te, ty thu pH) theo phng trnh phn ng: OCN - + O3 + 2H2O NH3 + HCO3- + 1.5O2 rong iu kin n, xyanat thy phn sn lng amoniac, s u b oxy ha bi ozon to thnh nitr te theo phng trnh phn ng s u y: CNO- + OH- + H2O NH3 + 4O3+ O3 NH3 + CO32NO3-+ H2O+ 4O2+H+

Thi gian phn ng cho qu trnh oxy ha xyanua hon thnh nhanh chng trong mt h thng l phn ng v i 10 n 30 pht thi gi n lu l in hnh C phn ng gi i on th h i l hm hn nhiu v i gi i on th nht hn ng ny thng c thc
h m th hin : 7 K53 p: H u -

34

I I

G H :

hin pH 10-12 t phn ng l tng i n nh. Nhit khng nh hng n tc phn ng ng k Bng 3.1: l ianua bng ozon [2]

Kt qu cho thy rng qu trnh oxy ha ca cyanide ph thuc ca vic b sung ozone. Qu trnh oxy ha ca cyanate bi ozone l mt phn ng chm so v i cc y nide, v do , y n te t h l y trong khi xy nu g n nh l hon ton oxy ha.

Hnh 3.2: nh hng ca nng xianua ban u v t l ozon vo tc ca qu trnh o y h a ianua [2] Hnh 3.2 cho thy qu trnh oxy h xy nu tng ng bi tng t l ozone v khng ph thuc vo nng xy nu n u trong dung dch. l ng r rng t con s ny, l xy nu trong dung dch gim tuyn tnh v i thi gi n, do ho thy rng tc qu trnh oxy h l khng i v tng t l thun v i s gi tng t l ozone.
h m th hin : 7 K53 35 p: H u -

I I

G H :

- Thi t b ozon ha c nhiu dng lo m, loi thp si bt...

u m: - T l dng: 4,6kg O3 cho 1kg CN Oxy ho n c thi xyanua bng Ozon, KMnO4, FeSO4, c nhiu u im v mt cng ngh hn dng lo v hng khng sinh r hp cht trung gi n y hi Oxy ho n c thi xyanua bng ozon thch hp ho trng hp c n x l khi lng n c thi l n m trong h tion ng, km nu khng c lm sch thm c th dng li n c sn xut c xng. - Gim c tng lng n trong n c x l do phn hy c xy nu v ui c ht oxi, nit v mt ph n H2CO3. - Ozon sn xut t khng kh ng h s dng mt my pht in ozon. ng Ozone kh nh u, t 5 n 25 mg / l khng kh, ty thu vo thng s my pht in ozone ( khng kh, dng hy, in my pht in, vv) v nng th t 35 mg / l v i oxy tinh khit. - Ozone l mt t nhn oxy h mnh m, n ung p li th m t ho khng phm hi hnh thnh s u khi x l n thi h xi nu - Khng i hi nhit o v p l . sn

N c m sn sinh r mt lng mmoni , hi ph ht phn ng /thit

h m th hin : 7 K53

36

p: H

u -

I I

G H :

2.1.4. Oxy ho bng hydroperoxyt (H2O2) [3] Hydroperoxyt ng l ht oxy ho mnh lit CN - thnh cht khng c phn ng c n c xc tc. Cu 2+ (x t x dng ho phn ng l kim loi huyn tip nh ng h t n, v n dium, vonfr m ho nng 5 - 50 mg / L) CN - + H2O2 OCN - + H2O (pH=9-10 / ht x t ) n phm phn ng H2O2 l cyanate (CNO-) l t hi hn so v i xy nu 1 000 l n v thng hp nhn ho x r ngoi mi trng phi duy tr pH = 9-10 trnh s hnh thnh kh hydrogen y nide (HC ) - phn ng th tng thm khi th y i mt s yu t nh: + + ng nhit ng liu lng ht x t

+ dng H2O2 d th d: + i 25 C v khng mt 2-3 gi ht x t , huyn i xy nu thnh y n te t do

+ i 50 C, mt gi ho t hn + hi thm 10 mg/l Cu s tng t gp 2-3 l n, trong mt thi gi n vt qu 20% hydrogen peroxide s lm tng t l khong 30% goi r , y n te th ph hy thng qu thy phn xit, to thnh dioxide v ammonia. hng trnh l: OCN - + 2H2 O2 CO2 + NH3 + OH r on

H ng thp, qu trnh thy phn ng nh nh hn: pH =2, thy phn C O trong 5 pht pH= 5 trong 60 pht. pH =7 trong 22 gi.

- T l dng 3,3 lt H2O2 35%/1kg CN Vic dng H2O2 hay O3 c th oxy ho c phc xyano ca st rt bn v xyanua hu
h m th hin : 7 K53 37 p: H u -

I I + i l

G H :

hn h thng peroxygen ph thu vo :

hi gi n phn ng

+ C sn phm mong mun ( y n te, ho CO2 v H3) + C loi xi nu ng x l (t do, xit yu phn ly, ho tr) + h nng kinh t H thng ny n gin, x l xi nu t do v hp ht xi nu (v i km, ng, ho dmium) i t k h thng peroxygen, pH 10/09 nn duy tr nu i nu mt, trnh s hnh thnh kh hydrogen y nide (HC ) u m d tha cht phn ng phn hy n c v oxy; ng i n gin hot ng. N c m ht phn ng tn k m, yu u o lng hnh x 2.1.5.X l ng Aci Peroxymonosulfuric(Caro axit) [3] Caro axit l mt sn phm c hnh thnh t cn bng hydrogen peroxide v acid sulfuric, v thng c sn xut ti ch bng cch s dng mt my pht in, m-un nh gn : H2O2 + H2SO4 H2SO5 + H2O Qu trnh ny s dng ti mt s im hot ng tinh luyn vng l n nht th gi i Axit ho hot ng quy m nh hn, aixd C ro th hun thng qu thy phn ,v d: amoni persulfate : (NH4)2S2O2 + H2O NH2HSO2 + NH2HSO2 (H2SO2 / hi) huyn i y nide y n te hon tt trong mt vi pht, theo CN- + H2SO2 CNO- + H2SO4 (pH 10) i sung d th axid C ro s thy phn cyanate thnh on t v nit trong ng mt : 2OH- + 2CNO- + 3SO52- 2CO32- + N2 + 3SO42- + H2O
h m th hin : 7 K53 38 p: H u -

i acid C ro, vi phng trnh s u:

I I

G H :

rong iu kin tnh xit, mt lng nh xit C ro s l n thit k t khi y n te thy phn (phn ng th h i d i y) l tng t rt nhiu. C phng trnh nh s u: 2H+ + 2CNO- + 3H2SO5 2CO2 + N2 + 3H2SO4 + H2O CNO- + 2H2O CO2 + NH2 + OH2.1.6. Oxy ho bng hydroperoxyt v natrihypoclorit H2O2 + NaOCl [9] 2CN - + H2O2 + OCl 2OCN - + Cl - + H2O y khng i hi pH o nh khi dng mt mnh mui hypoclorit, khng phi thc hin ch pH nghim ngt phng sinh r kh c. V khng c n thm nhiu OH iu chnh pH nn tit kim c 30% chi ph. 2.1.7. Oxy ho bng H2O2 + HCHO (focmandehyt) [10] * Ring H2O2: CN - + H2O2 * Ring HCHO: CN - + H-C =O + H2O H [Zn(CN)4]2- + 4HCHO + 4H2O * Hn hp H2O2 + HCHO: HO-CH2-C N + H2O HO - CH2 - C - NH2 O xc tc OHHO-CH2- C (glucolonitril) 4HO-CH2-C N + 4OH- + Zn2+ OCN - + H2O

N + OH-

i tc dng ca vi khun, sn phm ny phn hu thnh mui glucolat HO-CH2 COO- khng c hi. 2.1.8. Oxy ho bng KMnO4 [10] Kh n c thi bng KMnO4: thch hp ho nng sut nh v trang thit b vn hnh n gin nhng t do KMnO4 cao. Oxy ho bng KMnO4 xc tc Cu2+ 3CN - + 2MnO4- + H2O pH qu trnh l 9,5, pH ng 2MnO2 + 3OCN - + 20Ho th phn ng xy r ng nh nh

T l dng c n 4,05 kg KMnO4/1kg CN - h vy dng tc nhn oxy ho ny kh t v li nhng sn phm h n ton ho mi trng.
h m th hin : 7 K53 39 p: H u -

I I

G H :

I ht

hit dng th hin qu trnh oxy ho thng l loi khuy trn nu phn ng l th lng ho rn- lng v l loi thp nu l th lng- kh 2.1.9. Oxy ho bng oxy khng kh v than hot tnh khi c CuSO4 xc tc than hot tnh [10] 2CN - + O2 Cu2+ OCN - + H2O HCO3- + OH 2Cu2+ + 2OH- + CO3 2Vic xut hin kt t b sung cht xc tc. 2.1.10. c tc quan onn t HCO3- + NH3 CO3 2- + H2O CuCO3. Cu(OH)2 2OCN -

z ho thy xianat b thu phn; c th thm Cu2+

tan um d o de [2]

rong vi nm qu , x t qu ng ng ht n dn tinh th hiu i nh sng tinh th g n tm thy, hiu qu trong vi oxy h ht nhim hu nht nh n loi t nguy him hn theo iu kin phn ng nh hng php ny tm thy l th h hp ho qu trnh oxy h xi nu t do v xianuacomplexed ha tan trong n ht thi. Qu trnh ny hot ng ng h cho n thi kt hp v i nh sng mt tri v mt ht x t n dn Cht x t thng s dng l titanium dioxide (TiO2). Cht x t ny th trn ln vo trong n , vi to r mt n, ho nh vo mt kiu u tr mng tinh th n hy thng qu ho th s dng dng keo hi tip x v i nh sng mt tri, ht x t hp th photon nng lng cao t ph n ti tm qu ng ph mt tri, to r g hydroxyl. C g t do l oxidizers phn hy mnh m y nide v sn phm u tin qu trnh oxy h x t qu ng h xi nu trong s hin din iO2 tinh th trong mi trng n l C Ou im: loi hon ton sn phm khng mong mun h im: kh vn hnh; hi ph tn k m; yu u nng lng o 2.2. P n p p n phn [10] hng php ny d dng lm s h n c thi ca nhiu xyanua t cc b r ngc chiu, nhiu bc hoc cc dung dch xyanua hng c n hu b, c nng xyanua khng d i 500- 600 mg/l. Khi x l s sinh NH4+, xyanat, Na2CO3, ure, trn tot thng c kim loi thot ra. Anot c th l thp khng g c thi cha nhiu xyanua nn cho thm NaCl hoc NaOH ri m i in phn v khi ti anot ngoi oxy cn c ion ClO-,
h m th hin : 7 K53 40 p: H u -

I I

G H :

lm tng thm t dng oxi ho nng cao hiu qu lm s h n c v tit kim in nng tiu th oxy ho 1g xyanua c n t 0,4 n 2kWh. Khong cch gia ant v catot l 30-50mm. Mt dng in 1-2 A/dm2. Mui NaCl 3-6 g/l. 2.2.1. in phn dung dch cha CN rong mi trng kim ( z) dng c CN - c oxy ho thnh xianat: CN - + OH[Zn(CN)4]2- + 8OH i n t c to thnh b phn hu oxy ho: 2OCN - + 6OH2HCO3- + N2 + 3H2O + 8e Nu dung dch c nng CN - qu thp nn dng H2SO5 hay H2S2O8 oxy ho. 2.2.2. in phn dung dch cha CN - c thm NaCl (3-5%) Thc cht y l trng hp oxy ho CN - bng NaOCl v trong dung d h khi in phn th NaCl NaOCl, v: CN - + OClH2O + 2OCN - + 3ClOOCN - + Cl 2CO2 + N2 + 3Cl - + 2OHOCN - + H2O+2e Zn2+ + 4OCN- + 4H2O + 8e

C h ny u tin hn h in phn trc tip v n c th x l n c thi cha nhiu ho t xy nu u tt. Thit b ch to ClO kh n gin, c th tn dng thit b c sn v lp t ngay ti trm x l n c. Thit b c n dung t h l n cha c 1-5kg clo hot tnh. C 1kg clo hot tnh c n n 8- 10kwh in nng v 5-7kg mui n Sau khi oxi ha xyanua c n phi tch kim loi nng trong n c thi. Khu ny c tin hnh ng thi v i vic lm s h n c thi kim-axit c xng hay nh my. 2.3. Phng php to phc kt ta [10] y l phng php in nhng u im l chi ph thp v d thc hin. Tc nhn to phc kt ta l mui sunphat st hai hoc hn hp st hai v st ba. Cc phn ng din t nh s u: rong mi trng kim ( z) Fe O4 tc dng v i CN Fe2+ + 2CN Fe (CN)2 + 4CN [Fe(CN)6]4- + 2Fe2+
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Fe (CN)2 [Fe(CN)6]4Fe2 [Fe(CN)6]

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3Fe2+ + 6CN T l dng: 5,35 kg FeSO4 cho 1 kg CN -

Fe2 [Fe(CN)6]

Thc t trong dung tch c ln Fe3+ nn kt ta c m u xanh prusse hoc khi dng thm mui Fe (SO4)3.H2SO4 t thu c kt ta xanh prusse. [Fe(CN)6]4 - + Fe3+ 2.4. c k n k v o nc t n m [14] Gii php n gin nht kh xy nu l s khng kh vo n nhim xy nu h m n hp ph CO2 to r H2CO3 xit oni l loi xid yu nhng n vn mnh hn xit HC v nh vy n s y HC t mui xy nu HC ho l y hi h y huyn h thnh HOC t hi hn u HOC v i s mt oxy phn t s huyn h h y thy phn thnh moni v CO2: HOCN + H2O CO2+ NH3 Fe[Fe(CN)6]-M+ C kt t c tch khi n c bng phng php lng hoc lc

h i phn t H3 v mt phn t CO2 s to r ( H4)2CO3 mt phn t CO2 d s h t n trong n v li huyn ion xy nu thnh HC h vy qu trnh kh xy nu trong n thi s din r rt thun li do t p ngun CO2 qu trnh phn ng din r nh nh v hiu qu ngi t phi s khng kh n n vo n nhim. V hm lng CO2 trong khng kh thp nn l u phn ng to r HC din r rt hm hp, tuy nhin v s u CO2 to r ng y trong qu trnh kh xy nu nn phn ng n i trn s duy tr kh n n vo n nhim l vi tng i d lm nh my n n tu in, thit hy ng thy l h y s gi 2.5. P n p p s n c Enzyme x l c t thi xyanua, Cyanide hydratase [11]

Cyanide hydratase, hoc formamide hydro-lyase l mt enzyme c kh nng huyn ho cyanide trong n c thi cng nghip thnh amoniac v formate thng qua mt c phn ng Cy nide hydr t se c phn lp t mt vi loi nm v c to ra t nm khi nng xyanua thp hi c c nh, tnh bn c Cy nide hydr t se tng ln nhiu v enzyme t Gloeocercospora sprrghi bn vng hn t Stemphylium loti .Cyanide hydratase t nm thch hp x l cc cht thi cng nghip cha xyanua.

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Mt s vi khun Gram-(-) nh Alcaligenes denitrificans ng tit ra cyanidase c i lc bn cao v c kh nng loi xyanua nng rt thp, v d nh < 0 02 mg/ CN-. Sau ny, khi cng ngh sinh hc pht trin, ngi t t h c gen cyanidase t Pseudomonas stutzeri AK61 Pseudomonas pseudoalcaligenes. Hot tnh ca cyanidase khng b nh hng bi cc ion thng thng c mt trong n c thi (v d nh Fe2+, Zn2+ v Ni2+), hay bi cc cht hu nh t t, form mide, et mide v etonitrile pH ti u trong khong 7.8-8.3 v mt hot tnh hon ton, khng phc hi khi pH cao hn N o ra c n c Phng php thy phn chng ct CN- t thy phn trong n to thnh dung dch hydrogen cyanide v tip tc y hi to thnh kh hydrogen cyanide, nhit cao v p l l n, b bt trong thp hp th c r c hoc thng hi vo kh quyn. hng php n gin. u u nhit o, p l v khng kh ; n xut kh hydrogen y nide mt l n n kh khn x l . Phng php th m thu ngc p lc p dng trn mt n c cho i qu mt mng t bo, thm xyanua u u p l t n ngoi u, n c m ca cc p n p p [2]: hng php oxy h u im: nhanh, khng b nhim bn tr li v CN- b phn hy hon ton. h im: iu kin phn ng nghim ngt, cng ngh t tin. hng php in ha u im: cng ngh n gin hc: khng hon ton, tiu tn in c v nng lng nhiu. hng php to kt ta u im: ha cht r, cng ngh n gin h im: khng hon ton, hiu sut khng cao

hng php sinh h u im: hng php t nhin; C th x l C - m khng to r mt dng thi khc; Khng x l h ht thit , kim sot tn k m n thit; Chi ph l nh

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v i khi lng l n hn ht thi; hng sn phm ph hi, do thn thin v i mi trng h im: ng ngh h thit lp tt; khng th x l nng o hng php CO2/ khng kh u im:n gin, r tin, lm vi trong pH rng h im: n x l t hng php in phn u im: x l tt n thi xi nu t k nng no h im: khng n ton, tiu tn in v nng lng nhiu Cy nide hin ng x l h yu d trn ng ngh h h , nhng quy trnh x l sinh h g n y s dng thnh ng l n quy m hot ng i pht trin v ng dng ng ngh sinh h phn hy y nide gi i hn h yu i yu t vt l hng php x l sinh h thn thin v i mi trng v th xem l ng tin y v hiu qu kinh t r khi p dng ho t k qu trnh x no l n thit it hi tit tnh ht thi, v hnh thnh v n nh y nide phng php p dng th h hp 2. P n p p c n nn yanua sau k l nc t [10] ng xy nu n li khng vt qu 0,01 mg/l ferok lixy nu v ferik lixy nu khng vt qu 0,04 mg/l phn t x nh nnng xy nu s u khi x l thng dng phng php Colorimetr v i thu th pir zin ( C4H4N2 ) n gi l phng php iridin- ir zin hng php ny hnh x o, kh nng x nh nng xy nu vi ph n trm milig m xy nu trn mt lt - tin hnh phn t h ngi t phi ph h mt lot dung d h mu hun : y

Cn chnh xc 0,0508 g I2 ha tan trong 100ml CCl4 trong nh u nh m 20ml dung d h ny ph l ng ng CCl4 trong nh u nh m n 200ml y mu 1ml, l n lt ph l ng 1, 2, 3,9ml n ng v i nng xy nu t 0,1 n 1mg/l

nh vy t lot mu tng n phn t h,

- in hnh phn t h mu: ho vo nh o dung t h 25ml, 1ml dung d h s u ph lo ng ng 1ml n t

- ip theo ho thm 0,1ml dung d h lor min 1% ng ht nt nh o, l nh n thn u 1pht, thm 4ml thuc th pir zin, ng nt nh o, l nh n thn
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Dung dch pirazin c chu n b nh sau : n 0,5g pir zin ho vo 100ml n t 0 un dung d h ln 60 C, khuy u dung d h, s u khi lm lnh hop n n th t h yu u - hm 4ml piridin, y np nh o, l u dung dch, em so mu v i dung d h mu trn ng Colorimetr

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KT LUN Tinh bt sn hin nay l mt trong nhng ngnh cng nghip rt qu n tm i v i h u ht n ng pht trin y ng l mt ngnh sn xut s dng n tng i l n v nng cc cht nhim trong n c thi cao.V vy n c thi ra t cc nh my c n c quan tm mt h c bit v c n c gii php c th m bo c mi trng v li ch kinh t. V i ti l n c thi c nhim C trong qu trnh sn xut tinh t sn,qu qu trnh tm hiu tnh n c thi ti nh my nh s u:

Trong bi tiu lun ny hng ti r quy trnh ng ngh, phng php x l v phn t h u nh im ca tng quy trnh, phng php x l c hiu qu n c thi v lng C trong n c thi. Do kin thc kinh nghim cn hn ch.nn vic tm hiu v xy dng ti khng trnh khi thiu st rt mong nhn c s ng g p kin ca th y c v cc bn. Mt l n na chng em xin chn thnh cm n th y gio TS. Phm tnh ch bo v h ng dn chng em trong qu trnh lm bi tiu lun. un i tn

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1. Huynh Ngoc Phuong Mai - Integrated Treatment of Tapioca-Processing Industry Wastewater: Based on Environmental Bio-Technology/Wageningen: Wageningen University - PhD-Thesis Wageningen University, Wageningen, the Netherlands with summaries in English, Dutch and Vietnamese. ISBN 90-8504-441-3 2. Destruction of cyanide waste solutions using chlorine dioxide, ozone and titania sol J.R. Parga et al. /Waste Management 23 (2003) 183191. 3. Cyanide Treatment with Hydrogen Peroxide ( http://h2o2.com/industrial/applications.aspx?pid=106&name=Cyanide-Treatment ) 4. An Overview of Removal Methods of Cyanide from Industrial Wastewater 5. Tr n n hn, g h Nga. Gio trnh cng ngh x l n thi- NXB khoa h k thut- H Ni 2005. 6. n Mn Hc X c Thi c Cp - GVHD: Nguyn Xun Hon 7. Hong Kim Anh, Ng Th ng, guyn Xch Lin_Tinh bt sn v cc sn phm t tinh bt sn. Nh xut bn Khoa hc v K thut, H Ni _2006 8. Hin trng nhim v gii php x l n thi ho lng ngh tinh t Hoi Ho nh nh nh, guyn n h guyn h h nh hng, trng H h Khoa TP.HCM. 9. Tr n Ngc Qunh - G H : s ng im rit , X l n c thi xianua trong cng nghip m in ( http://www.scribd.com/doc/28738075/noidungmadien ) 10. Quy trnh ng ngh tiu hu ho ti s dng Xyanua 11. ng l i ng dng Enzyme trong x l ph thi- Tp ch Khoa h i hc Quc gia H Ni, Khoa hc T nhin v Cng ngh 23 (2007) 75-85. 12. http://orientbiofuels.com.vn/index.php?option=com_content&view=article&id=67%3 Atng-quan-v-cay-sn&catid=48%3Atng-quan-v-cay-sn&Itemid=68&lang=vi 13. http://xulymoitruong.com/xu-ly-nuoc-thai-san-xuat-tinh-bot-san-3-2283/ 14. http://yeumoitruong.com/forum/showthread.php?2468-M%E1%BB%99tbi%E1%BB%87n-ph%C3%A1p-%C4%91%C6%A1n-gi%E1%BA%A3nkh%E1%BB%AD-xyanua-trong-n%C6%B0%E1%BB%9Bc-th%E1%BA%A3i%C3%B4-nhi%E1%BB%85m

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Trang ....1 K I. G NG N 1 N D NG N....2 N B N3 ...2 NG QUAN V NGNH SN NG .3

1 Cu to kho i m.3 2. Phn loi khoai m .3 3. nh hnh sn xut tinh t sn it II. N N m v th gi i.4

4. Mt s quy trnh ng ngh sn xut tinh bt. ....7 P N NG NG N B N N B N 9

1. Thnh ph n cc cht trong n c thi ca nh my ch bin tinh bt sn 9 2 . ng ca cc cht trong n c thi 11 NG NG N P NG P P N NG N N N B N 12 A. P NG P P 12 12 12 13 13 14 15 N...17 17 18
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I. H G H C HC II. H G H HA III. H G H HA HC IV. H G H I H HC

1 l n thi ng phng php sinh h trong iu kin t nhin 2 l n thi ng phng php sinh h trong iu kin nhn to B. N N N B N N B I. quy trnh x l n thi

II. Thuyt minh quy trnh x l n c thi

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C. CNG NGH THCH HP X NC THI TINH BT KHOAI M......23 NG N NG N N SN XUT TINH BT SN 25 I. TNG QUAN V XYANUA ...............................................................25 1. Tnh cht l hc 3 c tnh ca axit xyanhydric v cc xyanua tan 25

2. Tnh cht ho hc..........................................................................................................25 26

II. P NG P P P N NH HM N G X Y A N U A N H I M ..............................................................................2 7 1 2 hng php nh tnh hng php nh lng 27 28

III. CNG NGH X L XYANUA ..................................29 1. hn A id ho x l n xi nu 29 2 C phng php x l xyanua 30 2.1. hng php oxi h 30 2.1.1 Oxy ho bng kh lo, n c giaven hay clorua vi. 32 2.1.2. Oxy ho bng ClO2..................................................................................................34 2.1.3. Oxy ho bng ozon..................................................................................................34 2.1.4. Oxy ho bng hydroperoxyt (H2O2) 37

2 1 5 l ng A id eroxymonosulfuri (Caro axit)38 2.1.6. Oxy ho bng hydroperoxyt v natrihypoclorit H2O2 + NaOCl.............................39 2.1.7. Oxy ho bng H2O2 + HCHO (focmandehyt)39 2.1.8. Oxy ho bng KMnO439 2.1.9. Oxy ho bng oxy khng kh v than hot tnh khi c CuSO4 xc tc than hot tnh 40 2 1 10 22 t qu ng it nium dioxide 40

hng php in phn 40

2 2 1 in phn dung dch cha CN - 41

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2 2 2 in phn dung dch cha CN - c thm NaCl (3-5%) 41 23 hng php to phc kt t 41 thi nhim42 2 4 khng kh vo n

2 5 hng php sinh h : Enzyme x l ht thi xy nu , Cy nide hydr t se 42 3 hng php x nh nng xy nu s u khi x l n thi44 K N 46 K 47

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