X L NC THI XYANUA TITLE TRONG NH MY SN XUT ETHANOLNhm: 7 GVHD: Trn Xun Ni

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Mc Tiu

Thnh phn, tnh cht nc thi

X l xyanua trong nc thi

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Ni DungTng quan v ngnh sn xut ethanol

B

X l nc thi trong nh my ethanol

C

X l xyanua trong nh my ethanol11/30/2011

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I. TNG QUAN V NGNH SN XUT ETHANOL

Chu Phi sn xut khong 85,2 triu tn nm 1997 Chu 48,6 sn xut 48,6 triu tn M La Tinh v Caribbean sn xut 32,4 triu tn

Tinh bt khoai m l thc phm cho hn 500 triu ngi trn Th Gii(theo Cock,1985; Jackson & Jackson, 1990)

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C Khoai m

Khoai m hay sn (danh php khoa hc: Manihot esculenta) cy lng thc n c c th sng lu nm, thuc h i Kch. Cy sn c ngun gc vng nhit i ca chu M La Tinh (Crantz, 1976) v c trng cch y khong 5.000 nm (CIAT, 1993) Cy sn cao 2-3 m, l kha thnh nhiu thy, r ngang pht trin thnh c v tch lu tinh bt, thi gian sinh trng 6 n 12 thng.

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1.1

Cu to c khoai m

C khoai m c dng hnh tr, vut hai u. Kch thc c ty thuc vo thnh phn dinh dng ca t v iu kin trng, di 0,1 1 m, ng knh 2 10 cm

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1.2

Phn loi khoai mAdd Your Text

Khoai m ng

Phn loiAdd Your Text

Khoai m ngtAdd Your Text

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1.3Thnh PhnNc %

Thnh phn ha hc cy khoai mTheo on D v cc cng s (1983) 70.25 21.45 1.12 70 221.1

Theo http://www.starch. dk.isi/starxh/tmstarch.htm

Theo Recent Process in research and extension, 1998

63-70 18-30 1.25

Tinh bt %Cht m % Tro % Protein %

0.40 1.115.13 5.13

0.85 1 1.20.08 2

Cht bo %Cht x % CN- %11/30/2011

0.001-0.004

173 ppm8

1 1.3

Gi tr kinh t ca c khoai mC M TI

THC

PHMNGI SC VT

BT CNG NGHIP NGNH CNG

RU CN

BT CNG Giy

NGHIPSt lt

NGHIP

Thc phm trc tip

Vin nn Bt Bt bn

Keo ,H Dt si

G , vn pCao su Giy

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1 2

Tnh hnh sn xut tinh bt snDin tch (triu ha) 16,43 Nm 1995 Nng sut (tn/ha) 9,84 Sn lng (triu tn) 161,79

Th Gii

16,2516,05 16,56 16,56 16,86 17,17 17,31 17,59 18,51 18,69 20,50 11/30/2011

19961997 1998 1999 2000 2001 2002 2003 2004 2005 2006

9,7510,06 9,90 10,31 10,70 10,73 10,61 10,79 10,94 10,87 10,90

158,51161,60 164,10 170,92 177,89 184,36 183,82 189,99 202,64 203,34 224,00 10

18,39 2007 12,16 223,75 Din tch, nng sut v sn lng sn ca th gii t nm 1995 2008 21,94 2008 12,87 238,45

Ti Vit NamNm Din tch (nghn ha) Nng sut (tn/ha) Sn lng ( triu tn)

2000 2001 2002 2003 2004 2005 2006

234,90 250,00 329,90 371,70 370,00 425,50 474,80

8,66 8,30 12,6 14,06 14,49 15,78 16,25

2,03 2,07 4,15 5,23 5,36 6,72 7,77

20072008

496,80557,40

16,0716,85

7,989,3

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Din tch, nng sut v sn lng sn ca Vit Nam giai on 2000 - 2008

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Ti Vit NamDin tch, nng sut v sn lng ca cc vng sinh thi Vit Nam nm2008 Din tch TT 1 Vng sinh thi ng bng sng Hng (1000 ha) 7,90 Nng sut (tn/ha) 12,92 Sn lng (1000 tn) 102,10

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Trung du v min ni pha BcBc Trung b v Duyn hi min

110,00168,80

12,0716,64 15,70 23,74 14,43

1.328,002.808,30 2.356,10 2.694,50 106,80

Trung4 5 6 Ty Nguyn ng Nam B ng bng sng Cu Long 150,10 113,50 7,40

C nc11/30/2011

557,40

16,87

9.395,8012

3

Quy trnh cng ngh sn xut tinh bt

C khoai mRa c Bc v v ra Mi xt Tch x, b Lc, ra Tch nc Phi sy Gel ha, p vin, sy Sn phm dng tinh bt

Sn phm dng vin ht (tapioca)

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Thi LanNc cpNc cp Khoai m ti Nc thi Ra s b, tch tp cht Bc v g, ra sch Bm nh Mi, nghin Trch ly, chic sut Lc Dehydrate ha Sy kh Khi thi14 Phi, my nn Song chn rc, cng trnh x l s b

Nc cp

Nc cp

B m Nc thi Trm x l nc thi

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Indonesia

Khoai m

Sy kh

Lng

ng

Qut ht

Tinh bt

Bm nghin

p

Lc

Qut ht

Quy trnh sn xut tinh bt ca Indonesia11/30/2011 15

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Nc thi nh my sn xut tinh bt sn

3.1 Thnh phn cc cht c trong nc thiThi vo ngun Ngun tip tip nhn dng nhn khc, cho mc ch tip Ngun ngoi loi sinh hot. A quy nhn c nh

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3.2 Tc ng ca cc cht c trong nc thi

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CHNG II TNG QUAN CC PHNG PHP X L NC THI TRONG NH MY SN XUT TINH BT SN

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A. CC PHNG PHP X L NC THI

1

Phng php c hc

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1

Phng php c hcNhng cng trnh x l c hc bao gm 1. Song chn rc 2. B lng ct 3. B lng 4. B lng ng 5. B lng ngang 6. B lng ly tm 7. B vt du m

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2

Phng php ha l1 Phng php keo t v ng t 2 Tuyn ni 3 4 5 6 7 Hp ph Phng php trao i ion Cc qu trnh tch bng mng

Phng php Ha l

Phng php in ho

Phng php trch ly21

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Phng php ha hc

1

Phng php trung ho2 3

Phng php oxy ho khKh trng nc thi

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Phng php sinh hc

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 c trong nc thi. Loi cc bng cn ra khi nc thi bng qu trnh lng.

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4.1 X l nc thi bng phng php sinh hc trong iu kin t nhin

H sinh vt

Cnh ng ti - Cnh ng lc

H sinh vt hiu kh

H sinh vt tu tin

H sinh vt ym kh

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4.2 X l nc thi bng phng php sinh hc trong iu kin nhn to B lc sinh hc nh git B lc sinh hc cao ti

B lc sinh hcB hiu kh bn hot tnh B Aerotank

Qu trnh x l sinh hc k kh - B UASB11/30/2011 25

B. QUY TRINH X L NC THI NH MY CH BIN TINHBT SN

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C. CNG NGH THCH HP X L NC THI TINH BT KHOAI M

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Hnh: Cng ngh thch hp x l nc thi ch bin tinh bt khoai m

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CHNG III:X L XYANUA TRONG NC THI NH MY SN XUT TINH BT SNCHNG III: X L XYANUA TRONG NC THI NH MY SN XUT TINH BT SN

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Chng III X l Xianua trong nh my sn xut tinh bt sn

I

Tng quan v Xianua :

Mui xianua kim

ixian -(CN)2

XianuaXianu a t do

Mui xianua kim th

1. Tnh cht vt lM= 27

Tan trong H2O, Ancol

Mi hnh nhn, v ng

d lng= 0.696 D hi = 0.968

Tdd = -14 Ts = 20

Axit Xyanhydric HCN

1. Tnh cht vt lTinh th trng

Tnh kim mnh

NaCl KClTan tt trong H2O, t tan trong Ancol

Phn hy bi H2O(h), CO2,SO 2

Mui

xianua kim

1. Tnh cht vt l

Xianua t do Rt cTn ti trong phc s bt c tnh Fe [Fe(CN)6]

1. Tnh cht vt lKh khng muHnh thnh do nhit phn mui xianua

cixianuaMi hnh nhn

Tan tttrong H2O, Ancol

2.Tnh cht ha hc HCN v (CN-) b oxihoa bi O2 trong khng kh 2CN- + O2 2CNO Dung dch long 1:5000 trong 5 thng s phn hy ht HCN + 2H2O HCOONH4 2HCN + 2H2S + O2 2HCNS + 2H2O Xyanua ca kim loi kim b phn hy bi CO2 2NaCN + CO2 +H2O 2HCN + Na2CO3 Alhit, ng cng ph hy HCN : C6H12O6 + HCN C7H13O6N

3. c tnh ca (CN-)H hp t bo

ng h hp

CN1mg/kg trng lng gy t vong

Vt thng ngoi da

I I

Cc phng php pht hin v xc nh hm lng xianua nhim

Cc phng php : PP nh tnh

PP nh lng

1. Phng php nh tnh.Fe2+ + 6CN [Fe (CN)6]4-

.4Fe3+ + 2 [Fe(CN)6]4Fe4[Fe(CN)6]2 xanh beclin

.

2. Phng php nh lng

PP chun th tch

Chun Iod

Chun Bc

CN - + I2 + H2O I2 + Tinh bt Chun Iod

CNO- + 2I - +2H+ Mu xanh

(CN)2] [Ag (CN)2] - + Ag+ Chun Bc

2CN - + Ag+

[Ag

2AgCN

III1

Cng ngh x l XianuaLa chn b acid ho x l nc thi Xianua

C s : Trong nc thi CN- tn ti di lianamarin. Di tc dng ca ca Enzim trong mi trng acid th Lianamarin b phn hy to thnh glucose, aceton, acid, cyanhydric.

Qu trnh phn hy CN- t lianamarin

Trong t nhin,lianamarin di tc dng ca enzim s chuyn ha theo c ch : CN- + O2 + enzyme = CNO-

CNO- + H2O = NH3 + CO2

Or : HCN + 2H2O = NH4COOH

th biu din kh nng phn hy CN- ti b acid ha

2

Cc phng php x l Xianua

PP in PP oxi phn ha

PP to phc kt ta

2.1. Phng php oxy haCht oxi haKh Cl2, nc Giaven, Clorua vi

OzonHydro peroxit

H2O2 + HCHO

(H2O2)

KMnO4O2 (than

ClO2

H2O2 + NaOCl

hot tnh+ CuSO4)

2.1. Phng php oxihoa Nguyn tc : - Oxi ha CN t do v phc ca n thnh hp cht t c hn nh : mui xianat, N2, CO2... -Cht oxi ha : Cl2, H2O2, NaOCl, CaOCl, KMnO4... iu kin tin hnh :oxi ha cc Xianua ph thuc vo : -Loi cht oxihoa dng. - Dng tn ti ca CN-, [CN-]. - pH v bin ng ca pH trong qu trnh x l.

2.1. Phng php oxi ha

H thng lm sch nc thi theo chu k

2.1.1. Oxi ha bng Cl2, nc Giaven, Clorua viCN- + OCl- CNO- + C l-

NaCN + NaOCl NaOCN + NaCl

2NaCN + Cl2 + 2NaOH 2NaOCN + 2NaCl + H2O

2.1.1. Oxi ha bng Cl2, nc Giaven, Clorua viOxi ho axynua phc hp tan c

2[Cu(CN)3]2- + 7OCl- + 2OH 6CNO- + 7Cl- + 2Cu(OH)2

[Zn(CN)4]2- + 4OCl- + 2OH 4CNO- + 4Cl- + Zn(OH)2

2.1.1. Oxi ha bng Cl2, nc Giaven, Clorua vi

S cng ngh lm sch nc thi Xianua lin tc bng kh clo2CN- + Cl2 2ClCN (pH = 11-12 )

2.1.1. Oxi ha bng Cl2, nc Giaven, Clorua vi 2NaOCN +3NaOCl + H2O 2NaHCO3 +N2 + pH = 5 - 3NaCl 8 2NaOCN + 3Cl2 + 6NaOH 2NaHCO3 + N2 + 6NaCl + 2H2O

8 < pH < 10

NaCN + NaOCl + H2O CNCl + 2NaOH CNCl + 2NaOH + H2O NaOCN + NaCl + 2H2O

2.1.2. Oxi ha bng ClO2Clodioxyt c ch to ti ch bng tc dng ca mui NaClO2 vi Cl2 hay axit clohydric:2NaClO2 + Cl2 2ClO2 + 2NaCl

5NaClO2 + 4HCl

4ClO2 + 5NaCl + 2H2O

2.1.3. Oxi ha bng ozon

CN - + O36OCN - + 8O3

OCN - + O26CO2 + 3N2 + 902

O3 t c hi hn Clo. Oxi ha trit CN- thnh cht khng c. T ,P khng cao. Lm gim tng lng H2O trong x l.

2.1.3 Oxi ha bng ozon

m bo TCVN 5945

Thit b loi m thc hin phn ng oxy ho bng ozon.

2.1.4. Oxi ha bng H2O2CN - + H2 O2 OCN - + 2H2 O2 OCN - + H2O CO2 + NH3 + OH -

- Hydroperoxyt cng l cht oxy ho mnh lit CN - thnh cht khng c phn ng cn c xc tc Cu 2+ - 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 c.

2.1.5.Oxy ho bng hydroperoxyt v natrihypoclorit H2O2 + NaOCl

2CN - + H2O2 + OCl -

2OCN - + Cl - + H2O

Khng i hi pH cao nh khi dng mt mnh mui hypoclorit. Khng phi thc hin ch pH nghim ngt phng sinh ra kh c. Khng cn thm nhiu NaOH iu chnh pH nn tit kim c 30% chi ph.

2.1.6.Oxy ho bng H2O2 + HCHO (focmandehyt)

H 2O 2

CN - + H2O2

OCN - + H2OHO-CH2- C N +

HCH OH2O2 + HCHO

OH [Zn(CN)4]2- + 4HCHO + 4H2O 4OH- + Zn2+ HO-CH2-C N + H2O xc tc OH-

CN - + H-CH =O + H2O

4HO-CH2-C N +

HO - CH2 - CO - NH2

2.1.7. Oxy ho bng KMnO43CN - + 2MnO4- + H2O 2MnO2 + 3OCN - + 20H Oxy ho bng KMnO4 ; xc tc Cu2+

Thch hp cho nng sut nh v trang thit b vn hnh n gin nhng t do KMnO4 cao. T l dng cn 4,05 kg KMnO4/1kg CN -. Dng tc nhn oxy ho ny kh t v li nhng sn phm cha an ton cho mi trng.

c im

2.1.8. Oxy ho bng oxy khng kh v than hot tnh khi c CuSO4 ; xc tc than hot tnh

2CN - + O2

2OCN -

OCN - + H2OHCO3- + OH -

HCO3- + NH3CO3 2- + H2OCuCO3.

2Cu2+ + 2OH- + CO3 2Cu(OH)2

2.2. Phng php in phn

PP in phnin phn dung dch cha CN Dung dch cha CN c thm NaCl (35%)

2.2. Phng php in phn CN - + OHH2O+2e[Zn(CN)4]2- + 8OH 4H2O + 8e

OCN - +

Zn2+ + 4OCN- +

2OCN - + 6OH+ 8e

2HCO3- + N2 + 3H2O

2.2. Phng php in phnNaCl NaOCl

.

CN - + OCl Cl .

OCN - +

H2O + 2OCN - + 3ClO2CO2 + N2 + 3Cl - + 2OH-

.

2.3. Phng php to phc kt taTrong mi trng kim (baz) FeSO4 tc dng vi CN-

Fe2+ + 2CN Fe (CN)2 + 4CN -

Fe (CN)2[Fe(CN)6]4-

[Fe(CN)6]4- + 2Fe2+Phn ng tng cng:

Fe2 [Fe(CN)6]

3Fe2+ + 6CN -

Fe2 [Fe(CN)6]

T l dng: 5,35 kg FeSO4 cho 1 kg CN Kt ta c mu xanh prusse

2.4.Sc khng kh vo nc thi nhimGii php n gin nht kh c xyanua l sc khng kh vo nc nhim xyanua. Nh m nc hp ph CO2 to ra H2CO3 axit cacbonic l loi axid yu nhng n vn mnh hn axit HCN v nh vy n s y HCN t mui xyanua. HCN hoc l bay hi hay chuyn ha thnh HOCN t c hi hn. Sau HOCN vi s c mt ca oxy phn t s chuyn ha hay thy phn thnh amonic v CO2:

HOCN + H2O

CO2+ NH3

2.4.Sc khng kh vo nc thi nhim

2.5.phng php sinh hc :Enzyme x l cht thi Xianua, Cyanide hydratase (cng ngh mi) Cyanide hydratase, hoc formamide hydro-lyase l mt enzyme c kh nng chuyn ho cyanide trong nc thi cng nghip thnh amoniac v formate thng qua mt bc phn ng. Cyanide hydratase c phn lp t mt vi loi nm v c to ra t nm khi nng xyanua thp. Khi c c nh, tnh bn ca Cyanide hydratase 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 Xianua.

2.5.phng php sinh hc :Enzyme x l cht thi Xianua, Cyanide hydratase (cng ngh mi) Mt s vi khun Gram-(-) nh Alcaligenes denitrificans cng tit ra cyanidase c i lc bn cao v c kh nng loi xyanua nng rt thp, v d nh < 0.02 mg dm-3 CN. Hot tnh ca cyanidase khng b nh hng bi cc ion thng thng c mt trong nc thi ( Fe2+, Zn2+ v Ni2+), hay bi cc cht hu c nh acatat, formamide, acetamide v acetonitrile. pH ti u trong khong 7.8-8.3 v mt hot tnh hon ton, khng phc hi khi pH cao hn.

u nhc im ca cc phng php1 Phng php oxy ha.

u im: nhanh, khng b nhim bn tr li v CN- b phn hy hon ton. Nhc im: iu kin phn ng nghim ngt, cng ngh t tin. 2 Phng php in ha u im: cng ngh n gin Nhc im : khng hon ton, tiu tn in cc v nng lng nhiu.

u nhc im ca cc phng php3 Phng php to kt ta u im: ha cht r, cng ngh n gin. Nhc im: khng hon ton, hiu sut khng cao 4 Phng php sinh hc u im: Phng php t nhin. C th x l CN- m khng to ra mt dng thi khc. Khng cn thit b x l ha cht. Chi ph l c nh vi khi lng ln hn cht thi Khng c sn phm ph c hi, do thn thin vi mi trng .

u nhc im ca cc phng php Nhc im: cng ngh cha c thit lp tt; khng th x l nng cao. 5 Phng php CO2/ khng kh u im:n gin, r tin, lm vic trong pH rng. Nhc im: nc c x l t. 6 Phng php in phn u im: x l tt c nc thi xianua bt ky nng no. Nhc im:khng an ton, tiu tn in cc v nng lng nhiu.

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Phng php xc nh nng xyanua sau khi x l nc thi.

Lng xyanua cn li khng c vt qu0,01 mg/l ferokalixyanua v ferikalixyanua khng vt qu 0,04 mg/l. phn tch xc nh nng xyanua sau khi x l thng dng phng php Colorimetr vi thuc th pirazin ( C4H4N2 ) cn gi l phng php Piridin-Pirazin

3

Phng php xc nh nng xyanua sau

khi x l nc thi.

Tin hnh pha dd mu chun : Cn chnh xc 0,0508 g I2 ha tan trong 100ml CCl4 trong bnh cu nh mc. Ly 20ml dung dch ny pha lang bng CCl4 trong bnh cu nh mc n 200ml. Ly mu 1ml, ln lt pha lang 1, 2, 3,9ml nc nh vy ta c lot mu tng ng vi nng xyanua t 0,1 n 1mg/l. Tin hnh phn tch mu: Cho vo bnh o dung tch 25ml, 1ml dung dch cn phn tch, sau pha long bng 1ml nc ct.

3

Phng php xc nh nng xyanua

sau khi x l nc thi.

Tip theo cho thm 0,1ml dung dch cloramin T 1%. ng cht nt bnh o, lc bnh cn thn. Sau 1pht, thm 4ml thuc th pirazin, ng nt bnh o, lc bnh cn thn. Dung dch pirazin c chun b nh sau : cn 0,5g pirazin cho vo 100ml nc ct. un dung dch ln 600C, khuy u dung dch, sau khi lm lnh chop nc n th tch yu cu. Thm 4ml piridin, y np bnh o, lc u dung dch . em so mu vi dung dch mu trn bng Colorimeter.

Kt lun Tinh bt sn hin nay l mt trong nhng ngnh cng nghip rt c quan tm i vi hu ht cc nc ang pht trin. y cng l mt ngnh sn xut s dng nc tng i ln v nng cc cht nhim trong nc thi cao.V vy nc thi ra t cc nh my cn c quan tm mt cch c bit v cn c gii php c th m bo c mi trng v li ch kinh t. Vi ti X l nc thi c nhim CN trong qu trnh sn xut tinh bt sn,qua qu trnh tm hiu chng ti a ra c nhng phng php x l c hiu qu, m bo mi trng v kinh t lng CN c trong nc thi.

Kt lunDo 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 gp kin ca thy c v cc bn.

Thank you !