XlTLY NUOC

KHOA HOC. CONG NGHE - CHUYEN GIAO

QUY HOACH THI/C NGHIEM NGHIEN CUU XlTLY NUOC RAC BANG QUA TRINH

PEROXONE

ThS. HOANG NGOC MINH

Vien KH&CN Moi trudng- DH Bach Khoa Ha Noi ThS.NGUYEN THU TRANG Vien Cong nghe Moi tnfdng - Vien KH&CNVN

ThS. NGUYEN VAN TRANG

Vien Cong nghe Moi trudng - Vien KH&CNVN

Tom tat .• Quy hoach thuc nghiem la tochirc thuc nghiem nghien ciJru mot qua trinh 6em6 phong, xdc 6inh md hinh toan va cac 6ieu kien toi uu cua qua trinh 6d vdi mot so thuc nghiem toi thieu. Bai bao trinh bay ket qua nghien ciru xCrly nudc rac tai bai rac Nam San - Sdc San (TP. Ha Noi) bang qua trinh oxy hda nang cao tren ca sd ozone (qua trinh Peroxone) va md hinh toan md phong qua trinh.

Abstract; Experimental planning method is the organization to stu6y processes for simulation, defining the mathematical cybernetic and optimal conditions with the minimum experiment amount.

This paper shows the results of landfill wastewater treatment of Nam Son landfill by Advanced Oxidation Process -AGP (Peroxone process) and mathematical cybernetic for the process simulink.

I.DAlV/iiNOi

XQ ly nudc rdc (nudc ri rac) tai cac bai chdn lap rac thai dd thj ndi chung cung nhu tai bai rac Nam Son - Sdc Son (Hd Ndi) la van de rat khd khan va phQc tap. Nudc rac chQa cac thdnh phan khdng phdn huy sinh hpc va khd phdn hOy sinh hpc ndn cac hd thd'ng xQ ly nudc rac phai td hgp cac qua trinh hda ly - sinh hpc - hda hpc mdi bao dam cac ydu cau ciia quy chuan mdi trudng. Cac qua trinh hda hpc dugc ap dung hidn nay phd bid'n la qua trinh Fenton, mdt trong cac qua trinh oxy hda nSng cao (Advanced Oxi- dation Processes - AOPs) dugc phat tridn trong khoang 20 n3m gan ddy. Qua trinh Fenton rat c6 hidu qua trong vide x^ ly chat hffu co khd phan huy sinh hpc (COD tro) va dd mdu cDa nudc rac. Tuy nhien, qua trinh Fenton cung cd han chd la chi cd hidu qua cr dieu kien pH » 3, do dd can tidu tdn nhidu hda chat de tao mdi trudng phan Qng va trung hda sau khi kdt thuc phan Qng. Odi vdi bdi rac Nam Son - Sdc Son, mdi ngay tidp nhan va xQ ly khoang 4.000 tan rac vd xQ ly khoang 1.500 m^ nudc rac thi khdi lugng hda chat (axit, xut) sis dung de dieu chinh pH va trung hda rat Idn. Ndu giam thidu se tidt kidm chi phi van hanh va cai thidn DKLV cho NLD.

Trong bdi bao ndy, chung tdi trinh bay ket qua nghidn cQu xir ly nudc rac bai rac Nam Son - Sdc Son (Ha Ndi)

bang qua trinh Peroxone thay cho qua trinh Fenton 6 quy md thQ nghigm trdn Pilot Study. Qua trinh Peroxone cd uu didm la tidn hdnh trong mdi trudng pH = 7 -^ 9, cd thd khac phuc han che cua qua trinh Fenton, vd chat oxy hda la ozone dugc san xuat tai chd, khdng phai van chuydn, cat giQ. Tuy nhien qua trinh Peroxone cung cd han chd Id thidt bj tao khi ozone kha dat tidn va phai nhap ngoai vi trong nudc chua dap Qng dugc ygu cau. Do dd, can cd nghign cQu day dCi va hd thdng trong vi6c ap dung cac qua trinh oxy hda nang cao trdn co sd ozone ndi chung va qua trinh Peroxone.

II. PHinmC PHAP NGHIEN Cl)U

1. Chuan bj thf nghiem: nudc rac dau vdo lay tai d hd chQa nudc rac H3, bai rac Nam Son, huygn Sdc Son ngay 27/2/2011. Sau dd xQ ly so bd bang keo tu vdi ham lugng chat keo tu 2g/l PAC, chat trg keo tu Id polymer vdi ham lugng 3mg/l. Nude rac sau khi keo tu xijr ly so bd c6 thanh phan:

COD = 2172 mg02/l; dd mau = 541 (R-Co); pH = 8,5;

BOD = mgOj/l.

2. Hoa chat:

Hda chat keo tu Poly Aluminium Cloride (PAC) cdng nghidp. Chat trg keo tu: Polymer A101 pha dung dich bSo hda. HjOj cdng nghigp, ndng dd 55%; H^SO^, NaOH tinh

12

Tfp chi Ir\r\MM

B A O HO LAO DONG 9/2011

KHOA H O C .

CONG NGHE - CHUYEN GIAO

khidt dung dd pha chd dung dich didu chinh pH (dunq dich

10%). V a .

3. Phircfng phap phan tich va thiet bj phan tich:

- Phdn tfeh tai phdng thi nghidm Vidn Cdng nghd Mdi trudng (Vidn KH&CNVN).

- pH xdc dinh theo TCVN 6492:1999, thidt bi do pH meter.

- COD xac djnh theo TCVN 6491:1999, thiet bi DRB.

- 06 mau xac djnh theo TCVN 6185:1996, thiet bj Quang phd kd UV-vis.

4. Thiet bj thi nghiem: thidt bi thQ nghigm Pilot Study TKM0311KOIKA Ozonaization Tester, 0R-i5-C, chd tao tai Han Qudc, cdng suat tao khi ozone max = 11 gOj/h, dat tai phdng thf nghidm Vidn Cdng nghd Mdi trudng (Vidn KH&CNVN).

5. Trinh tir thf nghiem:

Ap dung md hinh thdng kg dd xac djnh cac thdng sd tdi Qu vd ddng hpc qua trinh xit ly nudc rac khd phdn huy sinh hpc bang qua trinh oxy hda ndng cao trgn co sd ozone.

Vide xac dinh cac thdng sd md hinh nhd xQ ly sd Hdu theo phuong phdp thdng kg can cQ vdo cdc thuc nghigm theo cac kd hoach thuc nghidm.

Qua trinh xQ ly cac chat hQu co khd phdn hOy sinh hpc trong nudc rac bang qua trinh Peroxone thuc hidn trong didu kidn nhigt dd vd ap suat binh thudng, dang nhigt, luu lugng khdng khi khdng ddi.

Cac thdng sd qua trinh:

- Chat oxy hda:

Bdng 1: Bing ma hda cac bien thifc nghiem

+ Hdm lugng Ozone max = 3,175 g/h (0,= 3,175 g/

h);

+ Ham lugng Ozone min = 1,453 g/h (0 = 1,453 g/h) a)Z™« = 3,175g03/h;

b)Z,™ = 1,453 gOj/h 0)2,° = 2,314 g03/h

Hydrogen Peroxide H^O^:

a) Z2™«= 3.000 mg/1;

b) Z2™"= 0;

c ) Z / = 1.500 mg/1;

Thdi gian: 0 phut; 20 phut; 40 phut; 60 phut; 120 phut.

a)Z3™«=120phut;

b) Z3™" = 20 phut;

c)Z3''=70phut;

- Lugng ra:

a) y',: Gia trj tuydt ddi cOa ham lugng chat hffu co (COD) trong nude rac sau khi xQ ly; y,: Hidu qua xQ ly chat hQu CO COD (%);

b) y'j: Gia tri tuygt ddi dd mdu Pt/Co ciia nudc rac sau khi xQ ly; y^: Hidu qua xQ ly dd mdu Pt-Co (%).

- Ma hda cac bidn theo cdng thQc

Z ° = ' -"" ' ; A Z = ^ ^ 2

Z.-Z°

X, = • -•J = lk

Gia

c

Zi 3,175 1,453 2,314

trj cac ydu td trong )uy md tu nhign

1, 0 3.000 1.500

20

z,

20 70

Bi^n ma hda x,

+1 -1 0

X, -1 +1 0

Xi

-1 -1 0

Luang ra

Vl y,

^ 1

Trong dd AZ, Id don vi thay ddi hoac khoang thay ddi theo true Z.

Didm v6i toa dd Z,"', Z^, ...Z,° gpi Id tam cua kd hoach hay mQc co sd.

TQ hg toa dd Z,", Z / , ...Z; gpi id tdm cOa kd hoach chuydn sang hd toa dd mdi khdng thQ nguydn x,, Xj x,, theo cdng thQc:

Bang 2: Ke't qua thing!

SdfhUtu thf nghigm

1 2 3 4 5 6 7 8 9

}iem xCfly COD va dp mau nifdc rac bing qua trinh Peroxone Gid tri cac y^u td trong

quy md tu nhign

z,

1,453 3.175 1,453 3.175 1,453 3,175 1.453 3,175 2,314

z.

0 0 3.000 3.000 0 0 3000 3.000 1.500

Z3 20 20 20 20 120 120 120 120 70

Gia tri cac y€u 16 trong he tea dp khOng thU nguygn

x, -1 +1 -1 +1 -1 +1 -1 +1 0

x, -1 -1 +1 +1 -1 -1 +1 +1 0

x.

-1 -1 -1 -1 +1 +1 +1 +1 0

Lupng ra

Vl

1524 2011 744 1624 1440 1850 714 1507 735

VJ

243 500 142 40 66 117

99 11 78

9/2011 BAO HO LAO D0NC 13

KHOA HOC. CONG NGH§ - CHUYEN GIAO

Bang 3: Kit SolhUtuthi

nghiem 1 2 3 4 5 6 7 8 9

qua xurly COD va dp mau nifdc rac tlnh theo hieu qua % Gia trj cac ye'u td trong

quy mo tu nhien

Zi

1,453 3,175 1,453 3,175 1,453 3,175 1,453 3,175 2,314

z,

0 0 3.000 3.000 0 0 3.000 3.000 1.500

z.

20 20 20 20 120 120 120 120 70

Gia trj cac yeu to trong he toa dp khong thU nguyen

Xi

-1 +1 -1 +1 -1 +1 -1 +1 0

Xp

-1 -1 +1 +1 -1 -1 +1 +1 0

x., -1 -1 -1 -1 +1 +1 +1 +1 0

Lugng ra

y'i

11,50 7,41 12,98 15,28 16,38 31,78 16,49 21,39 16,95

yV

11,17 7,58 49,47 70,80 76,68 78,37 64,77 91,97 72,24 Bang

TT 1 2 3 4 5 6 7 8

' 4: Ma tran ke hoach thifc nghiem vdi cac he

Xn

+1 +1 +1 +1 +1 +1 +1 +1

Xl

-1 +1 -1 +1 -1 +1 -1 +1

X?

-1 -1 +1 + 1 -1 -1 +1 +1

Xi

-1 -1 -1 -1 +1 +1 +1 +1

X1X2

+1 -1 -1 +1 +1 -1 -1 +1

X2X3

+1 +1 -1 -1 -1 -1 +1 +1

X3X1

+1 -1 +1 -1 -1 +1 -1 +1

sotifdna ho

XiXjXj

+1 +1 +1 -1 +1 -1 -1 +1

yi

11,50 7,41 12,98 15,28 16,38 31,78 16,49 21,39

VJ

11,17 7,58 49,47 70,80 76,68 78,37 64,77 91,97

A Z .

•J = \,k

III. KET QUA VA TJNH TOAN 1. Ket qua cac thf nghiem Kdt qua thi nghiem xQ ly nudc rac bang qua trinh Peroxone dugc phan tich va dua ra trong Bang 2 dudi day.

Chuydn cac gia trj ra y1 va y2 thanh y1' va y2' tinh theo % hidu qua xQ ly COD va dp mdu nude rac, ta cd cac gia trj ndu trong Bang 3.

Dang cua phuong trinh hdi quy day dij vdi cac he sd tuong hd nhu sau:

Trong he toa dp khdng thQ nguyen, tpa dp eua mQc trdn Id +1 va mQc dQdi la -1, tdm la 0 va trung vdi gdc toa dd. Trong bai toan trgn, k = 3. Sd td hgp cd the N ciia ba ydu td trdn hai mQc bang N = 2" = 2^ = 8. Kd hoach tidn hdnh thi nghiem (ma tran kd hoach hoa) ghi trong Bang 1.

Gia trj y nhan duge khi thuc hien kd hoach hoa ghi d cdt cud'i. Kd hoach trong bang cd thd hinh tugng hoa trong dang hinh hop, 8 dinh eiia nd trung vdi tam didm thue nghiem.

Md hinh thd'ng kd bidu didn su phu thudc ciia hieu qua xQ ly chat hQu eo (COD) va hieu qua xQ ly mau (Pt/

Co) eiia nudc rac va cac bidn da ma hda ed dang:

k k k

/=l /,"=! /=!

Y, =b^+ /)| x, + ft,jc, + /),x, + h^^x^x., + b^yX^x + bj^x.x^ +/)| 123X1JC2JC3 (6)

(3)

Oe xac djnh cac hd sd b,^, b23, bj, (hieu Qng tac dung kep) va b,23 (hieu Qng tac dung ba) thi ta phai md rdng ma tran d Bang 3 thanh ma tran kd hoach d Bang 4.

Cac hieu Qng tac dung tuong hd dugc xac djnh tuong tu nhu hieu Qng tuyen tinh.

Can cQ vdo Bang 4 ta tfnh dQge gia trj cua cac hg sd eiia phQong trinh hdi quy day du. Cu the nhu sau:

Can cQ vao ma tran kd hoach ta cd the xac djnh dQpc cdc he sd b theo cdng thQc:

z

N

h . =

y

z

^{V / = 0 k}

(7) - } ,

Cu thd la 6 day, cu thd nhu sau;

/ / = /)(, + /)|X| + b.,Xj + bjXj + h^^x^x^ (4)

Ndu gia thidt md hinh tuydn tinh thi sQ dung kd hoach d Bang 2 de tinh cac he sd hdi quy eiia phuong trinh tuydn tinh:

Y] =bg+b^x^+ /),x, + bjXj (5) b . =

N V y = 0 , ^ ; (8)

a) Odi vdi phuong trinh hdi quy md ta hidu qua xCr ly chat hQu CO COD, hdmy,:

b(,= 16,65125; b, = 2,31375; b^ = 0,11625; b3 4,85875; b,2 = 0,51375;

bjj = - 2,45375; bj, = 2,76125; b.^j = 0,76375.

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KHOA H O C ,

CONG NGHE - CHUYEN GIAO

Ham hdi quy c d dang:

y, = 16,65125 + 2,31375x, - 0,11625x2 + 4,85875x3 + 0,51375x,x,- 2,45375x^X3 + 2,76125X3X, + 0,76375x,x,X3 b) Doi vdi phuang trinh hoi quy mo ta hieu qua xir ly mau (Pt/Co), ham y^

b „ = 56,35125; b, = 5,82875; b, = 12,90125; b3 = 21,59625; b,2 = 6,37;

b^j = - 1 2 , 4 9 1 2 5 ; b3, = 1,39375; b^^^ = 2,86625.

Hdm hdi quy ed dang:

y^ = 56,35125 + 5,82875x, + 12,90125x3 + 21,59625x3 + 6,37x,X2 - 12,49125X3X3 + 1,39375X3X1 + 2,86625x,X2X3

Tinh phuong sai lap:

o 2 _ ,, , I

Z (>'o» - yJ'

yo = Trong d d :

1

m

m - 1 Z (>'".. - 3^o)';.yo = — Z y.'- (9)

(10)

6 day:

S^L - phuong sai lap (phuong sai tai sinh);

m - sd thi nghigm d tam;

y^^- gia trj cua y d thi nghiem thQ a tai tam;

y^ - gia tri trung binh cQa y tai t a m .

Tidn hanh hai thf nghigm tai tam k d hoach (vdi x, = 0, X3 = 0, X3 = 0, tQc Z, = 2,314 g O j / h ; Z^ = 1.500 mgH.O^/l; Z ,

= 70 phut) thu dugc kdt qua:

Thucnghiem xCrly COD:

y" = 1 6 , 9 5 ; ^ ? = 1 6 , 4 5 ; ,^^^

-Thucnghiem ^' ' 11 xCrlydomau: y" = 7 2 . 2 4 ; . v ; ' = 7 2 , 5 0 ;

Ghi ehii: Trong cac cdng thQc (11) thi ehi s d (o) trong y ° khdng phai la s d mu eiia ky hieu todn hpe ma la ky hieu ma hda kdt qua nhan dupc tai thi nghiem trung tdm.

c) Doi vdi hieu qua xir ly chat hCtu ca khd phan huy sinh hoc COD:

v;' = l6.70;5/,=—.[(16.95-16.70)'+(16.45-16.70)=] = 0.125

^ " ' (121 0 125

• =0.015625 f'

Z-:

⁸

Vdibactudof2 = m-1 = 2 - 1 = 1 vamQeednghTap = 0,05, tra bing ta cd gia trj chuan sd Student t, „„„5 = 12,71.

Hd sd b se cd nghia khi:

k |> c , = J0,0l5625.12,71 = L58875 (^3) Cae hd sd b^, b,,, b^^^ khdng cd nghia vd md hinh thdng kd md ta su anh hudng ciia eae thdng sd qud trinh ddn hidu qua xCr ly chat hQu co khd phdn huy sinh hpc.

Ham hdi quy cd dang:

y, = 16,65125 + 2,31375x, + 4,85875x3" 2,45375X3X3 2,76125X3X,

d. Doi vdi hieu qua xir ly mau (Pt/Co):

.i;' = 71,87;.S';^ =^.[(71,24-71,87)'+(72,50-71,87)']=0,7938

(14) . S ; = - ^ = ^ ™ = 0 . 0 9 9 2 2 5

Z-;

Vdi bac t u do fj = m - 1 = 2 - 1 = 1 va mQc cd nghia p = 0,05, tra bang ta cd gia trj chuan sd Student t, ^ ^^^ = 12,71.

He s d b se ed nghia khi:

\h^\> .S'„^./|„„„5 = 0 . 3 1 5 . 1 2 . 7 1 = 4 , 0 0 3 6 5 (15)

Cac he s d b^, b,, b^ bj, b,^, b^j eiia phuong trinh hdi q u y c d nghia, cae he s d bj,, b,23 bj loai, va md hinh thdng kg md ta s u anh hudng cua cac thdng s d qua trinh de'n hieu qua xQ ly chat hQu c o khd phan huy sinh hpc. Ham hdi quy cd dang:

y^ = 56.35125 +5.82875x^ + 12,90125x^ +21.59625x^

+ 6,37x^x^ - 12,49125x/^.

2. Kiem tra sir ti/dng hdp cua phQdng trinh hoi quy mo ta hieu qua xQ ly chat 6 nhilm hQu cd kho phan huy sinh hpc bang Chuan sd Fisher:

F = S _lir

s-

⁽¹⁶⁾

Trong dd: S^ - phuong sai d u t i n h theo cdng thQc:

^l = ^t(yi-^'

A' - I , - i ⁽¹⁷⁾ I - s d he s d trong phQong trinh hdi quy;

y - g i d trj t h u c n g h i e m ;

/ 7 - gia trj tinh tuong Qng theo phQong trinh hdi quy.

Dd'i vdi hidu qua xQ ly chat hQu c o khd phdn huy sinh hpc ta tinh dQpc:

' - i ( j ^ , - : ^ - ^ = 7,575 (19) S' =

- 3 _{/ = i -} Gia trj Chuan s d Fisher

SL 7,575

F ^ S

_i.i. ^0,03125

268,83

(20)

Chua'n s d Fisher vdi bac t u do ciia phuong sai d u /, = W - / = 8 - 3 = 5; bac t u do eiia phuong sai lap f^=^, gia trj chuan s d Fisher F0.01(f,, fj = 5763,65, vay F < F 0.01(f1, f2) nen phuong trinh hdi quy tuong hpp.

9/2011 BAO HO LAO DONG 15

KHOA HOC. CONG NGHE - CHUYEN GIAO

3. Kiem tra sir tircfng hgp cua phiTdng trinh hoi quy mo ta hieu qua xufly mau bang Chuan sd Fisher:

F = 1 ^ (21)

Trong dd: S^ - phuong sai du tinh theo edng thQc:

sL =

¹

A^ • T ( y , - ^ ' (22)

Trong dd:

- N la sd hd sd trong phQong trinh hdi quy - y, la gia trj thuc nghidm

- yB ia gia trj tinh tuong Qng theo phQong trinh hdi quy Ddi vdi hieu qua xQ ly chat hQu co khd phan huy sinh hpc ta tfnh duge:

'^<l = ^ Z ( > ' , - : ^ ' = 3 2 9 , 8 9 (23) Gia tri Chuan sd Fisher

f = ^ = ^ ? M i = 4l5,58

Sj, 0,7938

⁽²⁴⁾

- Chuan sd Fisher vdi bac tu do eua phuong sai dQ f,

= W-/ = 8 - 3 = 5;

- Bac tQ do cua phuong sai lap f^ = 1,

- Gia trj chua'n sd Fisher F 0,01 (f,, f) = 5763,65, vay F

< F 0,01(f1, f2) ndn phuong trinh hdi quy tuong hgp. Md hinh phu hgp vdi thue td.

IV. KET LUAN

- Md hinh todn md ta qud trinh xQ ly chat hQu co va dd mau cua nude rac dQpc thidt lap trgn co sd kdt qua theo quy hoach thuc nghigm phu hgp vdi thuc td vd cd the ap dung de lua chpn cac chd dd lam vide khac nhau cua qua trinh xiJ ly nude rac bang qua trinh Peroxone tuy theo ygu cau chat lugng dau ra cua nudc thai sau xd ly.

- Cd thd td chQe thge nghiem xQ ly nQde rac bang cac qud trinh khac nhu qua trinh keo tu tidn xd ly, qua trinh Catazone (xQ ly bang ozone kdt hgp chat xuc tac) va td hpp cac qua trinh hda ly, hda hpc.

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