Nghiên cứu đánh giá hiệu quả xử lý nước thải nhà máy thuốc bảo vệ thực vật bằng hệ oxy hóa nâng cao o3 UV h2o2

TRU^NG B^I HOC AN GIANG
KY THUAT - CONG NGHE - MOITRUO

HO THI TRUC LIA

NGHIEN ClTU DANH GIA HIEU QUA Xf LY
NU'6C THAI NHA MAY THUOC BAO VE THUC VAT
BANG HE OXY HOA NANG CAO (O3/UV/H2O2)
TRIJONG DAI HQC
AN GIANG

THUVIEN
KHOA LUAN TOT NGHIEP

GVHD: ThS. TRlTONG KlEN THO
GVPB: ThS. NGUYEN THANH HUNG
ThS. LE THI CAM CHI

An Giang, 05/2013


LOT CAM ON

Trong qua trinh hoc tap tai Truang Dai hoc An Giang, dugc quy Thay Co
true tiep giang day, truydn dat nhung kidn thuc bo ich, do chinh la nhung nen
tang ca ban, la nhung hanh trang vo ciing quy gia. Dae biet, trong qua trinh thuc

hien dd tai khoa luSn t6t nghiep iin dau tien dugc tidp can vai viec nghien ciiu de
tai thuc nghiem nen gap khong it kho khan nhung nhd dugc sir giup da tan tinh
va nhilng lcri dong vien quy gia cua moi nguai da giup toi hoan thanh bai khoa
luan t6t nghiep nay. Qua day, toi xin dugc gai lefi cam on den ho:

Cam an Ban giam hieu Truang Dai hoc An Giang, Khoa Ky thuat - Cong
nghe - Moi truang, quy Thay Co trong Bo mon Moi truang va Phat trien Ben

vung da trang bi kien thuc cho toi trong suot qua trinh hoc tap.
Toi chan thanh cam an thay Truang Kidn Tho, du rat ban ron vai cong viec

nhung thay van danh thai gian chi bao, huang dan, tao didu kien de toi co the
hoan thanh bai khoa luan.
Ben canh do, toi cung xin dugc g&i loi cam an tai cac c6j chu, anh, chi

trong Trung tarn ting dung Tien bo Khoa hoc va Cong nghe, Xin cam an chu
An, chi Trinh, anh Han, a Quoc. Cam on moi nguai da giup da, dong gop ^kien
cho toi trong qua trinh thuc hien de tai.
Cam an thay Nguyen Trung Thanh, co Nguyen Hong Nhat, can bo phu
trach phong thi nghiem Khoa Ky thuat - Cong nghe - Moi truang da giup da va
ho trg toi trong qua trinh thi nghiem.
Cam an Ban Giam d6c nha may thudc bao ve thuc vat huyen Chau Thanh
va a Tam da nhiet tinh giup d& trong qua trinh lay mau nuac thai.
Ngoai ra, toi xin gai lai cam an rlt muc chan thanh dSn cac ban cua toi.

Cam an cac ban trong nhung nam qua cung gin bo, cimg hoc tap, da giup da toi
trong qua trinh thuc hien mo hinh nghien cuu, da co vu, dong vien tinh thin toi
khi nghien cuu gijp vin d^.
Trong qua trinh nghien cuu de tai va viSt bai khoa luan vai kiSn thuc va thai
gian con han chS nen noi dung khdng tranh khoi nhung thiSu sot. Kinh mong
nhan dugc sir gop y, nhan xet tir phia quy Thiy, Co!
Toi xin chan thanh cam an!
LongXuyen, ngay 2 thang 5 nam 2013
Sink vien thvic Men
H6 Thi True Lia

NHAN XET CUA GIANG VIEN Hl/OfNG DAN

Long Xnyen, ngay ... thang ... nam 2013

Th.S Trirong Kiin Tho


NHAN XET CUA GIANG VIEN PHAN BIEN

LongXuyen, ngayftfT thang ^. nam 2013

Th.S Nguyln Thanh Hung


NHAN XET CUA GIANG VIEN PHAN BIEN

LongXuyen, ngay ... thang ... nam 2013

Th.S Le Thi Cam Chi


NGHIEN CUtT BANH GIAHIEU QUA XU"LY NUOC THAI NHA MAY

THUOC BAO VE THlTC VAT BANG HE OXY HOA NANG CAO
(O3/UV/H2O2)

Tom tat: Nghien criu nay sir dung cac qua trinh oxy hoa bac cao la: O3/UV
va O3/UV/H2O2 nham danh gia hieu qua xir ly COD, TSS va anh huong cua pH

den qua trinh xir ly, tir do so sanh hieu qui xir ly cua he O3AJV/H2O2 doi vdi he
O3/UV. Hieu qua loai bo COD va TSS dugc khao sat bang each thay d6i n6ng dp
nuoc thai theo he so pha loang va lidu lupng H2O2 trong thai gian 4 gia, ham
luong ozone sri dung la 4 g/h va cong suat den UV la 30W. KSt qua nghien ciru
cho thay, xri ly nuac thai thuoc BVTV bang qua trinh oxy hoa bac cao dung
O3/UV/H2O2 dat hieu qua cao han khi chi dung O3/UV vai hieu suit xir ly COD
va TSS cao han tuang ring la 23% va 58,32%. Dong thai, trong qua trinh nghien
ciiu cac gia tri pH chenh lech khong Ian nen khong anh huong nhieu den ket qua
phan tich. Qua trinh oxy hoa bac cao dung O3AJV/H2O2 co the ring dung nhu mot
phuang phap hieu qua de xir ly nude thai thuoc BVTV.


RESEARCH OF EVALUATION EFFICIENCY WASTEWATER
TREATMENT OF COMPANY DRUG PLANT PROTECTION BY

SYSTEM ADVANCED OXIDATION (OZONE COMBINATION WITH
HYDROGEN PEROXIDE AND UV-RADLATION)

Abstract: This research application of advanced oxidation processes

including: O3/UV and O3/UV/H2O2to evaluate treatment efficiency of COD, TSS
and pH influence to treatment process, which compare efficiency treatment of

O3/UV/H2O2 with of O3/UV. The efficiency of COD and TSS removal is
investigated by changing concentration wastewaters dilution coefficent and dose
of H2O2 in time 4 hour, content ozone use is 4g/h and lamp power is 30W. The
research results showed that wastewater treatment of drug plant protection by

advanced oxidation process use O3/UV/H2O2 to get efficiency higher when only
used O3/UV with efficiency treatment COD and TSS higher corresponding is

53% and 58,32%. Beside, this research process about pH different don't large, so
don't more influence to analysis result. Advanced oxidation process using

O3/UV/H2O2 is applied as a possible method for drug plant protection
wastewaters treatment.


Khda ludn tdt nghiepL&pDHlOMT

MUC LUC
Trang

MUC LUCi
DANH MUC fflNHiii
DANHMUCBANGiv

DANH MUC TlTNGU'VlfiTTATv
CHl/ONG 1: MO flAU1
CHLfOfNG 2: LU"0C KHAo TAl LIEU3
2.1.T6ng quan vSthu^c BVTV3
2.1.1.ThuSc BVTV la gl?3
2.1.2.Phan loai thudc BVTV3
2.1.3.Tdc hqi cua thudc BVTV.3

2.2.T6ng quan v cong nghe xu ly nuac thai thu6c BVTV4
2.3.Tong quan ve qua trinh oxy hoa nang cao trong nuac thai5
2.3.1.Binh nghia ve qua trinh oxy hoa nang cao5
2.3.2.Nhiing hqn che cua qua trinh oxy hoa hoa hoc bang cdc tdc nhan oxy

hoa thong thuang5

2.3.3.Cdc qua trinh tqo ra gdc Hydroxyl (*OH)6
2.3.4.Nhiing im viet cua qua trinh phan huy oxy hoa bang gdc tu do

Hyroxyl(*OH)7
2.3.5.Phan loai cdc qua trinh oxy hoa nang cao10
2.3.6.Cdc qua trinh oxy hoa nang cao tren caso ozone11
2.3.7.Cdc qua trinh oxy hoa nang-cao nhd tdc nhan dnh sang13

CHUONG 3: PHUONG TIEN VA PHlTONG PHAP NGHIEN CUtf17
3.1.Doi tugng nghien cuu17
3.2.Thai gian nghien cuu17
3.3.Muctieu nghien cuu17
3.3.1.Muc tieuchung.17
3.3.2.Muc tieu cu thi18

GVHD: Ths. TruongKien ThoTrang i
SVTH: Hd Thi True Lia


Khoa ludn tdt nghiepLapDHlOMT
3.4.Noi dung nghien ciiu18
3.5.Phircrng tien va vat lieu nghien cuu18
3.6.Phircrng phap nghien cuu18

3.6.1.Phuongphap tham khao tai lieu18
3.6.2.Phuong phap lay mau18

3.6.3.Phuangphapphdn tich19
3.6.4.Phuangphdp bo trimohinh thucnghiem20

CHtTONG 4: KET QUA THAO LUAN24
4.1.Mo hinh xur ly nude thai thudc BVTV blng he O3/UV24
4.1.1.Chi tieupH.."24

4.1.2.ChitieuCOD25
4.1.3.ChitieuTSS:26
4.2.Mo hinh xu ly nude thai thudc BVTV bing he O3/UV/H2O229
4.2.1.ChitieupH.29

4.2.2.ChitieuCOD30
4.2.3.ChitieuTSS31

CHlTONG 5: KET LUAN VA KIEN NGHI34
5.1. K^t luan34
5.2.KiSnnghj34

TAI LIEU THAM KHAO36

GVHD: Ths. TruongKien ThoTrangii
SVTH: H6 Thi True Lia


Khoa luqn tdt nghiipLdpDHWMT

DANH MUC HINH

Trang
Hlnh 3.1. Mo hinh he ozone + tia cue tim (O^UV)22
Hinh 3.2. Mo hlnh he ozone + lia cue tim (UV) + H2O2 (O3/UV/H2O2)23
Hlnh 4.1. Bleu do bleu dien su thay ddipHtheo he so pha hang24

Hlnh 4.2. Biiu dS biiu diin su thay ddi ndng do COD trudc vd sau khi xu ly theo
he so pha hang25
Hlnh 4.3. Biiu do biiu dien su thay ddi nong do TSS trudc vd sau khi xit ly theo
he so pha hang27
Hlnh 4.4. Mdu nude thai thudc BVTV sau 4 gid xu ly bdng he O3/UV theo he sd
pha hang28
Hinh 4.5. Mo hinh xit ly mtdc thai bang he O3/UV dang hoat dong28
Hinh 4.6. Biiu do bieu dien su thay ddi chisopH theo lieu luong H2O229
Hinh 4.7. Biiu dd biiu diin su thay ddi ndng do COD theo liiu luongH2O2 ...30
Hinh 4.8. Biiu dd biiu diin su thay ddi ndng do TSS theo liiu luong H2O232
Hinh 4.9. Mdu nude thai sau qua trinh xu ly bdng hi O3/UV/H2O2 trong thai

gian 4 gid33
Hinh 4.10. Md hinh thuc nghiim xu ly nude thai thudc BVTV33

GVHD: Ths. TruongKiin ThoTrang in
SVTH: H6 Thi True Lia


Khda luqn tdt nghiepLdpDHlOMT

DANH MUC BANG

Trang
Bang 2.1. Khd ndng oxy hoa ciia mot so tdcnhdn oxy hoa7

Bang 2.2. Cdc hap chat him ca hi oxy hoa bai gdc Hydroxyl (*0H) da dupe
nghiencuu9

Bang 2.3. Cdc qua trlnh oxy hoa ndng cao khdng nha tdc nhdn dnh sang10

Bang 2.4. Cdc qua trlnh oxy hoa ndng cao nha tdc nhdn dnh sang.11

Bang 2.5. Dae trungphd biecxq dien tie cua dnh sang14
Bang 3.1. Tiin dp thuc Men di tai17
Bang 4.1. Chi so pH dduvdo vd sau qua trinh xie ly theo he sdpha loang24
Bang 4.2. Ndng do COD ddu veto vd sau qua trinh xie ly theo he so pha loang

25
Bang 4.3. Ndng do TSS ddu vdo vd sau qua trlnh xie ly theo he so pha loang....26

Bang 4.4. Chi so pHdduvdo vd sau qua trlnh xie ly theo lieu luang H2O229
Bang 4.5. Chi so COD ddu vdo vd sau qua trlnh xie ly theo lieu luang H2O2 ...30

Bang 4.6. Ndng do TSS ddu vdo vd sau qua trinh xie ly theo lieu luang H2O2 .. 31

GVHD: Ths. TruangKien ThqTrang iv

SVTH: Hd Thi True Lia


Khoa luan tdt nghiepLap DHJOMT

DANH MUC TIT NGU" VIET TAT

AOP (Advanced Oxidation Process)Qua trinh oxy hoa n^ng cao
BVTVBao ve thuc vat
COD (Chemical Oxygen Demand)Nhu cau oxy hoa hoc
FAOT6 chuc Ltrcrng thuc ThS gioi

PPhotpho

PGS. TSPho Giao su TiSn sT

TPThanh ph6
TSS (Suspended Solids)T6ng chit rib lo lung
USEPA (US Environment Protection Agency)Co quan bao ve moi truong My
UVTia cue tim

G VHD: Ths. Truong Kien ThoTrang v

SVTH: H6 Thi True Lia


LOI CAM ON

Trong qua trinh hoc tap tai Truang Dai hoc An Giang, dugc quy Thay Co
true tilp giang day, truyln dat nhung kiln thuc b6 ich, do chinh la nhGng nen
tang ca ban, la nhung hanh trang vo ciing quy gia. Dae biet, trong qua trinh thuc

hien dl tai khda lu^n t6t nghiep lln dhu tien dugc tilp can vdi viec nghien cuu de
tai thuc nghiem nen gap khong it khd khan nhung nhd dugc su giiip da tan tinh
va nhung Icfi dong vien quy gia cua mpi ngudi d3 giup toi hoan thanh bai khoa
luan t6t nghiep nay. Qua day, toi xin dugc gdi lai cam an dgn ho:
Cam an Ban giam hieu Truong Dai hoc An Giang, Khoa Ky thuat - Cong
nghe - Moi truang, quy Thay Co trong Bp mon Moi truang va Phat trien Ben
vung da trang bi ki^n thuc cho toi trong suot qua trinh hoc tap.
Toi chan thanh cam an thay Truang Kien Thp, du rat ban rpn vai cong viec
nhung thay van danh thai gian chi bao, hudng dan, tao dieu kien de toi co the
hoan thanh bai khoa luan.
Ben canh do, toi ciing xin dugc gai lai cam an tai cac co, chu, anh, chi
trong Trung tam Ung dung Tien bo Khoa hoc va Cong nghe. Xin cam an chu

An, chi Trinh, anh Han, a Quoc. Cam on mpi nguai da giup da, dong gop y kien
cho toi trong qua trinh thuc hien de tai.
Cam an thay Nguyen Trung Thanh, co Nguyen Hong Nhat, can bp phu
trach phong thi nghiem Khoa Ky thuat - Cong nghe - Moi truang da giup da va
ho trg toi trong qua trinh thi nghiem:
Cam an Ban Giam doc nha may thuoc bao ve thuc vat huyen Chau Thanh
va a Tam da nhiet tinh giiip da trong qua trinh lay mau nude thai.
Ngoai ra, toi xin gdi ldi cam an rat muc chan thanh d^n cac ban cua toi.

Cam an cac ban trong nhung nam qua cung gin bo, cung hoc tap, da giiip da toi
trong qua trinh thuc hien mo hinh nghien cuu, da co vu, dong vien tinh than toi
khi nghien cuu gap van de.
Trong qua trinh nghien cuu de tai va vi^t bai khoa luan vdi kiln thuc va thai
gian con han che nen npi dung khong tranh khdi nhung thilu sot. Kinh mong
nhan dugc su gop y, nhan xet tir phia quy Thay, C6!
Toi xin chan thanh cam an!
LongXuyen, ngay 2 thang 5 nam 2013
Sink vien thuc Men

H6 Thi True Lia


Khoa lugn tdt nghiepLap DH10MT

CHT/ONG 1:
Sir phat tridn cua nganh ndng nghiep hien dai ludn gdh lien vdi viec sir dung
cac phuong tien hoa hoc va sinh hoc trong san xuat, bao quan va che bien, trong

do co cac hoa chit phong tru dich hai. Theo thdng ke ciia To chuc Luong thirc

Thd gidi (FAO) hang nam, thiet hai mua mang do sau, benh gay ra trung binh
mfit khoang 20 - 30% t6ng san luong. Viec su dung cac hoa chit BVTV da too
thanh mot trong nhtrng phuong tien kinh td nhlt trong cong tac phong tru dich
hai va bao quan nong san, dam bao an ninh luong thuc. VI vay, nganh hoa chat

BVTV tren th^ gioi cung nhu a Viet Nam ngay cang chiSm vi tri quan trong va
trd thanh lihh vuc khong the thiSu trong chi^n luge phat trifin nganh cong nghiep
hoa chat cua moi quoc gia.

Viet Nam la nuoc nong nghiep vdi dien tich canh tac Ion, dieu kien khi hau
thuan Icri, chung loai cay tr6ng phong phii nen dich hai phat trien da dang va
quanh nam. Vi vay, nhu c&i su dung cac thuSc BVTV la rdt cdn thi^t.
Tuy nhien, vdi tinh hinh lam dung thudc BVTV trong nong nghiep mot
each khong kiSm soat nhu nude ta hien nay gay ra ton du mot luong ldn cac chat
huu co doc hai, khd phan hiiy, tich tu lau dai trong moi truong tac dong true tiep
den sue khde con ngudi. Bac biet, d nude ta co rat nhieu cong ty sang chiet thuoc

BVTV va nude thai thuoc BVTV la nguon thai doc hai, khd xu ly bdi thanh phan
nude thai chua cac chat huu co mach vong nhdm clo, nhdm P khd phan huy sinh
hoc.

Hien nay, ca nude co 93 nha may, co so san xuat, gia cong, sang chai, ddng

gdi va 28.750 dai ly, diim ban le thudc BVTV, hon 100 co so san xuit, kinh
doanh va 2.250 dai ly, didm ban le thude thu y. Hdu hdt cac co so san xult thudcBVTV nam trong cac khu cong nghiep (chiem khoang 2/3), con lai nam rai rac
ben ngoai, xen ke trong khu dan cu (Mai Phuong, 2012).

Nude thai tu nha may thudc BVTV la mot hong nhung ngudn d nhilm
ddng, phat trien day truyen gdm rat nhieu thanh phan cac chat, hop chat vd co,
huu co.... Neu viec xu ly nude thai tir cac nha may thudc BVTV khong dung

each se la moi nguy hai rat ldn cho moi truong va sue khde cong ddng. Do do,
cong tac bao ve mdi truong nhat la mdi truong nude trong san xuat, kinh doanh
va su dung thudc BVTV la vdn dd cfin duoc dac biet quan tarn va giai quydt mot
each hai hoa de dam bao phat trien kinh te nong nghiep va bao ve mdi trudng,
bao ve sue khde ngudi dan.

GVHD: Ths. Truang Kien ThoTrang 1
SVTH: H6 Thi True Lia


Khoa lugn tot nghiepLapDHlOMT
, Trudc nhiing yeu cau va thach thuc ngay cang cao cua moi trudng, cac nha

khoa hoc va cong nghe da tien hanh nhieu cong trinh nghien ciiu theo hudng tim
cac cong nghe cao (advanced technologies) de ho trg cac cong nghe truyen thong
trong van de xu ly nude thai.

Cac qua trinh oxy hoa nang cao (AOPs) ngay nay dugc xem la nen tang cua
cong nghe xu ly nude va nude thai d the ky 21. Viec nghien cuu ap dung cac
thanh tuu khoa hoc mdi trong lmh vuc moi trudng de xay dung cong nghe xu ly
nude thai nha may thuoc BVTV la cap bach va can thiet. VI the, chiing toi thuc
hien de tai "Nghien civil iltinli gid liien qua xiv ly nu&c thai nha may thuoc bdo
ve thuc vat bdng he oxy hoa nang cao (O/UV/H2O" nhdm gdp phan cai thien
moi trudng do thuoc BVTV gay nen va de xuat mo hinh xu ly hieu qua cao ve
mat kinh te.

GVHD.Ths. Truong KiinThoTrang 2
SVTH: H6 Thi True Lia

Khoa lugn tdt nghiepLapDHWMT

CHUONG 2: LI/OC KHAO TAI LIEU

2.1. Tdng quan vl thudc BVTV
2.1.1.Thudc BVTV Id gi?
Thudc BVTV la loai hoa chdt co thd tieu diet hoac phdng trir dich hai. Dich
hai la sinh vat, vi sinh vat, cac loai sau hai, cac loai gam nham ... co kha nang gay

hai cho cay trdng va lupng thpc.
2.1.2.Phan loai thudc BVTV
Thu6c BVTV dupe phan thanh hai loai chinh la:
-Thudc tru sau
-Thuoc trir c6

Thudc BVTV co hieu lire d6i vdi dich hai bSng nhidu each khac nhau nhu
qua dudng rupt, qua mieng, qua da, qua hit thd....

2.1.3.Tdc hai cua thudc BVTV
Trong tir nhi^n co rat nhieu loai sSu hai khac nhau, co loai sau an nup dudi
la, co loai due vao than cay, co loai lai chui vao ddt, nen phai dung nhieu loai
thudc khac nhau d6 tieu diet chung. Viec nay gay kho khan cho nguoi su dung,
nhat la nhung ngudi nong ddn co trinh dp van hoa thap. Nhieu ngirdi chi thich
mua thuoc re de phun, khong can biet pham vi tac dung cua chung ra sao. Co

ngudi hay phun qua lieu chi dan de cho "chac an", lam tang luong thuoc thua tich
dpng trong dat va nude.

Cac loai thuoc tru sau thudng co tinh nang rpng, nghia la cd the diet dupe

nhieu loai con trung. Khi dung thuoc diet sau hai mot so con triing cd ich cung bi
diet luon, dong thdi anh hudng tdi cac loai chim an sau, vi chim an phai sau da
trung dc. Ndi each khac, sau khi phun thudc tru sau, sd luong thien dich ciia
nhieu loai sau cung giam.

Cac loai thudc trir sau ddu cd tinh ddc cao. Trong qua trinh dung thudc, mot
lupng thudc nao do co thd di vao trong than cay, qua, hoac dinh bam chat tren la,
qua. Ngudi va dpng vat an phai cac loai ndng san nay cd the bi ngp ddc tuc thdi
den chet, hoac nhiem ddc nhe, tir tir gay anh hudng nghiem trong den sue khoe.
Mot so loai thudc trir sau cd kha nang bay hai manh nen gay khd chiu, met
mdi, th^m chi choang ngat cho ngudi true tiep phun thudc sau tren ddng rudng^
nhat la trong trudng hop khdng cd cac bien phap phdng tranh tdt.
GVHD: Ths. TruongKiin ThoTrang 3
SVTH: H6 Thi Trite Lia


Khoa luan tdt nghiepLap DH10MT
Viec dung thuoc tru sau lien tuc se sinh chiing nhdn thuoc. Vi the moi loai
thuoc trir sau chi co tac dung manh mot so nam dau sur dung. Be han che benh

nhdn thuoc, tang kha nang diet trir sau ngudi ta thudng tang dan nong dp thuoc,
tang so Ian diing thuoc. Mat khac, no lam 6 nhiem moi trudng manh hon, do
lupng ton du trong moi trudng nhieu len.

Mot so loai thuoc trir sau co tinh nang hoa hoc on dinh, khd phan huy nen
se tich luy trong moi trudng. Sau nhieu Ian su dung luong tich luy nay co the cao
den muc gay doc cho moi trudng dat, nude, khong khi va con ngudi. Do thuoc

tdn dpng lau khong phan huy nen co the theo nude va gio phat tan tdi cac vimg
khac, theo cac loai sinh vSt di khap moi noi.

Noi torn lai, thuoc trir sau, diet co khong chi co tac dung tich cue bao ve
mua mang ma con gay nen nhieu h6 qua moi trudng nghiem trong, anh hudng tdi
he sinh thai va con ngudi.

2.2. T6ng quan ve cong nghe xu- ly nude thai thudc BVTV
He thong xu ly nude thai hoa chat dupe su dung cac thiet bi trung hoa, hap
thu than hoat tinh, ozone, sau do theo muong thai chay ve he thdng ao xu ly sinh
hoc co lot day blng mang HDPE chdng thlm. Ngudn nude thai sau xu ly dupe
Iuu giu trong ao chua, khong thai ra ben ngoai. Ngoai ra, nude mua chay tran

dupe thu gom vao he thong muong thai trong khuon vien khu vuc va dupe thoat
vao he thong h6 chiia va ao sinh hoc de dam bao loai trir cac nguon thai bi rua
troi each li va phan huy an toan thanh phan cac loai thuoc BVTV cuon theo nude
mua chay trim.

Dua tren dac tinh chung cua cac loai thuoc BVTV lit tan dupe trong nude,
cong nghe diing nude de pha loang thuoc ddn nong dp can thiet, sau do dua vao
xu ly nude chiia thudc BVTV. Qua trinh xu ly thuc hien trong nude tudn hoan
tao thanh mot vdng Iuu chuyen tu8n hoan, diem dau la nude chua thuoc BVTV
can tieu huy, diem cuoi la nude dS xu# ly sach. Tir day, lay chinh nude da xd ly
dem^hoa tan thudc BVTV mdi d^ tidp tuc qua trinh. VI thd hieu qua xu ly cao va
rat an toan, nude sau khi xu ly dupe su dung lai de bo sung vao qua trinh tao
thanh chu trinh khep kin chu khong he thdi ra ngoai, khong gay hai cho moi
trudng. Theo cac chuyen gia danh gia, phuong phap nay co nhidu uu di^m an
toan tuyet doi cho moi trudng do khong co khdi va nude thai ra ngoai, chi phi
nang lupng thap, phuong phap tieu huy thuoc BVTV khong dot nay so vdi chi
phi xu ly re hom each diing Id ddt ddn 50% - 60%. Tdng chi phi dlu tu thiet bi chi
khoang 1 ti dong, do vay rat thich hop vdi trinh dp cong nghe va vdn ddu tu d
nongthon (Phuong Nguyen, 2010).
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Khoa luqn tot nghiepLap DH10MT
Nude thai thu6c trir sau la mot trong s6 cac ngudn thai doc hai, khd xur ly
bdi thanh phan nuac thai chiia cac hop cht him ca mach vong nhdm Clo, nhom
P kho phan huy sinh hoc. Tai cac cong ty san xuat thuoc trit sau, lupng nuac thai
nay khong nhieu nhung doc tinh lai rat cao. Thong thudng tai cac cong ty nay
dung cong nghe xii ly nang do pH trudc de thuy phan cat mach. PGS.TS Nguyen
Van Phudc cung nhom nghien cuu Dai hoc Bach khoa TP. Ho Chi Minh da
nghien cuu va dua ra mot mo hinh xu ly mdi bang each dua nuac thai qua be loc

sinh hoc ki khi vdi vat lieu dem la so dira. Chi tieu c3n chii y ctia nude thai khi
qua be loc nay la chi tieu ve COD, pH. Sau do, nude thai duqc tiep tuc dua qua
be biin hoat tinh roi bun sinh hoc hieu khi va cuoi chng la be oxy hoa. Tai day
tilp tuc dung he chSfFenton d^ oxy hoa mlu nude thai sau keo tu, xac dinh
lugng FeSO4 va H2O2 thich hop. K^t qua cho thdy nude thai qua be loc ky khi dp
pH biSn dpng, COD giam din. Diu nay chung to sinh vat da thich nghi dan va
cd hieu qua. Dae bi6t qua trinh ki^m hoa giam 30 - 50 % COD, qua trinh sinh
hoc xu: ly 94,8 % COD con lai. Tigp dSn qua trinh hoa hoc xii ly triet dg cac chit
6 nhiem, nude sau xii ly dat tieu chuan nude thai (Bich Ngoc, 2006).
2.3. Tong quan ve qua trinh oxy hoa nang cao trong nude thai
2.3.1.Dinh ngMa ve qua trinh oxy hoa nang cao

Qua trinh oxy hoa nang cao (Advanced Oxidation Process - AOP) la sii
dung cac goc hydroxyl (*OH). Nhu mot chat oxy hoa manh de pha hiiy nhQng
hon hop ma khong the la nhung chat oxy hoa nhu oxy va clo truyen thong. Hieu
qua cua he thong dupe th6 hien qua khi h^ng so phan ling cua nhung goc
hydroxyl vdi da so nhung chat gay 6 nhiim him ca bac cao. Hydroxyl phan ling
vdi mot trieu tdi mot ti chat 6 nhiem va oxy hoa hoc nhanh chong han nhu ozone

va nude oxy gia (Cokay, 2002).
2.3.2.Nhung liqn die cua qua trinh oxy hoa hoa hoc bang cac tdc nliiin

oxy hoa thong thufrng
Trong cong nghe xii ly nude va nude thai truyen thong thudng su dung cac
chat oxy hoa thong dung sau day:

> Clo (CI2)
Clo la chat oxy hoa hoa hoc tot dupe sii dung dS khii Fe2+ trong nude ngam
hoac nude mat, trong khii trung nude sau khi xu ly. VI clo la chSt oxy hoa manh,
re tien va de sd dung nen dupe su dung pho bien trong llnh vuc xii ly nude, nude
thai cho den ngay nay. Tuy vay, nhupc diem cua clo la trong qu^ trinh khu s^t va
khii trung b^ng clo da tac dung vdi cac chdt huu ca thien nhien, tao ra hop chat

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KhoalugntdtnghiepLap DH10MT
huu cff chiia clo co nguy ca gay ung thu cho ngudi sii dung (Trdn Manh Tri,
2006).
>Kali permanganat (KMnO4)
Kali permanganate la chat oxy hoa dugc sur dung rpng rai trong xii ly
mice. Day la chat oxy hoa manh hern clo, co the lam viec trong khoang pH rpng
nhung.dat tien. Them vao do, qua trinh nay tao ra Mangan dioxit d dang khong

tan va phai tach ra bang phuong phap hoa hoc hoac lang; vi vay kha nang tang
them chi phi cho qua trinh xu ly la dieu khong the tranh khdi.
y Hydrogen peroxit (H2O2)
Hydrogen peroxit la chat oxy hoa manh hon clo va kali permanganat

nhung ydu hem ozone (O3) va dupe su dung rat ph6 bidn trong xii lynudc thai de
phan My cac chit huu ccr va khu mau cua nude thai nganh gidy hoac det nhupm.
Ngoai ra, uu diem cua hydrogen peroxit la khong sinh ra chat doc hoac chat co
mau trong qua trinh su dung. Tuy nhien, kha nang oxy hoa cua hydrogen peroxit

khong du manh de khoang hoa hoan toan chat 6 nhiem huu co nhu yeu cau da dat
ra (Trdn Manh Tri, 2006).

>Ozone (O3)
Ozone la chat oxy hoa manh nhat trong cac chat oxy hoa thong dung ke
tren. No dupe su dung lam chat khil trung, phan huy cac chat huu ca hoac de khu
mau nude thai, khu mui hoi, khu sat hoac mangan,....Uu diem cua mangan la tu

phan huy, khong de lai cac phu pham la va nguy hiem trong nude sau khi phan
ling. Tuy vay, ozone kem hoa tan trong nude va la hpp chat khong ben, thai gian

ton tai chi vai phut. Vi vay, de dat dupe so lupng ozone hoa tan trong nude du
ldn cho qua trinh oxy hoa, phai dua vao he mot so lupng ozone ldn. Ngoai nhupc
diem tren, khi su dung ozone lam chat oxy hoa trong xii ly nude va nude thai la
phai san xuat ozone tai ch, ngay trong day chuydn xu ly.
2.3.3. Cac qua trinh tao ra gdc Hydroxyl (*OH)
Do goc Hydroxyl (*OH) co kha nang oxy hoa rdt manh, t6c dp phan ling
oxy hoa rat nhanh va khong chpn lira khi phan ling vdi cac hpp chat khac nhau,
nhieu cong trinh nghien ciiu trong may thap ki qua la cac qua trinh tao ra gdc
hydroxyl tren ca sd cac tac nhan oxy hoa thong thudng nhu ozone, hydrogen
peroxit thong qua phan ling hoa hoc (H2O2/Fe2+, O3/H2O2, O3/xiic tac) hoac nhd
biic xa cue tim UV (O3/UV, H2O2/UV, O3 + H2O2/UV, H2OATJV, TiO2/UV) va
cac ngudn nang lupng cao (sieu am, tia gamma, tia X, chum electron).

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Khoa ludn tdt nghiepLapDHlOMT
2.3.4. Nhieng uu viet cua qua trinlt phan huy oxy hoa bang goc tu do

Hyroxyl (*OH)
> Goc tie do Hyroxyl (*0H) va kha ndng oxy hoa ciia goc Hydroxyl
Oxy hoa la qua trinh trong do electron dirqc chuyen ttr chat bi oxy hoa sang
chat oxy hoa, tao ra mot hieu the dirqc hien thi bang volt (V) dtra tren hieu the
dien cue hydro bang 0. Moi tac nhan oxy hoa dieu co mot the manh oxy hoa khac

nhau va dai ltrqng nay duqe dung de so sanh kha nang oxy hoa manh hay yeu cua
chung.

Kha nang oxy hoa cua cac tac nhan oxy hoa duqc thi hien qua the oxy hoa
va duqc sap xep theo thii tut trinh bay trong bang dudi day:

Bang 2.1. Kha ndng oxy hoa cua mot so tac nhan oxy hoa

STT

Tac nhan oxy hoa

ThS oxy hoa, V

1

Goc Hydroxyl

2,80

2

Ozonee

2,07

3

Hydrogen peroxit

1,78

4

Permanganat

1,68

5

Hydrobromic axit

1,59

6

Clo dioxit

1,57

7

Hypocloric axit

1,49

8

Hypoiodic axit

1,45

9

Clo

1,36

10

Brom

1,09

11

Iod

0,54
(Nguon: Trdn Manh Tri, 2006)

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Khoa luan tSt nghiepLap DH10MT
Trong cac tac nhan oxy hoa tren, goc tu do Hyroxyl (*OH) la tac nhan oxy
hoa manh nhat. Qua bang 2.1 ta thay, the oxy hoa goc Hydroxyl la 2,8 V, cao
nhat trong so cac tac nhan oxy hoa thuong gap, gap 2,05 Ian clo va 1,52 Ian
ozone.

Dae tinh cua goc tu do la trung hoa ve dien trong khi cac ion dieu mang
dien ti'ch duang hoac am. Goc tu do dugc tao thanh trr sir tach ra hai phan bang

nhau cua lien ket hai electron, vi du: khi quang phan H2O2 se thu dugc 2 goc
*OH nhu sau:

HO:OH + hv -> *OH + *OH
Moi goc *OH deu khong mang dien, hai goc *OH co the ket hop tro lai
thanh HOOH cung khong mang dien. [Luu y: ky hieu * cho biet la goc tu do va
bieu thi mot electron le doi]. Goc tu do nay khong ton tai sdn trong moi truong
nhu nhung tac nhan oxy hoa thong thuong ma chi san sinh ra ngay trong qua
trinh phan ling, co thai gian song rat ngan, khoang vai nghin giay nhung lien tuc
dugc sinh ra trong suot qua trinh phan ling (Trdn Manh Tri, 2006).
> Co chephan img vaphuong thucphan ung cua goc Hydroxyl (*OH)
Mot khi goc tu do dugc hinh thanh, lap tiic xay ra hang loat cac phan ling ke
tiep theo kieu day chuyen vdi nhtlng goc hoat dong mod. Vi vay, sir hinh thanh
g6c Hydroxyl dugc xem nhu la mot sir khoi mao cho hang loat cac phan ling xay

ra ke tiep trong dung dich. Vi phan ling ciia goc Hdroxyl xay ra khong chon lua,
nen trong qua trinh do tao ra nhieu san pham trung gian khac nhau, kho tien don
tat ca nhttng san pham oxy hoa trung gian co the tao ra trong qua trinh.

G6c Hydroxyl (*OH) co thi tac kich vdi cac chit 6 nhilm theo cac kiiu sau:
-Phan ling cong vai cac hgp chat khong no day thing hoac vong thom, tao ra
goc moi Hydroxylat hoat dong:
*OH + CH2 = CH2 -^ *CH2-CH2(OH)
-Phan ling tach hydrogen tir cac hop chit no hoac khong no, tao thanh nude va
goc mdi hoat dong:
*OH + CH3 - CO - CH3 ^ *CH2COCH3 + H2O
-Phan ling trao dien tur tao ra goc ion mdi hoat dong:
*OH + CH3-S-C6H5 ^> [CH3-S-C6H5]+*+ OH"

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Khoa lugn tot nghiep

Qua trinh phan ling tiep tuc phat trien nhd cac goc tu do mdi sinh ra theo
kieu phan ung day chuyen cho den khi vo co hoa (khoang hoa) hoan toan hoac
day chuyen bi dut.
Muc dich mong muon cuoi cung trong qua trinh oxy hoa cac chat 6 nhiem
trong nude thai la de vo co hoa hoac khoang hoa, tuc chuyen chat 6 nhiem huu
ca thanh cac chat vo co ion gan va khong doc hai.

Dae diem chung cua cac chat oxy hoa bang cac tac nhan oxy hoa thong

thudng la khong th^ xay ra vdi mpi chat va khong the xay ra triet de. Trong khi
do, dac trung quan trong ciia g6c *OH thi ngugc lai la hau nhu khong chon lua
khi phan ung vdi cac chat khac nhau de oxy hoa va phan huy chung.

Bang 2.2. Cac hap chat huu ca bi oxy hoa bai goc Hydroxyl (*OH) daduac
nghien curu

STT

Nhom
Axit

Hop ch^t
Fomic, gluconic, lactic, malic, propionic,
tactaric

Alcohol

Benzyl, tert-butyl, etanol, etylen, glycol,
glyxerol,iso-propanol,methanol,

propenediol

Aldehyd

Axetaldehyl, benzaldehyd, focmaldehyl,
glyoxal,iso-butyraldehyd,
tricloroaxetaldehyd.

Aromatic

Benzen, clorobenzen, clorophenol, creozot,
diclorophenol, hydroquinon, p-nitrophenol,
phenol,

toluen,

triclorophenol,xylem,

trinitrotoluene.

Amin

Anilin,

amin

vong,

dietylamin,

dimetylfocmamid, BDTA, propandiamin,
n-propylamin

Thuoc nhuom

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Antraquinon, diazo, monoazo

Trang9


Khoa luqn tot nghiepLdpDHlOMT
7Eter•

Tetrahydrofuran

8KetonDihydroxyaxeton, metyl-etyl-keton

(Ngudn: Tr&n Manh Tri, 2006)

2.3.5. Phan loai cdc qua Irinh oxy hoa nang cao

Theo Co quan bao ve moi truong My (USEPA), dua theo dac tinh cua qua
trinh co hay khong co su dung ngudn nang luong biic xa tu ngoai UV co the
phan loai cac qua trinh oxy hoa nang cao thanh hai nhora trong cac bang sau day:

Bang 2.3. Cdc qua trinh oxy hoa nang cao khong nha tdc nhdn dnh sang

STT Tac nhan phan ting
1H2O2 va Fe2+

Phan ting dac trungTen qua trinh
H2O2 + Fe2+-> Fe3+ + OH" +Fenton

*HO
2H2O2 va O3

H2O2 + 2O3-> 2*HO + 3O2Peroxon

3O3 va cac chit xiic tac 3O3 + H2O ——> 2*HO +Catazon

4O2
4H2O va nang luoug

H2O

"" > *HO + *HOxy hoa dien

dien hoahoa
5H2O va nang luong

H2O

"'" > *HO + *HSieu am

siSuam(20-40 kHz)

6H2O va nang lugng
cao

H2O —"-^> *HO + *HBiic xa nang
,

,„

.luong cao

(1-10 Mev)• &

(Ngudn: USEPA, 1998)
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LapDHlOMT

Khoa ludn tot nghiep

Bang 2.4. Cdc qua trinh oxy hoa ndng cao nha tdc nhdn dnh sang
Tac nhan phan
Phan ling dac trung

STT

T^n qua trinh

u-ng

1

H2O2 va nang

lugng photon UV

2

03 va nang lugng
photon UV

3

4

UV/FI2O2

H2O2 —^ 2*H0
(A = 220 nm)
O3 + H2O —^ 2*HO
(A= 253,7 nm)

H2O2/O3 va nang

H2O2+O3 + H2O -^ 4*HO

lugrng photon UV

+ O2 (A = 253,7 nm)

H2O2/Fe3+ va nang

Fe3++H2O -4^->*HO +pe2++

lugng photon UV

UV/O3

UV/H2O2+ O3

Quang Fenton

H+
Fe2+ + H2O2 —^^-> Fe3++ OH"

+*HO

5

TiO2 va nang
lugng photon UV

TiO2

*" ) e" + h*

Quang xuc tac

ban din
(A>387,5nm)

h+ + OH" -> *HO + H+

(Ngudn: Trdn Mqnh Tri, 2006)

2.3.6. Cdc qua trinh oxy hoa ndng cao tren casd ozone

> Sir dung ozone trong qua trinh oxy hoa ndng cao

Ozone la mot trong so nhung chit phan ling duroc dung trong qua trinh oxy
hoa nang cao. Nhir mot chit oxy hoa, ozone hilm khi co thl kit hop true tilp voi
cac chat oxy hoa khac. Nhirng ngay nay, ozone dugc su dung vdi nhung chat oxy

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Kh'oa lugn tdt nghiepLapDHlOMT
hoa khac nhy UV, H2O2 va TiO2. Ozone la chit oxy hoa manh vdi nhung chit
gay 6 nhiem bat nguon tir nude thai cong nghiep. Hieu qua xur ly co the dtdi 99% vdi su oxy hoa ozone trong nhung dieu kien toi uu. Nhttng su ket hop
ozone vdi nhung chat oxy hoa khac co the se xu ly nude thai trong cong nghiep
thanh cong hon. Trong cong nghiep lam giay; dp pH trong phuong phap su dung
ozone rat quan trong (Amat, 2005).

Thi oxy hoa khu cua ozone la (+ 2,07 V). Ozone la mot chat oxy hoa manh
ma it hoac khong co san pham phu nao dupe hinh thanh trong qua trinh xu ly
nude thai chiia xyanua. Ozone dupe su dung trong nhung thi nghiem da xac nhan

ring mang ciia xyanua dupe oxy hoa bdi ozone. Trong khi mot ket qua nghien
ciiu loai bo cyanid nay la dat din 99,9% trong 20 phut (Parga, 2003).
Nhung nghien cuu gan day chi ra rang xd ly ozone co hieu qua trong viec
loai bo nhung chat gay 6 nhiem htru ca. Nhu vay, oxy hoa hoa hoc dang su dung
ozone la each de giam bdt cac chat 6 nhiem trong nude thai va tir day hieu qua
xu ly sinh hoc dupe the hien khi chit 6 nhilm bi oxy hoa bdi ozone (xu ly chua
triet de) no se bi giam hoat tinh do do qua trinh su ly sinh hoc trd nen de dang
hon. Toe dp oxy hoa ozone phu thupc gia tri pH hay them chat phan ling Fenton
hoac buc xa tu ngoai vi su phat sinh nhung goc hidroxyl ( OH) (Monieagudo,
2005).

UV la nhung song dien tu. Buc xa dien tu anh sang tu-ngoai tu 10 va 400
nm va dupe chia nhd ra thanh vai vung. Pham vi anh sang UV khong nhin thay
dupe co budc song tu 400 nm trd xuong (Masschelein, 2002).
Phuong phap oxy hoa buc xa dang su dung anh sang UV va them H2O2 nhu
mot phan cua cong nghe oxi hoa bac cao va to ra rat hieu qua loai bo nhung chat

gay 6 nhiem huu co doc dupe tim thay trong moi trudng nude (Cokay, 2002).
> Qua trinh Peroxon (O/U2O2)
Qua trinh oxy hoa cua ozone vdi su co mat cua hydrogen peroxit (O3/H2O2)
dupe gpi la qua trinh Peroxon hoac Perozone. Su khac nhau co ban giua hai qua
trinh Ozone va Peroxon la d cho: qua trinh Ozone thuc hien qua trinh oxy hoa
cac chat 6 nhiem chu yeu true tiep blng phan tu ozone trong nude trong khi do
qua trinh Peroxon thuc hien su oxy hoa cac chit 6 nhilm chu ylu la gian tilp
thong qua goc hydroxyl dupe tao ra tir ozone.

Khi ozone hoa de thuc hien qua trinh oxy hoa, lupng ozone khong hoa tan
het, con du thoat ra d dang khi, trong khi do d qua trinh Peroxon, do su co mat
hydrogen peroxit da gia tang dang ke qua trinh tieu thu va phan huy ozone la cho
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