Tap chi Khoa hoc va Ky thudt.-So 170(8-2015) - Hoc vien KTQS
NGHri;N ClTu TONG HOP POLYME CATION Ttr DICYANDIAMIDE VA FORMALDEHYDE (DCD-F)
ITNG DyNG xtr LY Nirdc THAI DET N H U O M Bo Huy Thanh, Le Minh Bong, Vu Ngoc Boan*
Bai bio trinh bay phuang phip t6ng h^p polyme cation DCF-F tii hai chit ban diu la dicj^ndiamide v^ formaldehyde. Khao sat cac ygu t6 inh hucmg den kha nang phin iing va hieu qui xii ly nhu nhi^t do, xue tac, n6ng dp cac chat... nhim xii ly nudc thii d^t nhuom.
San pham thu du(?c co hi$u su^t xii ly dp mau trln 90% vi xii ly COD tren 75%.
1. M& dau
Qua trinh det nhupm sir dung mpt lurpng nudc kha lan phyc vu cho cac cong doan san xuat, tu do cung thai ra mpt lupng nudc thai bmh quan 12-300 mVtdn vai. Ngu6n 6 nhilm chinh la nudc thai tu cong doan d6t nhupm va nlu tiy. Cdc chi phi ciia qua trinh xijr ly nudc thai d nudc ta cdn rit cao, nhit Id trong gjai doan xu ly dp mau vk COD.
Tren the gidi cd rat nhieu phuang phap xii ly nudc thai det nhupm, trong do phuang phdp xu ly mau tir polyme cation DCD-F, dupc cac nhd khoa hpc Nhgt Ban Ryuichi vd Michiaki nghien ciiu tim ra tu nhung thdp nien 90 cua thS ky 20. Tir khi ra ddi din nay da cd nhilu sdn phim xu ly mdu biln tinh tu nln DCD-F cd dac tinh khu mdu rat tot [1,2]. Carbone [3] vd cac ddng nghiep cho NH4CI vdo trong phdn iing thdnh 2 lin, moi lan each nhau 15 phut, sdn phim dupc sii dung xir ly man cho nhd mdy det:
Vdi kit qua dp man gidm 82,6%, COD gidm 61,7%. Trong bdo cdo cua .H. A. Kapejnni [4], hexamethylenetetramine duac sir dung thay cho NH4CI. Trong moi truang axit ciia phan ung trung ngung, san pham thu duac neu sii dimg dpc lap thi hi?u qud xir Iy thdp, khi tde gid bo sung chit trp lang thi hi?u qua xu Iy tang len. Fei Yue C. cung ding nghidp da biln tinh DCD-F bang ure [5, 6] vdi rauc dich ha gid thdnh sdn phdra va tang tic dp keo tu cua polyme. Ddu thi ky 21, sdn phdm thuang mai tu DCD-F da dupc sir dung rpng rai tr6n thi trudng do cd cac tinh nang uu vi?t nhu: quy trinh dieu chl dan gidn, tan tdt trong nudc, tinh dn dinh cao phu hpp vdi khi hau nhi^t ddi, gjam d nhiem moi trudng vd hi$u qud kinhte cao.
Vdi mong muon h^ gia thanh san phdm, nhdm tac gid budc dau tim ra quy trinh dilu chl DCD-F (dupc dat ten Id DF-01) trong phdng thi nghiSm, cd hieu qud xir ly dp mdu, COD cao, phit hpp vdi diSu kien sdn xudt va su dyng thirc te trong nudc.
• HQC vien KTQS.
Joumal of Science and Technology.-N.] 70(8-2015) - Military University of Science and Technolosv ^
2. Thirc nghiem
H6a chat dicyandiamide, ammonium chloride, formaldehyde va cac phu gia khac tu hang Sigma, Tmng Quoc; nuac thai dugfc ldy true tiep tu lang nghe (lang lya Van Phiic). Cac phan ling dieu che dugc th\rc hien trong binh cau 3 co, on dinh nhiet bing dun each dau. Tien trinh phan ling ducrc theo doi bang sac ky ban mong, su dung dung dich chat chi thi /7-anisaldehyde hoac den UV. Pho hong ngoai IR dugc do tren may Perkin Elemer Spectrum IR 400 tai Bo mon Thu6c phong - Thufle n6. Hoc vi$n KTQS.
Do dp mau ciia nuac thai bang phuang phap trSc quang tren may phfl quang ki 752 Trung Quoc (Bg mon CN Hoa hoc - Hgc vi$n KTQS).
2.1. Tdng hfp DCD-F (DF-01)
Cho l k lugt 3,53 gam dicyandiamide, 8,5 ml formaldehyde (37%), 1,5 gam amraoniuin chloride vao binh cSu 3 cfl. Hon hgp dugc khuiy trgn d&i, dun hfli luu a nhiet dS 4042°C.
Sau thai gian 30 phiit, thSy dicyandiamide tan hoan toan trong formaldehyde, cho higng con lai 0,74 gam ammonium chloride va 1 gam chSt phu gia vao phan ling. Ti&i hanh phm ling tning ngung g nhiet do 70-80''C, thoi gian 2-4 gig. San phim thu dugc khflng mau trong sudt, CO inh kim, dp nhat r| = 5,09, phan tu khfli ttung bmh M«4500 (dvQ.
Quy ttinh tflng hgp dugc thuc hien theo sg do ttong hinh 1.
NH-CH,OH ^^^^^,
H2N-C-NH-CH2OH
II 4. ^
N H2N-C=NH HsN-C-NH-CHjOH
N*
H2N-C=NH
H2N-C-NH-CH2OH N*
H2N-C-NH-CH2OH HjN-C-NHCHj
N*CI H2N-C-NHCH2-
-N-C-NHCH2-
H 'f'"'
-N-C-NHCH,-
- N H - C - N H C H 2 O H N'*"CI - N H - C - N H C H 2 O H
Hinli 1. Quy trinh tong ht^ DF-Ql 2.2. Phumg phdp xic ajnh pluin ti IchSi trung binit
B6 xac dinh phan tti khfli trung binh dung phuang trinh Mark-Houwink:
II = K. M ;
ttong do, M - khfli lugng phan tu trung binh cua polyme; T, - dfl nhgt dac ttung cua polyme; K va a - nhiing hing s6 phy thuoc ban chJt dung moi va nhiet do.
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Tap chi Khoa hoc va Ky thudt.S6 170(8-2015) - Hoc vien KTQS
Xac dinh dd nhdt cua san phim dua vao nhdt ke Ostwald, tu dd xay dung dudng chuan xac dinh T] d?c tnmg tiiay vdo phuang trinh Mark-Houwink d nhiet dp (20 ± 5)°C vdi K = 1,99.10"^; a = 0.659 [7], tim dupc phdn tu khdi tmng binh cua sdn pham.
2.5. Phucmg ph^ xu- ty nu&c thai det nhugm
Ldy 200 ml radu nudc thai det nhupm cho vao cdc thi nghiera khuay deu bang rady khuay tu tde dd v = 300 vdng/phut d nhiet dp phdng, them 1 lupng xdc dinh chit khu mdu DF-01 va PAC, sau dd khudy diu trong thdi gian 2 phiit Them 1 lupmg chit trp keo tu AIOl, khuay deu 3 phiit, dl ldng va lpc ldy phdn nudc trong. Sau dd dung may quang phd ke 752 xac dinh dp hap thu quang. Ap dung phuang phap hdi quy theo dudng chudn xay dyng theo TCVN 6185:2008 xac dinh hieu suit xu ly mdu ciia sdn phdm DF-01.
a) Xdc dinh hieu sudt JOT ly mdu
Hieu suit xii ly radu //% = ^^—^ x 100%
A
trong do, A-Ao hdp thu quang sau xir ly; An - dp hap thy quang trudc xd ly.
b) Xdc dinh COB bdng phirang phdp trdc quang K2Cr07
Hieu suat xii ly COD CODf^-COD, COD^ ^ x l O O %
trong dd, CODcio - gia tri COD trudc khi xu ly; CODcr - gia tri COD sau khi xu ly.
3. K i t qua va thao luSn
3.1. Anh hu&ng cm ty le mol cdc chdt ten hieu qud xir ly mdu
Ldy mau nudc thai d$t nhudm sau khi pha loang (dp mau 1676 Pt-Co, gid tri COD I123(mg02/1)).
Hinh 2. Anh hudng ty l^ mol chdt phdn ung 3en hieu qud xu ly mdu
Joumal of Science and Technology. -H. 170(8-2015) - Miiilary University of Science and Teclmology
Ta thiy, khi ham ty le giua HCHO:DCD = 2,5:1 thi dat hieu qua xu ly mau dfe 84,6%. Khi tang ham higng HCHO dto ty le 3:1 thiy hi?u qua xii ly mau giam xuflng nhanh, nguyen nhan la do san phim cfl do nhat cao, khfli lugng phan tii cao, kha nSng tan trong nuoc kem din den hieu qua xu ly dp mau giam xuong th%). Vay voi ty 1$
HCHO:DCD = 2,5~2,7:I san phim co dp nhgt tflt, tan tflt trong nuac, hieu qua xii ly cao.
3.2. Anh hirdng cUa nhift do trong qud trinh dieu che sdn pham
Nhi?t dp la tac nhan quan ttpng ttong diflu chj san phAm DF-01, tir hinh 3 co the thay dugc anh huang ciia nhiet dp trong qua trinh dieu che den hieu qua xu ly mau.
fiinh 3. Anh huang cUa nhiet dg phan img den hi^ qua xu iy mau cua sdn pham Hieu suat xii ly mau ciia san phim tang khi nhiet phan ling tang tir 60-80°C va dat cvc dai 6 75-80°C (hifu suit xur Iy mau dat 89,7%). Tuy nhien, khi nhiet phan iing fing qua cao den 90°C thi hieu qua xii ly mau giam xuong, dilu nay dugc giai thich la: Khi ting nhiet dp ciia phan ling thi se lam tang dp nhat cua san phim len cao, khoi lupng phan hi himg bmh qua lom, ttong mpt sfl ttiiflng hgp con hien tugng dflng ran, tii d6 lam giam tinh tan ciia san phim trong nuoc din dfln hieu qua xu ly kem. Thi nghiSm chon nhift do tfli uu 6 75°C vi g dilu ki?n dfl phan ung xay ra thuan lgi, an toan, tilt ki?m chi phi trong qua trinh dilu chl san phim.
3.3. Phdn tich pho hdng ngopi
Phfl hong ngoai cua san phim DF-01 thu dugc trong hinh 4.
Tii hinh 4 cho thiy: pic dao dpng fl tin sfl 3546.5 cm' la nhom O-H, pic dao dpng vcri tan sfl 3400 cm'' la dao dgng hfla tri cua lien kit N-H ttong amin bJc 1, cac pic dao dgng bien dang ««« 1564 cm' mufli amin b|ic 1 va dao dpng UNH 1 UO cm' amin bac 2.
Djc bift, pic dao dpng hfla tti djc trung cua nhflm P'^H a 2179 cm'. Tu cdc nhflm djc ttung tten nhan dinh chit khii mau mang dien tich duong [9].
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Tap chi Khoa hgc va Ky thugt -So 170(8-2015) - HQC vien KTQS
Hlnh 4. Pho hong ngoai IR cua DF-01 3.4. Xdc d(nh phdn tir khoi trung binh cda DF-01
Da tiln hdnh xdc dinh khdi lupng phdn tu ciia san phdm tao thanh DF-01 theo phuang phap do dp nhdt. Do thi moi quan h? giiia dp nhdt dac trung vd ndng dp dupc the hien dhinh 5.
l s r «
5.5 ;
5 • Bfl
a E 4.5 • u S 4-
s
5 3 , 5 -
» i . - X « =
1
y - -S0.7I+ 5.09
^ R' - 0.976
^ ^
^•^-^
0 0.01 0.02 • cieiinS) 0.03 0.04 Hinh 5. Bo thi xdc dinh dg nhat ddc trung cua sdn phdm Tu dd thi hinh 5, tim dupc dp nhdt dac trung cua sdn phim y\ = 5.09. Dua vao phuang trinh Mark-Houwink, phan tu khdi trung binh sdn phim la M W4500 (dvC).
3.5. Anh hu&ng cda ndng dp DF-01 t&i qud trinh xu ly mdu
Ham lupng DF-01 dnh hudng rat ldn den qua trinh xir ly nudc thdi, ngodi ra Id yen td quylt dinh den hieu qud x^ ly nudc thdi, chi phi cua cd qua trinh sdn xudt.
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Joumal of Science and Technology.-N. 170(8-2015) - Military University of Science anjfechnology
10« T-
''°Hffl.r^Digftl<fS>V
700 800 900 Hinh 6. Anh hudng nong dp DF-01 den hi?u qud xii ly mduDa khao sat dnh hudng ndng dp DF-01 ddi vdi mpt sd thudc nhudm pho bien dling trong qud trinh det nhudm. Ham lupng cua ndng dp thudc nhupm pha theo ty 1?
vdo 200 ml nudc cat. Ket qud thye nghiem dupc the hi?n trong d l thi hinh 6, nhan thiy rang khi tang nong dp DF-01 thi hieu qud xu ly tang, hi$u qud tang nhanh trong khoang nhd hon 200 ppm. Khi tang nong dp DF-01 len tren 200 ppm thi hieu qua xii ly cd tang nhung tang eham hoac khdng dang ke, hon nua c6 hien tupng gidm hipu qud xii ly. Khi lupng DF-01 vupt qua 600 ppm tW Iai co hien tuang gidm hiSu qud xic ly. Tii kit qua thye nghiem cung nhan thiy rang, d ndng dp 400 ppm hieu qud xii Iy mdu tren hai loai thudc nhudm 2B-MD vd nudc thai det nhudm !d tdt han, dat d i n 9 4 % vd 90%, cdn d6i vdi Ioai thudc nhupm trye tilp VSF thi kem h a a
3.6. Anh hu&ng cua dgpHt&i hi^u qud xd" ly nu&c thdi
Nghien cim dnh hudng cua dp pH trong ddi tii 4-12 tdi hieu suit xir ly nudc thai dupc chi ra d hinh 7.
Hinh 7. Anh hudng pH dk hieu qud xti ly do mau, COD oia sdn pham
Tap chi Khoa hoc va Ky Ihudt.-So 170(8-2015) - HQC vten KTQS
Ket qua tten hinh 7 cho thiy, khi tang pH tii 4-8 thi hieu suit xii ly mau va COD tang din. Ci vung pH = 8 thi hifu qua xii ly tflt nhit vai dp mau dat 91,5%, COD dat den 73,2%. Tuy nhien, khi tilp tue tang pH > 8 thi hieu qua xu ly mau, COD giam xuflng nhanh, co the do san phim DF-01 hi phan huy, til dfl lam giam tinh nang xii ly mau vaCOD.
3.7. Anh hitdmg cUa chdt trcr keo din hieu qui xu 1^
100 ; - 90 •
g
a
10 20 30 40 50 Hamluqn^ chat ti^ keo (mg/l)
Hinh 8. Anh hu&ng cua chat tra keo tii din hieu qud xu ly nu&c thdi Ket qud d hinh 8 nhan thay su dung chat trp keo tu d ndng dp Id 40 mg/l dat hieu qud xu ly nudc thdi tot nhat dp mau dat 94,2%, COD dat 75,3% . Khi tang chdt trp keo ty thi hieu qua xii l;y mdu van dat hi^u qud tit, tuy nhien hiSu qua xir ly COD gidm xudng, nguyen nhan khi tang lupng keo ty chinh Id tang cac nhdm hiiu ca trong nudc xir Iy, do dd cd thi ldm cho chi sd COD tang len.
4. Kit lu^n
Bdi bdo da xdy dyng duac quy trinh tdng hop san phdm DF-01 vdi cac trang thilt bi Clia phdng thi nghiem vd dieu kien trong nudc, co the phat trien thdnh san phim thucmg mai vdi kha nang xii ly mdu hieu qua cao. Phdn ung thuc hien d ty le DCDiHCHO = 1:2,5 (mol) vd mOt lupng phy gia, nhiet dp tiln hdnh la 75"C, thdi gian phan ling 3 gjd. Dieu kien xir ly nudc thai: dp pH = 8, chit trp keo ty AlOI sii dyng 40 mgi, hdm lupng DF-01 xii ly Id 400 ppm, hieu qud xu Iy mau dat din 94,2% va COD d?t 75,3%. Cdc ket qud thu dupc dang tin cay vd sdn phdm dang dupc tiep tyc nghien ciiu dl nang cao han niia hieu qua xir ly mdi trudng.
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Joumal of Science and Technology.-N. 170(8-2015) - Military University of Science and Technology
Tai lieu tham khao
1. Michiaki Takimoto, Toichi Ebisuno. The reaction of cyanoguanidine with of formandehyde - hydroxymethylation. and methoxymethylation of cyanoguanidine. Bull. Chem. Soc. JpE, 56,1983, pp. 3319-3322.
2. S. Ryuichi, T. Michiaki. Reaction of N-Cyanoguanidine with formaldehyde - Preparation of new flocculants for anionic colloidaleparticles. Bull. Chem. Soc. Jpa, 66, 1993, pp. 2452-2453.
3. John N. Carbone, George S. Dominguez, Jayanti V. Isharani, et al. Dye waste-water purifitication. Ger.offen.2633636 1977.2.17/Us.appl.600534, 1975.7.31.
4. 51. A. KapejiHH, E. IT. ,HKy6oBCKHii, B. H. ,HpoMCKHH. Hoebiu (^jioKyjumm djin o-Hucmm eodbi. 1989,628.16.9.
5. U^%M^M^¥^. &&^DCD+Ure+HCHO. Patent: 1233593, 1994.
6. Dong Xueliang, Sun Ximeng, Liu Xiaopeng, Li Zhongxian, Xu Dan. Synthesis and application of a high-efficiency reactive decolorizing flocculant. Chemical industry and engineeringprogress, 30,2011, pp. 896-897.
7. Qingda Zhang, Zhoumei Li. Synthesis of a new cation dicyandiamide macromer and its copolymerization. Environmental Technology, 27, 1998, pp. 526-531.
8. Tiiu chudn Nhd nu&c CHXHCN Viet Nam, Chat luang nuac - kiem tra vd xdc dinh dg mdu.
TCVN:6185,2008.
9. Zhang Wenyi, Liu Mingyuan. Synthesis of cationic decoloring agent of DCD-F polymer and its application in dyeing wastewater. The Chinese joumal of process engineering, 06: 1217-5,2010.
iVgov nhgn bdi: 10 thdng 3 ndm 2015 Ngdy nhgn bdn sHa ldn cudi: 04 thdng 6 ndm 2015
