Nghiên cứu chế tạo vật liệu hấp phụ sét hữu cơ organoclays trên cơ sở nguồn nguyên liệu bentonit và ứng dụng để xử lý các chất hữu cơ độc hại trong nước
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DAI HOC QUOC GIA HA NQI TRl/OfNG DAI HOC KHOA HQC i V NHIEN DE TAI NGHIEN CUtJ KHOA HQC DAC BI?T CAP DAI HQC QUOC GIA NGHI EN Ciru CHE TAG VAT LIEU HAP PHV SET HUtJ CO (ORGANOCLAYS) TREN CO SOf NGUON NGUYEN LIEU BENTONIT VA iTNG DUNG DE XlT LY CAC CHAT HUU CO DQC HAI TRONG NUOfC Ma so: QG-06-10 Chu nhiem de tai: PGS.TS Nguyen Van Noi DAI HOC QUOC GIA HA NOI_ TRUNG TAM THONG TIN THU V I E N uL^eLKt(Wk J Ha Noi - 2008 BAO CAO TOM TAT KET QUA DE TAI NGHIEN CUU KHOA HQC BAG BEET GAP DAI HQG QU6C GIA Ma so: QG-06 -10 l.Tendetai: Tilng Viet: "Nghien ciru chi tao vat lieu hdpphu set hitu ca (organoclays) tren ca so nguSn nguyen lieu bentonite va vmg dung di xic ly cdc chat hiru ca doc hgi nirac" Tilng Anh: ''Development of organoclays based on bentonite and their use in the treatment of hazardous organic chemicals in water and wastewater'' Chu tri de tai: PGS.TS Nguyin Van Noi, Khoa Hoa hoc, Truang DHKHTN Cac can bo tham gia: PGS TS Nguyen Dinh Bang, Truong DHKHTN PGS TS Nguyen Die Vinh, Truang DHKHTN TS.NguylnVietHung, Truang DHKHTN CN Tran Dinh Trinh, Truang DHKHTN HVCH Duong Thi Hanh, Truang DHKHTN Thoi gian thyc hien: B^t d^u tu thang nam 2006 den thang nam 2008 Muc tieu cua de tai: Nghien euu kha nang sir dung nguyen lieu khoang set bentonite de che tao vat lieu set huu ca va ung dung qua trinh xu ly cac nguon nuac bi nhiem cac chat huu ca doc hai Buae dau nghien cuu xay dung qui trinh cong nghe su dung set hiru ca de tach loai cac chat huu ca doc hai cac nguon nuac bi nhiem Tom tat noi dung nghien cihi cua de tai va ket qua dat dvac - Noi dung + Che tao va xac dinh cau true cua vat lieu set hiju ca + Khao sat kha nang xu ly cua vat lieu che tao duge - Phuong phdp nghien ciru: + Nghien cuu sir hinh set huu ca nha qua trinh trao doi ion cua bentonite vai cation huu ca dang [(CH3)3NR]" Cau true ciia set Huu ca dugc xac dinh bang cac phuong phap XRD, IR, SEM, TEM Dien ticH b^ mat rieng duge xac dinh bing thi6t bi Hap phu bl mat NOVA 2200 - Quanta CHROME + Danh gia kha nang sir dung set huu ca che tao dugc de xu ly cac chat huu ca doc hai nu6c thai det nhugm - San pham cong nghe: + Vat lieu set hmi ca ung dung xu ly nguon nuac bi nhiem boi cac hoa chat pham nhugm doc Hai - Kha nang irng dung thicc te: + Kha nang ung dung thuc te cua vat lieu set Huu ca che tao dugc de xu ly nuac thai bi nhiem boi cac hoa chat pham nhugm doc hai - Ket qua ddo tao: + So cu nhan dugc dao tao khuon kho de tai: - So thac sT dugc dao tao khuon kho de tai: - Da cong bo 01 bdo cdo tai Hoi nghi Khoa hoc quoc te, 01 bdo ado tai Hoi nghi Khoa hoc Truang DHKHTN, 02 bdi bdo pham vi thuc hien de tai Tinh hinh kinh phi cua de t a i : - Tong kinh phi dugc cip 60.000.000 dong - Da chi theo dung noi dung hgp dong : 60.000.000 d6ng XAC NHAN GUA KHOA PGS.TS Trinh Ngoc Ghau GHU TRI DE TAI PGS.TS Nguyen Van N^i CO QUAN GHU TAI DE TAI UlCTt I -rry\ rf^,jr P G S T S ^ ^ ^ ^ ^ SUMMARY OF THE PROJECT Project Title: ''Development of organoclays based on bentonite and their use in the treatment of hazardous organic chemicals in water and wastewater" Project code: QG- 06- 09 Project Leader: Assoc.Prof Dr Nguyen Van Noi Participants: Assoc.Prof Dr Nguyen Dinh Bang, Assoc.Prof Dr Nguyen Dae Vinh, Dr Nguyen Viet Hung , BSc Tran Dinh Trinh, Master student Duong Thi Hanh Objectives and contents: - Development of organoclays by modifying bentonite with HDTMA and TIOT -Characterization of organoclay structure by XRD, Thermal analysis, IR and SEM methods s - Sorption of some textile dyes such as direct dye, acid dye and reactive dye on Nabentonite, HDTMA-bentonite and HDTMA-TIOT-bentonite was investigated - Application of organoclays in the treatment of wastewater from Duong Noi textile handicraft village in Ha Dong town Project results Research results - Sorption materials-organoclays received from chemical modification of bentonite by HDTMA and TIOT - Organoclays were successfully applied in the treatment of wastewater from Duong Noi textile handicraft village Publication - 01 scientific report on the international Symposium (the third ISAMAP in Korea) - 01 report on the scientific conference of Hanoi University of Science - 02 papers Education results Graduated Students (MS): Undergraduated Students (BS): MO DAU O Viet Nam bentonite la mot loai khoang set re tien, c6 tru lugng Ian va duge su dung rgng rai nhieu nganh cong nghiep nhu xay dung, luyen kim, khai thac va che bien dau mo Dae biet, nha kha nang hap phu va trao doi ion tot nen Bentonite Cling da dugc ling dung rgng rai xu ly moi truang Viee nghien cuu che tao va su dung vat lieu hap phu set huu ca (Organoclay) dua tren ca sa Bentonite bien tinh da dugc phat trien manh me khoang thai gian 10 nam gan day va da ma nhung ung dung to Ian viee xu ly cac nguon nuac bi nhiem chat huu eo Nha kha nang hap phu va kha nang trao doi ion tot nen bentonit da dugc ung dung rat nhieu xu ly moi truang Bang each gan ket vao bentonit mot goe huu CO, bentonit duge bien tinh vat lieu ua huu ca Hon (set huu ca) Set huu ca dugc sir dung la vat lieu c6 kha nang hap phu tot cac chat nhiem c6 nguon goc huu co nhu cac loai pham nhugm O nuac ta, viee nghien cuu, ung dung set huu ca chu yeu llnh virc dlu khi; set hiru ca da dugc nghien cuu cong de pha dung dich khoan goe dau Tuy nhien, viee ung dung set hiJu ca xu ly nuac thai moi chi a nhijmg buae ban ddu D^ tai nghien cuu dugc xay dung'nham tan dung nguon khoang set bentonit re ti^n, c6 tru lugng Ian lam vat lieu xu ly cac chat huu ca doe hai, dac biet la hoa ch4t det nhugm, nuac thai mot each hieu qua Viee nghien cuu che tao vat lieu hip phu set huu ca tren ca so bentonit bien tinh va ung dung xu ly nuac thai nganh det nhugm c6 y nghia khoa Hoe va thuc tien Ion, gop phan hoan thien He vat lieu hip phu su dung ITnh virc xu ly nuac thai cong nghiep va sinh hoat PHAN 1: TONG QUAN 1,1 Gidi thieu ve vat lieu Set h(ru ca du^ tren cor so* bentonit bien tinh LLl Khdt qudt vi khoang set bentonit [5,7] Bentonit la khoang set theo ggi theo ten cua mo set "Benton", c6 phan chinh la montmorillonit vai cong thuc hoa Hgc tong quat dang (OH)4Al4Si802o.nH20 Ngoai bentonit mot so khoang khae nhu caolinit, mica, canxit, thach anh, cac muoi kiem Thanh phan hoa Hgc cua montmorillonit, ngoai hai nguyen to kim loai chinh la Si va Al c6 cac nguyen to khae nhu Fe, Ca, Mg, Ti, K, Na Ty le AI2O3: Si02 nam khoang 1:2 den 1:4 Bentonit dugc chia hai loai: - Bentonit truang no eo phan chinh la montmorillonit Na, hay ggi la Bentonit natri Khi bao hoa nuac bentonit natri eo the truang no den 20 Ian - Bentonit khong truang no c6 phan chinh la montmorilonit canxi, ggi la bentonit canxi 7.2 Cau true tinh the vd phan hoa hgc cua Montmorillonit Trong Montmorillonit cac nguyen tu Si nam a tam cua mang tu dien eon cac nguyen tu Al nam a tam cua mang bat dien va mot s6 ion nhom bi thay th6 bing ion magic, cong thuc tong quat nhu sau: (Na, Ca)(Al, Mg)6(Si40]o)3(OH)6.nH20 (Hydrated Sodium Calcium Aluminum Magnesium Silicate Hydroxide) • Silic o Oxi • Magie M: Kim loai den bu dien tich X: so ion magie Hinh 5: Mang cau true Montmorillonite Montmorillonit la aluminosilicat tu nhien c6 ciu true lap ki§u 2:1 diota Tinh th^ montmorillonit duge cau tao tu hai mang tu dien k^t vai mot mang bat dien a giua Giua cac lap cau true la cac cation trao d6i va nuac hydrat Khoang each giua cac lap ciu true ca ban cua Montmorillonit la 9,6 A° Khoang each bi thay doi nhieu hay it thugc vao s6 lugng, ban chat cation trao doi va lugng nuac hap thu, thuong len tai 15A° Khoang each c6 the tang den 40A° cac cation bi thay the boi ion v6 ca phan cue, cac phire ca kim, polyme v6 ca, cac phan tu huu ca Ducri day la so cau true khong gian mang luoi ciia lap Montmorillonit trung hoa dien d mang bat dien Al^" thuong bi thay the boi Mg^", mang tu dien Si'*" bi thay the boi Al^"hoac Fe^" Lugng Si'*" bi thay the boi Ap"^ khong vugt qua 15%, Su thay the dong hinh tren lam cho be mat tinh the montmorillonit xuat hien cac dien tich am cac cation kim loai thay the c6 dien tich duang thap Han, Cac dien tich am dugc trung hoa boi cac cation kim loai kiem (Ca, Na, Li, K) nam giija hai phien set Cac cation de dang bi hydrat hoa va/hoac dugc thay the bang cation khae Lap set M"" n H2O Cation kim loai bi hidrat hoa Lap set Hinh 6: Sa cau true khong gian ciia Montmorillonite 1.1.3 Cdc tinh chat cia set bentonit [5] a Tinh chat trao doi cation Nhu da trinh bay phan truae, mang cau true cua montmorillonit thuong xay sir thay the dong Huih cua cac cation Ket qua cua su thay thi la xuit hien cac dien tich am tren be mat philn set D6i vai bentonit, su thay the d6ng hinh chu y^u xay lop bat dien giua Hay lap tu dien cua phi6n set Lien kit cua cac cation vai b6 mat philn set la tuang doi yeu, vi vay cac cation de dang di ehuyin va trao ddi vai cac cation khae Kha nang trao doi cation cua bentonit phu thugc vao hoa tri va ban kinh cation trao doi Thong thuong, cac cation c6 hoa tri nho va ban kinh nho de bi trao d6i Han CJ cung nong kha nang thay tH6 cua cac cation theo trat tu sau: H" > Al^" > Ca^" > Mg^"^ > K"" > NHU" > Na" Dung lugng trao doi cation CEC (cation exchange capacity) dugc dinh nghia la t6ng s6 cation trao doi tren mot dan vi kh6i lugng set, thong thuong dugc tinh bang mili duang lugng gam (meq) tren lOOg set kho Vi tri trao doi ben ngoai o o n^ Vi tri trao doi ben Hinh Cdc vi tri trao doi cation tren hat set Dung lugng trao doi cation ciia set gom hai phan: dung lugng trao doi cation tren b§ mat phien set c6 gia tri khoang 5-10 meq, dung lugng trao doi ben a giija cac lap cau true vao khoang 40-120 meq Do kha nang de dang trao doi ion nen khoang set eo rat nhiet ung dung cac ITnh vue khae Vi du su trao doi Ca^" bang Na" da chuyen hoa bentonit canxi kem truang no bentonit natri eo truong no cao, ung dung de pha che dung dich khoan goe nuac Hoae trao doi ion kim loai vai caCvamin bac de tao set huu eo lam thay doi tinh chat eo ban cua set, tu set ua nuac set ua dau Set huu CO duge sir dung lam dung dich khoan goe dau, lam phu gia che tao vat lieu composit, lam vat lieu xu ly moi truang b Tinh chat truang na Trucmg no la mot nhiing tinh chat dac trung cua khoang set Khi tiep xuc vai nuac hoae moi truang khong am set bi truang no, the tich eo the tang len 15-20 Ian so vai the tich kho ban dau Trong qua trinh truang na, nuac xam nhap vao va dugc giu lai khoang khong gian giira cac phien set Lugng nuac hip phu phu thugc rat nhieu vao kha nang hydrat hoa cua cac cation Kha nang hydrat Hoa cua cac cation tang theo thu tu sau: Li" > Na" > NH4^ > K" > Mg^" > Ca^" > Al^" > H" KicH thuae, Hinh dang cua cac cation giua cac lap cung anh Huong den kha nang Hydrat hoa va truang no set Cac cation c6 ban kinh hydrat hoa Ian se lam cho khoang each giija hai phien set rgng ra, tao dieu kien cho sir trucmg no set Ben canh do, sir lien ket ciia cac cation kim loai va dien tich tren be mat phien set ciing anh Huong ddn su truang na c Tinh chat hdpphu Tinh chat hap phu cua bentonit dugc quyet dinh boi tinh chat be mat va cau true lap cua chung Dien tich be mat cua bentonit vao khoang 200-760 mVg Dien tich be mat cua bentonit gom dien tich be mat ngoai va dien tich be mat Dien tich be mat dugc xac dinh boi khoang khong gian giua cac lap cau true tinh the, dien tich be mat ngoai phu thugc vao kich thuoc hat, hat cang nho thi dien tich be mat ngoai cang Ian, do kha nang hap phu cang cao Su Hap phu a be mat cua bentonit chi xay chat bi hap phu la chat huu CO dang cation hoae chat hiru eo phan cue Doi vai cac chat dang cation thi bentonit hap phu chung theo eo che trao doi cation Sir hap phu trao doi phu thuoc vao dien tich, hinh dang, kich thuoc cua cation trao doi va dung lugng trao doi cation cua khoang set Cac chat huu eo phan cue c6 kich thuoc va khoi lugng nho bi hap phu bang each lien ket true tiep vai cac cation trao doi nam giua cac lap hoae lien kk vai cac cation qua cau H2O Con chat huu ca phan cue eo kich thuoc va khoi lugng Ian, lien ket true tiep vai oxi day cua tu dien mang luai tinh the bing lire Van der Wall 1.2 Vat lieu hap phu set hihi ca (Organoclay) Set huu ca hay ggi la set ua dau (organophilic clay) la san pham cua phan ung trao d6i ion giua set montmorillonit hoae Heetorit c6 cac cation trao d6i Na", Ca^" nam a giua cac lap set vai cac cation huu ca chu y6u la hgp chit amin Phuong phap trao doi cac cation giira eac lop cua Bentonite vai cation amin bac eo dang [(CH3)3NR]" R thuong la nhom alkyl mach dai tao nen mot dang Bentonite bien tinh ggi la Organoclay, eon dugc ggi la Set huu co Hay set ua diu Bent-Na + f(CH3)sNRJ^= Bent-NRfCHjJs + yVa" Sir CO mat cua eac cation bac khong gian giua hai philn set khong chi lam cho khoang each giua cac lop philn set (dooi) tang len ma lam cho set co tinh chat ua dau Khi do, set se co kha nang truong no va phan tan duqc cac dung moi huu CO khae 10 DAI HOC QUOC GIA HA NOI DE CUdNG DE TAI NGHIEN CUU KHOA HOC DAC BIET CAP DHQG HN Ten de tai: Tieng Viet: Nghien ciai che tao vat lieu hdp phu set hilu ca (organoclays) tren co' so nguon nguyen lieu bentonite va laig dung dexu ly cdc chat huu cadge hgi nitor Tieng Anh: Development of organoclays based on bentonite and their use in the treatment of hazardous organic chemicals in water and wastewater Thdi gian thuc hien: 24 thang Bk dau tij thang 1/2006 den thang 12/2007 De tai thuoc linh vue uu tien: De tai co trung vdi mot de tai da hoae dang tien hanh khong? D6 tai khong triin vai ddtai nao da hoae dano; tien hanh •to 5, Chu tri de tai - Ho vd ten: Nguyin Van Noi Nam K - Nam sinh: ngdy thang nam 1959 - Chuyen mon ddo tao: Hod hgc - Hgc ham, hgc vi: Tien sT - Chiic vu: Pho Chu nhiem Khoa - Dan vi cong tac: Khoa Hod hgc, truang DHKHTN, DHQGHN - Dia chi lien he: 19 Le Thanh Tong, Hd noi - Sddien thogi: 84 825 3503 Fax: 84 824 1140 Email: noinv(a)ncst.ac.vn Nil I Tom tit hoat dong nghien ciiu cua chu tri de tai (Cdc chuang trinh, de tdi nghien citu khoa hgc dd tham gia, cdc cong trinh dd cdw.^ bo lien quan tai phuang huang cua de tai) Then gian Ten de tai/cong trinh 2004 Nghien cuu che tao cac loai vat lieu hap phu tren co so phe thai nong nghiep va ung dung xu ly cac nguon nuoe bi nhi^m dau va kim loai nang Nghien cuu che tao mot so vat lieu tu cac loai phe thai ung dung qua trinh xu ly cac nguCn nuac bi nhi6m dau va cac chat huu ca doc hai khae Chu tri Di tai NCKH cap Dai hoc Quoc gia Ha noi Chu tri De tai NCKH cap Dai hoc Quoc gia Ha noi Synthethis of zeolites from coal fly ash and their uptake properties of zinc and nickel ions Ngucfi viet Development of adsorbents from rice hulls and their use in removal of nickel from contaminated wastewaters Nguai viet Proceedings of the second symposium on advanced materials in Asia-Pacit'ic Rim pp 106-108, Hanoi, April 24, 2005 Proceedings of the | Symposium of 8' Eurasia Conference, Hanoi, February ! 10-12,2004 Design system for wastewater treatment by means of activated sludge Nguai viet 2002 2005 2004 2003 2002 Tu each Cap quan ly/noi cong b ^ tham gia Development of biosorbents from Gracilaria Nguai biomass for removal and recovery of heavy viet metals from contaminated groundwaters i Proceedings of the international workshop: "Technology of municipal solid waste treatment: Experiences and Challenges"\ pp 125-129, Hanoi, March 12-13,2003 | ! i i Proceedings (CD-ROM) of j R ' - " World | February 12-15, Geneva Switzerland 2002 2001 2001 Nghien cuu kha nang tach loai, thu hoi Nguai Chi va Cadmi dung dich bing vat lieu Viet che tao tir rong tao bien The use of gracilaria biomass for removal of some heavy metals from aqueous solution Nguai viet H Tuyen tap cdc cong trinh | khoa hoc - Nhan dip ky niem 45 nam lap Khoa Hoa Truong Dai hoc Khoa hoc Tu nhien Ha Noi 2001 Tap chi Hoa hoc, vol 39, No 89-22(2001) Tom tit hoat dong dao tao sau dai hoc cua chu tri de tai nam tra lai day Thai gian Ten nghien cuu sinh Ten hoc vien cao hoc 2003 - 2005 Dao Thi Phuang Thao Do Khdc Toan 2003 - 2005 Duong Thi Hanh 2004 - 2006 Nguyen Thi Tlianh Thuy 2004 - 2006 Pham Nguyet Tii 2005 - 2009 Ca quan phoi hgp va cong tac vien chinh cua de tai TT Ca quan phoi hop Trudng Truong Trudng Truang Trucmg Truang Trucmg Trudng DHKH'm DHKHTN DHKHTN DHKHTT^ DHKHTN DHKHTN DHKHTN DHKR-m Cong tac vien Chuyen nganh Ho va ten Hoa V CO Nguyen Dinh Bang Hoa Moi trudng Nguygn Viet Hung Nguyin Ddc Vinh Hoa Cong nghe Hoa Moi trudng Tran Dinh Trinh Trinh Thang Thuy Hoa Moi tarang Hoa Moi truang Duong Thi Hanh Pham Nguyet Tu Hoa Moi truang Hoa Moi truang Nguygn Thanh Trung | | Thuyet minh su can thiet hinh du an d Viet Nam bentonite la mot loai khoang set re tien, co trii luang lan va duac sir dting rong rai nhi^u nganh cong nghiep nhu xay dung, luyen kim, khai thac va che bien d^u mo Dac biet, nhcf kha nang hap phu va trao dCi ion tot nen Bentonite cung da dugc ling dung rgng rai xu ly moi truang Viee nghien cuu che tao va su dung vat lieu hap phu set huu ca (Organoclay) dua tren ca sa Bentonite bien tinh da dugc phat trien manh me khoang thai gian 10 nam gan day va da ma nhung ung dung to Icfn viee xu ly cac nguon nuac bi nhilm chat hiru ca Tinh hinh ngliien ciru ngoai nuac Bentonile la loai khoang set tu nhien thugc nhom montmorillonh Cong thiic cua khoang set nhom montmorillonit la (Na, Ca)(Al, Mg)^(SifiIQ)^(OH)^ nH.O Die'm dac biet vi cau tnic cua khoang set nhom montmorillonit la ion Si"^'" (tam ciia tii dien) co the' bi thay the bai nhijng cation co dien tich be han nhu AP""; Fe-^"^, cation AP"^ (tam ciia bat dien) co the bi thay the boi cac cation nhu Fe^"*"; Mg^"^ ; Zn'"" Su thay the lam cho toan bo mang luai cua khoang set nhom tich dien am Cac cation Na"^; Ca'^; Mg'^ thuang dugc bii vao dien tich thieu hut va dugc phan bo a giiia cac lap Cau true cua nhom khoang set Montmorillonit nhu sau: \ \ '^m Q PGS TS hgc vj TU.GIAM TRIWNG BAN KHOA HQC; C6NG NGHf Kiten Dong dau r.SjS.^iwu)^^^'^ PGS.reKH ^^ 32 ^ U ^ ^ ... den 1:4 Bentonit dugc chia hai loai: - Bentonit truang no eo phan chinh la montmorillonit Na, hay ggi la Bentonit natri Khi bao hoa nuac bentonit natri eo the truang no den 20 Ian - Bentonit. .. dyes such as direct dye, acid dye and reactive dye on Nabentonite, HDTMA-bentonite and HDTMA-TIOT-bentonite was investigated - Application of organoclays in the treatment of wastewater from Duong... hdpphu set hitu ca (organoclays) tren ca so nguSn nguyen lieu bentonite va vmg dung di xic ly cdc chat hiru ca doc hgi nirac" Tilng Anh: ''Development of organoclays based on bentonite and their