P E T R O V I E T N A l\̂ PK Xay diTng quy trinh xac djnh ham Itrcrng hcfp chat huTu ca de bay hdi trong mdi trUdng khong khi nham danh gia va giam sat 6 nhiem khong khi KS Tran Khanh Tung Vien Ddu kh[.]
PETROVIETNA l\^PK Xay diTng quy trinh xac djnh ham Itrcrng hcfp chat huTu ca de bay hdi mdi trUdng khong nham danh gia va giam sat nhiem khong KS Tran Khanh Tung Vien Ddu Viet Nam Hoat dong cua cong nghiep dau khf va cac nganh cong nghiep co lien quan thiidng tao nhieu hop chat huTu co de bay hoi (Volatile Organic Compounds, VOCs) Day la nhufng hop chait huTu co de bay hoi d nhiet t h u d n g , phan Idn dUOc xac djnh la co dpc tinh va de gay chay no VI vay, viec tang cUorng giam sat ham luong cac cau tufVOCs moi trUcrng khong la dieu can thiet nhdm phuc vu cong tac kiem soat ve an toan, sure khoe va moi trUcrng De xac dinh ham lupng cac cau tur VOCs phat sinh, chung ta can xay dUng quy trinh lay mau va phan tich Quy trinh xay dUng se dUpc ap dung cong tac danh gia tac dpng moi trUorng va giam sat moi trUdng L G l d l THIEU Do vay, cung vdi sU phat trien cua eae nganh cdng nghiep, chung ta can tang cudng giam sat Trong phan thai t d cdng nghiep dau va t d cae ngudn khae (edng nghiep hda ham lupng cae VOCs phuc vu cdng tac kiem soat ve an toan, sde khde va mdi trUdng mau, giao thdng ) t h u d n g tdn tai mdt lUpng dang ke cac hpp chat hdu co de bay hoi (VOCs) Cae VOCs cd dac tinh chu yeu sau: -I- La nhdng hpp chat de bay hoi d nhiet dp t h u d n g (cd dang mach thang, mach nhanh, mach vdng) nUdc ta hien ndi chung va nganh Dau ndi rieng chua cd tieu ehuan hoae hUdng dan, quy djnh thdng nhat phuong phap lay mau va phan tich mau xac djnh ham lUpng VOCs Do do, chung ta can xay ddng mdt bd quy trinh chi tie't de hudng dan phuong phap lay mau va phan -I- Thanh phan cau tao ehu yeu g d m cacbon va tich nham xac djnh ham lUpng eae eau t d Bd hydro, ngoai ed the cd mdt sd nguyen td khac quy trinh se dUpe sd dung cho cdng tac danh gia n h d oxy, nito, luu huynh, va giam sat d nhiem mdi trudng khdng tai eae -I- Nhieu VOCs dUpe xac djnh la chat dpc, cd edng trinh dau kha nang gay cae benh nhU ung thU, viem Quy trinh dUpc xay dUng tren eo sd ap dung p h d i va de gay chay nd cung nhU anh hUdng nguyen tac cua tieu chuan ASTM D3686-08 va den mdi trudng xung quanh D3687-07 (American Society For Testing and -I- Sd lupng cae VOCs thue te rat Idn va Materials - Hoa Ky) ed bd sung, eai tien eae bude len den hang ngan cau t d thude nhieu n h d m khae thUe hien de phu hpp vdi dieu kien thde tien tai Viet Nam DAU KHI - s 1/2011 41 AN TOAN - MOI TRUdNG DAU KHI PHUONG PHAP Pham vi nghien cuTu NGHIEN CUU Chung tdi Ida ehpn va lap danh sach eae cau tCl Cae phUPng phap ehinh sau day 6\jgc ap d u n g : VOCs (Bang 1) Day la cac eau t d ed t r o n g phan -I- PhUPng phap ngien edu tai lieu cac san p h a m cua nganh cdng nghiep Ipe dau va hda -1- PhUPng phap thde dau nghiem (lay mau, phan Bang Danh sach ciu tu phan tich va cac thdng sd dac trung tich mau, tinh toan ket T h o n g so qua) STT Cau tu' C o n g thLFC P h a n tu' lipcyng phan tip (g/mol) (°C) Methane CH4 16 30 44 58 58 72 78 92 106 106 106 -161,6 -88,6 -42,1 -10,2 -0,6 -1- P h U P n g p h a p so sanh va phan tich t h d n g ke (ap d u n g cac ky t h u a t t h d n g ke t r o n g phan tieh de danh gia dp lap, dp t h u hdi tren mau ehuan cua phdPng phap ) Ethane C2H6 Propane C3H8 iso-Butane C4H10 n-Butane C4H10 Pentane C5H12 Benzene CeHe Nhiet soi 36,1 80,1 110,6 Toluene C7H8 Ethyl Benzene CaHio o-Xylene CsHio ehuyen gia 10 11 p-Xylene CsHio m-Xylene CsHio 106 NOI DUNG 12 13 Vinyl chloride C2H3CI 62,5 139 -13 14 Propylene C3H6 42 -47,6 -1- P h u o n g phap NGHIEN cCru 136 144 138 3.2 X a y dipng q u y trinh Viec xay d i / n g quy trinh du'p'c t h y c hien theo s a s a u : Thu thap tai lieu, bien djch 3.3 Tieu chuan ASTM-phUPng phap lay mau va phan tfch i 3.3.1 Tieu chudn ASTM D 3686-08 Xay dLPng 611 thao quy trinh lay miu va phan tich Standard Practice far Sampling Atmospheres to Collect Qrganic Compound Vapors (Activated Charcoal Tube Adsorption i Method) Tieu chuan dUa phuong phap lay mau khdng de than hoat t i n h chda dng thuy tinh sd dung b o m hut thich 3.3.2 Tiiu chudn ASTM D Phan tich mau, kiem soat ch^t lu'p'ng phan Standard Practice for Analysis of Qrganic Compound Vapors by Method Cae VOCs khdng dupe hap phu len be mat than hoat tinh va dUpc giai hap bang dung mdi CSj, sau dd dUOc xac djnh bang sac ky dau dd ion hda ngpn Ida (GC/FID) Phuong Khong 20 TCf 3.7.3 Kiem tra hiiu sudt thu hdi chdt them dd tinh SBL- Bddc dau tinh gidi han phat hien eua tin Hieu sua't thu hdi chat them eung cd the sd dung de danh gia dp chinh xae cua phUPng phap phan tieh Kiem tra hieu sua't thu hdi chat them bang each them mdt lupng chat ehuan da biet trUde ndng dp vao mau, sau dd tien hanh phan tich va tinh toan hieu suat thu hdi chat them theo cdng thde sau: hieu nen, ky hieu la LODy: L0DY = Ymin-YBL = 3xsBL Sau dd lay LODy chia cho he sd gde b phuang trinh hdi quy Y = a -i- bW de tinh SBL,„ va LOD: LOD = X SBL,W HSTHiVo) C,huun+mau C,•huan * J QQ 3.8 Ti'nh toan ket qua phan tfch + Ket qua phan tieh mau kiem soat chat lUdng Trong dd: - Op lap: Cac gia trj ghi nhan dupe bien thien Gia tri cua mau cd them chat ehuan khoang 4-19% da biet ndng dp Bang Ham luang cac ciu tu C1-C5 (gia tri trung binh cho tirng tram) Ham lu'gng (mg/m^) Ki hieu mau CH4 C2H6 C3H8 n-C4Hio isoC4H10 C5H12 C3H6 Cong xuat LPG trudc day DC-1 5,44 3,23 3,35 2,32 0,925 2,10 0,982 Bdn chira Condensate DC-2 3,51 2,13 2,11 2,68 1,13 1,23 1,12 Bon ehifa xang pham PO-1 0,895 1,51 1,83 1,96 1,72 2,12 0,958 Bdn chira xang pham PO-2 1,02 0,927 1,01 2,20 1,53 3,89 0,828 Ngoai hang rao PO-3 0,894 0,098 0,095 0,925 0,456 0,145 0,095 Khu VUG cong nghe PM-1 2,13 2,60 0,082 0,095 0,069 KPH 0,099 Khu wc cong nghe PM-2 1,57 1,98 0,102 0,074 0,072 KPH 0,078 STT Dja diem Dinh Co PVOil Nhua vaHC Phil My Vjtri 46 DAU KHi - s6 1/2011 PETROVIETNAI Gi&i han phat hien LOD LOD (mg/m^) CH4 C2H6 C3H8 n -C4H10 iso-C4Hio C5H12 C3H6 0,024 0,038 0,022 0,023 0,022 0,028 0,023 Bang Ham lugng cac ciu tu BTEX va vinyl chloride (gia tri trung binh cho tung tram) STT Dja diem Dinh Co Vjtri Cong x u i t LPG tru'dc (Jay Bon chira Condensate iVIIu Benzene Toluene m,p-Xylene o-Xyiene Ethylbenzene Vinyl chloride DC-1 0,094 0,068 0,038 0,033 0,044 KPH DC-2 0,628 0,407 0,056 0,045 0,053 KPH Bon chira xang pham PO-1 1,68 0,064 0,053 0,053 0,064 KPH Bon chira xang pham PO-2 2,23 0,051 0,040 0,045 0,068 KPH Ngoai hang rao PO-3 0,060 0,036 < 0,0130,029 0,027 0,043 KPH Khu vLrc cong nghe PM-1 0,021 < 0,0130,018 < 0,0140,018 < 0,0130,041 0,068 Khu v y c cong ngh? PM-2 KPH KPH KPH0,040 < 0,0190,029 PVOil Nhira vaHC Phil My < 0,014 0,020 0,019 KPH Gi&i han phat hien LOD LCD (mg/m') Benzene Toluene 0,009 0,014 m , pxylene 0,013 -xylene 0,014 Ethyl- Vinyl- benzene chloride 0,013 0,019 COI A [8*C(X>^t*W*TC«BTEXDC-'-iOi - Do tai lap ndi bd: Cac gia trj dp lech bie'n thien khoang 4,4 - 9,2% - Op thu hdi: Phep phan tich dp thu hdi dugc thUe hien d mde ndng dp eau td ehuan, gia trj dp thu hdi dao ddng khoang 76-81% -I-Tai Nha may xd ly Dinh Cd Chung tdi phat hien hau het cae eau td C1-C5 va BTEX Ngoai trd methane vdn tdn tai mdi trUdng khdng vdi ham lupng nhat djnh, cac cau td dupc phat hien cdn lai tUOng ddi phu hpp vdi thUc te hoat ddng cua Nha may xd ly Dinh Cd vdi san pham chinh la khd (trong phan chu yeu la Cl va mdt phan C2), LPG (chda nhieu C3-C4) va condensate (chda nhieu eau td mach cacbon Idn hon) Trong qua trinh hoat ddng eua nha may, mdt phan cac cau td neu tren cd the theo ddng hoi san pham thoat ngoai mdi trudng khdng xung quanh Hinh Sic GC/FID tieu biiu cho miu BTEX (mau tai Dinh Cd) DAU KHi-s6 1/2011 47 AN TOAN - MOI TRUdNG DAU KHi + Dda chi tie't phUPng phap pha dung djch -I-Tai t d n g kho PVOIL Tai t d n g kho PVOIL cung phat hien hau het cae ehuan g d m chuan cau t d nghien cdu va ndi chuan eau t d C1-C5 va BTEX Trong khudn vien nha may, -I- Chuan hda cac thao tae phan tich va thao tac ham lupng cac eau t d nhin ehung eao hon gia trj van hanh he t h d n g sac ky, vi du qua trinh bom CS2 tUPng dng tai tram ngoai hang rao Tdng kho PVOIL vao vial chda than d trang thai kin Oiem can luu y la la t d n g kho xang dau nen mdi t r d d n g khdng b a m t r o n g xy lanh vao loop mau eho mau ed khuynh hudng tdn tai hoi eua eae cau t d nang phan bd deu t r o n g loop; n h u BTEX -I- Tai Nha may Nht/a va hda chat Phu My + Dda ta quy t r i n h t i n h che d u n g mdi CSj cd nhiem Benzene; + Dda ta gidi han phat hien va phuang phap tinh Cac cau t d Cl -C5 dupe phat hien d mde kha thap so vdi eae edng trinh khac Tuy nhien, cau t d vinyl chloride dupe phat hien tai day Oieu cung phu hpp vdi thUc te vl monomer vinyl chloride dugc nha may dung lam nguyen lieu de tdng hpp nhUa PVC SO SANH QUY TRINH XAY DLTNG DUOfC VCfl QUY TRiNH CUA TIEU CHUAN ASTM LOD Tren co sd ket qua d a f dupe, eae quy trinh lay mau va phan tieh mau dupe danh gia la ed the ap d u n g t r o n g edng tae quan trae mdi trUdng khdng nham xac djnh ham lupng cae VOCs n h d da neu SOAN THAO QUY TRINH Quy trinh laiy mau Ket thue qua trinh thiJe nghiem, nhdm tae gia da - Oiem gidng nhau: DiJa tren phuang phap hap phtj eae VOCs bang than hoat tinh Oay la p h u o n g phap hap phu ehu ddng dupe dng dijng rdng rai xay d u n g dUpe quy trinh sau: -I- Quy trinh lay mau: Xac djnh ham lUpng hpp chat hdu ea de bay hai t r o n g mdi t r u d n g khdng phan tich -I- Quy trinh phan tich: Xac djnh ham lUpng hpp - Oiem cai tien: Quy trinh ma chung tdi xay diJng chat hdu ca de bay hai t r o n g mdi t r u d n g khdng da ket hpp vdi phuong phap lay mau triJe tiep bang xy lanh dung phan tieh cac C1-C5 4.2 Quy trinh phan tich mau KET L U A N Cac quy trinh phan tieh VOCs da ddgc xay dung - Oiem gidng nhau: Dua tren phuong phap giai cd tinh thi/c ti#n eao, da neu dUpe cac ndi dung ve: hap phu cae VOCs tren than hoat tinh bang dung mdi pham vi ap d u n g , nguyen tae, d u n g cu, hda chat, cac CS2 va phan tieh bang he sac ky GC/FID bude tien hanh thUc nghiem, p h u o n g phap kiem soat chat lupng phan tieh - Oiem eai tien: Quy trinh da ket hpp t h e m phUPng phap phan tieh mau thu dupe bang phuang phap lay mau trUe tiep sd dung xy lanh Cd the ap dung quy trinh de phan tieh cac cau t d khac cd tinh chat hda ly tUOng t d cac cau t d thupc pham vi nghien edu Vi du nhU dung than hoat tinh de Quy trinh da neu dupe nhdng ndi dung ehi tiet nham giup ngUdi phan tieh ed the trien khai edng hap phu eae eau t d phan CIJ'C khac (eyelohexane, cyelohexanol ) va phan tich tren edt phan cdc DB-VRX viee mdt each nhanh chdng va phu hpp vdi tinh hinh thuc tien, cu the nhU sau: -I- Chi rd eae diem can luu y cung n h u trang thiet bj bao hd chuyen dung can thiet sd dijng d u n g mdi CSj; DAU KHI - s o 1/2011 Cae quy trinh sau ban hanh cd the ap d u n g de xac djnh ham lupng cac VOCs quan trae mdi t r u d n g eae edng trinh dau hoae cac nganh cdng nghiep khae cd lien quan PETROVIETNA Small Numbers of Observations Analytical chemistry, TAI LIEU T H A M K H A O Vol 23, 1951, p p 6 - Cu Thanh Long, 2007 Phuang phdp Thdng ki ThUc nghiem Hda hgc Nha xuat ban Giao due PDC, 2008 Bdo cda gidm sdt mdi trUdng dinh ky Tdng kho xdng ddu Vung Tdu and Accessories Catalogue, European Instrument Edition Adsorption Vapors (Activated to Collect Charcoal Qrganic Tube Method) Collected by the Activated Compound Charcoal Tube 99-74-45 of NIOSH Validation Tests NIOSH Standard HSM 9 - - Personnel report Levadie, B., and Maeaskill, S.M Analysis Simplified Technique.Ar\aiyt\ca\ of Vapors Adsorption Method chemistry, Vol 48, No 1, 1976, pp.76-78 10 OSHA Standard CFR 1910 General OSHA Safety and Health ASTM 03687-95, ASTM D3687-07 Standard Practice for Analysis of Organic CDC Organic Solvents Taken on Charcoal Tube Samplers by ASTM D3686-95, ASTM D3686-08 Standard Compound Documentation Standard Sampler Pump For Charcal Tubes, Final Agilent Technologies, 2005 The Practice for Sampling Atmospheres N I O S H Industrial Standard 11 Turner, B.C., and Glotfelty, D.E Field Sampling of Pesticide Vapors with Polyurethane Foam Analytical chemistry Vol 49,1977, pp.7 - ™ Dean, R.B., and Dixon Simplified Statistics for DAU K H i - s o 1/2011 49 ... dijng rdng rai xay d u n g dUpe quy trinh sau: -I- Quy trinh lay mau: Xac djnh ham lUpng hpp chat hdu ea de bay hai t r o n g mdi t r u d n g khdng phan tich -I- Quy trinh phan tich: Xac djnh ham... lam nguyen lieu de tdng hpp nhUa PVC SO SANH QUY TRINH XAY DLTNG DUOfC VCfl QUY TRiNH CUA TIEU CHUAN ASTM LOD Tren co sd ket qua d a f dupe, eae quy trinh lay mau va phan tieh mau dupe danh gia... cai tien: Quy trinh ma chung tdi xay diJng chat hdu ca de bay hai t r o n g mdi t r u d n g khdng da ket hpp vdi phuong phap lay mau triJe tiep bang xy lanh dung phan tieh cac C1-C5 4.2 Quy trinh