KHOA HQC, CONG NGHE CHUYEN GIAO NGHIEN cDu CONG NGHE KHI HOA CHAT THAI ^ GIAY DA OE THU NHIEN LIEU NGUYEN QUdc BINH Vi^n K^ thu$t Nhi^t ddi vi BVMT Tli S Lfe TRONG THANH Trudng Dai hgc Cdng nghiip TP[.]
KHOA HQC, CONG NGHE - CHUYEN GIAO NGHIEN cDu CONG ^NGHE KHI HOA CHAT THAI GIAY DA OE THU NHIEN LIEU NGUYEN QUdc BINH Vi^n K^ thu$t Nhi^t ddi vi BVMT Tli.S Lfe TRONG THANH Trudng Dai hgc Cdng nghiip TP H6 Chi Minh Tdm tat: Bio cio gidi thiiu ket qua nghiin eUu thue nghiim eong nghi hda chat thai trin thiet bl kiiu tdng co dmh Vdi dieu kiin hda dnhiit dd tit 850 - QSO^C, ehe edp a< 0,4 lugng gas thu dugc tmng binh 2,0Nm^/kg chit thii; nhiit tri tit 1.062,3 -1.566,5 Kcal/Nm^; hiiu suit chuyin hda nhiin lieu tmng binh tir 43 - 63% Khi gas cd thi sir dung lim nhiin lieu eho chay tua bin khi, ndi hcri, nau kim loai Sin pham gas chiy thii eie chitt d nhiem dat tiiu chuan thai QCVN19:2009/BTNMT Abstract: The report presents the results of gasification experiment in the fixed bed equipment At the experimental conditions of 850 - dOO'C; a 1200°C, qud trinh ndy tao pham gas thu duge ed nhiet trj Q tfl 1.000 -1.500 kcal/ khf tdng hgp, chfla phin Idn CO va H2(hon 85% thd tfch) N.m^ ed thd sfl dung phat dien hoac mdt sd qui trinh cdng vd mdt phan nhd CO2 vd CH^ vd mdt sd chat khdc [2] - Khf hda nhiit dd thd'p (low-temperature gasification) nghiip khic tidn hdnh d nhiet dd < lOOO^C, qua trinh ndy tao khf tdng Hiln nay, tfl nganh SX giay da d khu vue TR Hd Chf Minh vd cae tfnh lan can hang ngdy thai hang tram tan hgp ngodi CO vd H2 cdn Iflgng Idn hydrocacbon (ehii ydu chat thii, mdt phin duge ddt tan dung nhu mdt dang nhiln Id mitan vd mdt sd hydrocacbon de bay hoi khae) dilu lilu nhu tai ISIM Xi mang Holeim - Hdn Chdng (Kiln Giang), kiln ndy cd mdt phin phin flng chuydn CO va H^ mdt phin duge ddt tai mdt sd Cty xfl ly chat thii, cdn phin CH^ (phin flng 11,12 nlu d mue d) Tie nhdn hda Id khdng khf, hoae oxy nguyin chat Idn vin thii bd mdi tmdng Chat thai gidy da ed thdnh phin chfl ydu Id cao su, cd the cd sfl tham gia cOa hoi nude Vdi sin pham khf chdy nhua, vii, da cd nang cung ci'p nang lugng cao, vi vay thu dugc tfl qua trinh khf hda duge dCing eho ddng co ddt cd thd dugc nghiln eflu tan dung, thu hdi nang lugng trong, turbine khf hoac ndi hoi, say ndng 11/2011 BAO HO LAO DONG 21 KHOA HQC, C N G N G H § - CHUYEN GIAO Qui trinh hod trii qua giai doan flng vdi viing thilt bi khf hda [2]: a Siy kho (Drying): Ldm bay hoi am chfla nguyin lilu Nguyin lilu nap vdo Id dflgc sd'y khd tai vung ndy b Nhiit phin (Pyrolysis): Ldm cit mach liln kit C-C ciia nguyin lilu tao khf nhiit phin (pyrolysis gas) vd can cacbon Tai viing nhiit phdn (viing bdn cdc), nguyin lilu bi phdn hiiy tao thdnh hdn hgp khf bay hoi va can rin Sin phdm ciia qui trinh nhiit phdn d viing bdn ed'c khdng thoit ngodi md tiip tuc di qua vung chdy Qud trinh nhiit phdn thdt su xiy tai khoing nhiit dd 280 - 700°C, dd s l tao thdnh mdt lugng Idn hie in, mdt sd hgp chit hflu eo ed hdng trdm chit khic nhau, dugc hinh thinh vd gas chfla CO^ c Oxy hda (Oxidation): Vi nguyin lilu rin ed nang chiy duge ciu thinh tfl nhflng nguyin td C, H, 0; dd phin flng chiy xiy ra, oxy hda hydrocacbon tao thdnh CO^ vd H^O theo phuong trinh (1)vd (7) d Khit (Reduction): Day Id giai doan khfl phin can cacbon edn lai dd tao thdnh gas CO vd H^ Sau viing chdy, lugng can cacbon edn lai va san phd'm chdy nhu CO^ vd hoi nudc dugc chuyen v l vung khfl, tai ddy cdc phin flng khfl (3,4,5), (8,9,10) xiy vd kl't qui hinh thdnh CO vd H^ Cdc phin flng hod hgc cua hod [2-3] Id: A//(KJ/mol) +394,1 + 0^ = COUj (1) +110,4 20 + 0^ = 2C0 (2) Gifla than vdi hoi nude: -135,0 C + H p = CO + H^ (3) -96,6 C + 2Hp = CO2 + 2H2 (4) 2C+2H2O = COj + CH, (5) Nhflng phin flng thfl cip cua sin phim cdc phin ung so cap 2C0 + Oj = 200^ +283,7 (6) 2H2 + 0^ = 2Hp +245,3 (7) 00^ + = 200 -173,3 (8) +38,4 CO + Hp = CO2 + H^ (9) C + 2H2=CH, +84,3 (10) 2CO + 2H2=CH, + C02 +274,4 (11) 2C0 + 3H = CH, + H^O (12) Thdnh phan sin phdm hod bao gdm hdn hgp khf gas nhu hydro (H^), caebonmonoxit (CO), methane (CHj, nito (Nj) vd cdc hgp chat hydrocacbon cao, ddng thdi cung cdc tap chit khdc nhu bui, tro, hie in, Nguyin lilu ed thd chfla Iflu huynh, nito, oxy vd cic chit khic Chiing tao qui trinh khf hoi cic khf nhu HjS, COS, NH3, HCN vd H^O Su chuydn ddi lugng COS vd HCN thdnh H^S vd NH, dua vdo phin flng thuy phdn, phu thudc vdo vile sfl dung gas cudi eung Cac chit khde (tro hodc kim loai) loai tfl khf hod tdn tai dang xf hoic sin phdm binh kim loai Cic yeu to inh hudng tdi qui trinh hda gdm: phin vd tinh chit vit lilu hda, nhiit dd hoi nudc, ap suit van hdnh, cha't xiic tie, nhiit trj, tdc nhdn khf hda die loai thiet bi hda: thiet bj khf hda ting cd dinh (fixed bed) vd thiet bj hda ting sdi (fluklised bed gasifiers) H Ddi TU0NG VA PHUUNG 63 Tro (% khdi luong) Khdi luong riing (kg/m^) _ 12 350 20 Nhiet trj ciia rdc: Q = 5.222 kcal/kg Bang 2: Thinh phin hda hoc cua chi't thil C H O N Thdnh phin hflu eo khd (% khdi Iflong) 65,49 3,31 18,81 1,89 Nhiet trj eiia rdc: Q = 5.222 kcal/kg Jfp ehi 22 BAO HO LAO DONG 11/2011 NGHIEN CUU Dd'i tugng Ddi tugng nghiln eflu hda Id rdc thii eiia ngdnh ddy da Phuong phip nghien cflu 2.1 Nguyin lliu Nguyin lilu sfldung nghiln cflu Id rdc thii cua ngdnh gidy da lay tai DN tu nhdn Tdn Phdt Tdi - Biin Hda -Oong Nai Ode tinh ly hda, thdnh phin hda hoac dua Bing 1,2 2.2 Thli'tbf, dung cu thi nghiim a Thiit bi gas Thilt bj TESTO 360, cd thd thdnh phin nhu sau: CH,, CO, hoi nude, CO^, SO^, NO^ Bingl: Mdt sd't fie tinh hda ly cua chi't thil Thinh phin hflu co bay hoi Cdc bon cd djnh Odam (% khdi luong) (% khdi luong) (% khdi lugng) PHAP S 0,5 KHOA HQC, C O N G NGHt - CHUYEN GIAO Bang 3: Chidd thu'c nghiim cflu thuc nghilm hda theo che dudi ddy:(Xem Bing 3) Luong hoi nudc cap vdo Nhiet (°C) Chi cap a Cfng vdi mdi thf nghilm, ta tidn hanh (% KL hoi/ KL can Carbon) ndng dd ede sin pham khf sinh bao gdm: 850,900, 950 70 0,2-0,3-0,4 CH,, CO, hoi nude, CO^, H^ vd mdt sd khac Cic miu gas duge trung binh phiit, May sac ki Perkin Elmer: ede chf tiiu H^ vd cdch 2-3 phiit lai lay mau gas dd mdt lan hydrocarbon khae Thf nghilm dfldc thuc hiln theo ehi dd ngfloe ddng - Cdc dung cu thilt bj phu trg khdc {Updraft) b Md hinh nghien eUu hda I I I K £ T QUA VA BAN LUAN Md hinh thi nghilm trin hinh 1(hinh inh mo hinh thiet bl thi nghiim xem Hinh 2), ed cdc thdng sd thidt bi nhu sau: III.I.Ketqui Cdt phin flng (gasifier) la mdt d'ng hinh tru, cd tdng Kit qui kidm tra thdnh phan trung binh khf gas vd nhiit chilu ddi Id 1000 mm Phin thdn trin ed chilu ddi 750 tri khf hda chd't thii duge dua cdc bing 3^5 mm, dudng kinh 160mm, phin dudi hinh cdn cd chilu Diin bil'n chd't lugng khf ga theo thdi gian hda ddi 250 mm xem trin Hinh 11.3 Cach tien hdnh thf nghiem III.2 Nhan xet Sau gia nhiet tdi nhiit can thilt, nap nguyin Tfl cdc bing H- cho tha'y: vdi dilu kiln khf hda da lieu tfl phlu chfla lilu (hoper)d phfa trin cdt khf hda vdo nghiln cflu, d 03 chd dd nlu trin khf gas thu dugc cd nhiet budng phan flng Moi me phin flng nap 1,0 - 3kg nguyin trj Q tmng binh tfl 1.062,3 ^ 1.566,5 keal/N.m^ Od chuydn lieu tliy theo dang ddi hay dang viln ep (nguyin lilu dugc hda tmng binh tfl 42,6 -H 63,2% Kdt qui nghiln eflu nghiln cflu d ddy Id rdc thai thdnh phan tinh chd't nhu da eung khd tuong ddng vdi kit qua nghiln eflu edng nghe nlu d bing 1,2) Nguyin lieu cd kich thudc tfl 0,5 -1 em Kd hda ede thdnh phan hflu eo tro rac thii sinh hoat, cd Q thfla cdc nghiln eflu tmdc cua nhdm nghiln cflu v l dieu tmng binh tfl 1.053 -^ 1.380 kcal/Nm^ chuyen hda tmng kiln nhiet phdn, hda chat thii, de tai tiln hanh nghiln binhTitfl49-^64%I1] Sang cho thd'y: tang ehd dd cap tfl 0,2 - 0,4 thi chat lugng khf gas cd xu hudng giim (thdng Nfldc qua nhiit trj) khoing 20 lanh 30%, vi tang chd dd ci'p khf llic oxi da d xi hda mit mdt phin H^ vd CH, Khf GAS Tuy nhiln gifla tfl 0,2 -^ 0,3 chat lugng khf gas ed giim nhung hiiu sud't Khong khf A1 chuydn hda r\ vdn dat >50% Khong khf Vdi su thay ddi nhiet thi nghilm Khdng khoang 850-900-950''C, chi't lugng gas thay ddi GHI CHU: khdng nhiiu, nhiet trj tmng Hopper chfla lilu binh d cic nhiet dd tuong Cpt phin flng flng trin Id 1225 1299 Cin 1358 kcal/Nm^ Thflc t l Thiet bj lam nguoi van hdnh Id hda c i chd dd thf nghilm trin H/nh 1: Md hinh thf nghiim cdt khf hda (gasifier) cho tha'y nhiet phan flng T9P chf 11/2011BAO HO LAO DONG 23 KHOA HQC, CONG NGHE - CHUYEN GIAO w\ budng phin flng, die bilt nhiit dd budng chiy bidn ddng phflc tap nhiit dd nhiiu liic vflgt qua 1.000''C Cic kit qui phin tfch eho thay !• d nhiit dd khf hda tang thi him Iflgng CH, c6 chilu hfldng giim ngugc lai him lugng Hj khf gas lai cao hon Chfnh vl viy md nhiit tri ciia khf gas thay ddi khdng rd dit •-^BNI Hinh 3, kdt qui thuc nghilm cho thiy gas i - -w • MM* • Wt ^ H ^ ^ ^ B « j thu dugc cd thd chiy dflgc (gidu khf chdy) thfldng nim khoing thdi gian diu 60 70% tdng thdi gian khf hda mdt m l chit thii Giai doan cudi ttWnj^^^rwlw ~ •*'J i khf hda (30 - 40% tfidi gian cdn lai), chit lugng khf • gas giim rd dit, hdm lugng CH,, H^, CO miu thu lin thfl d cic ehd dd diu cdn rit thip, Q ta < 500 kcal/N.m^ khdng ed nang tu bat chdy I^I^^H^H^^^*^''*^ J cd mdi Ifla / / M f ; / / M inh md hinh nghiin edit Kit qui tfnh toin so bd cho du i n hda thuc nghiim cdng nghi hda chit thii cdng suit 200 - SOOkg/gid eho mdt sd Cty d phfa Nam du kiln hgp t i c tridn khai vdi Bing 3: Thinh phi'n khfgas d chidd thi nghiim khoing 85(fC nhdm nhiln cflu cho thay: Hiiu suit chuydn Q H2O H2 CO CO2 CH4 gid thdnh SX khf gas vdo (Kcal/Nm') (%V) (%V) ' hda ri(%) (%V) (%V) (%V) khoing 580 d/Nm' (ndu 59,4 1472.2 4.0 9,5 10,2 0,2 8,0 20,1 tfnh chi phi thu dugc tir 45,9 1138.0 11,8 4,8 9,9 19,0 0,3 6,5 vile xfl ly chat thii gia thdnh se giim xudng 44,1 1094,3 13,6 21.4 12,6 0,4 4,6 3.1 ding kd) Gii thdnh tham Bing A.Thinh phin gas d chi thf nghiim khoing OOifC khio cfla mdt sd nudc Hiiu suit chuyen Q CH4 H2 CO2 H,0 CO nhu: Trung Qudc vdo (%V) (Kcal/ Nm^) (%V) " hda Ti(%) khoing 580 d/Nm' 1504,5 11,2 12,4 18,9 9,6 7.2 60,7 0,2 Sirilanea vao khoing 1331,7 10,5 19,6 540 d/Nm^ 9,4 5,2 9,4 53,7 0.3 ill S* mil ^^'Wf n til 0.4 3,3 13,0 18,6 11,0 7,1 1062,3 42,8 Bang 5: Thinh phin khf gas dchJdd thf nghiim khoang SSCfC Hiiu suit chuyen H2 Q CO H2O CO2 CH4 (%V) (%V) (Kcal/ Nm') (%V) (%V) " hda n(%) (%V) 14,6 1566,5 8,8 26,0 4.2 8,1 63,2 0.2 0,3 3,7 24.3 11,7 9.4 11,8 1395,2 56.3 0,4 2,6 21,8 15,8 13,6 7.8 1111,8 44,8 Bing 6: So sinh i^hinhphin khigas theo cic chidd dp khiic CH4(%) C0(%) Q (Kcal/ Hiiu sud't chuydn °C H2(%) Nm') " hda Ti(%) 0,2 850 - 950 6.5 21,7 9.4 1514 61 0.3 800 - 950 5.1 20,9 8,7 1288 52 0,4 800 - 950 3.5 20,6 6,0 1089 44 Tfip chi 24 BAO HO LAO DONG 11/2011 IV K E T NGHj L U A N VA KliN Kdt qui nghiln cflu bude diu v l cdng nghi hda chat thai gidy da cho thay cha't lugng gas thu dugc cd thd sfl dung phuc vu chay miy phit diin, ddt ndi hoi hay cap nhiit cho mdt sdqui trinh cdng nghiip vd sinh hoat khae Id hodn todn quan Nhiit trj thu dugc tfl qui trinh hda ric gin tuong duong so vdi nhiit tri cfla khf hda THUC TIEN KINH NGHIEM - DOI M | -Q = 2,5 H-3,8 kcal/Nm3:ed thd thay thd ddt tu nhiln, hoae sfl dung nhfl Id nguyin lilu diu tdng hgp hda hgc - Q > kcal/ Nm' hodn todn thay thd khf tu nhiln Idm nhiln lilu ddt eho edng nghiip, nhiit diin Q (kcal/Nm3) Dien bien nhiet ti i JEHS theo thifi gian ctT = 850°C 2000 •a = 0,2 • a = 0,3 Tdi iieu ifhoa hoc a = 0,4 [1] NguySn Qu6c Binh De tii "Nghiin ciru itng dung qui trinh nhiit phin, hda m^ts6 chit thii thu nhiin Miu liiu" Sd KH&CN TP.HCM 2009 [2]./^exanderKlein Gasi^cation: Hinh 3: Dien biin chit lUffng gas theo thi^ gian hda An Alternative Process for Energy Recovery and Disposal of Municipal Solid Wastes Department of Earth and Enthan md mdt sd Cty dang tridn khai (Q «1.300 kcal/Nm') vironmental Engineering-Columbia University 2002 Cdc chit d nhilm q u i trinh ddt gas thu dugc d i u [3] Krigmont, H., IBGCC power generation concept: Agatenam gidi han eho phip eiia QCVN19:2009/BfNMT way for a cleaner future Allied Environmental Technologies White Theo mdt sd tdi lilu [3-4], nang flng dung eiia khf gas Paper, 1999 [4] Morris, M., Electricity Production from Solid Waste Fuels nhu sau (theo gia trj nhiit tri eiia gas thu duge): Using advanced Gasification Tectmologies TPS Termiska - Q = 0,9 -^ 1,8 kcal/ Nm': ed thd sfl dung khf gas thu ProcesserAB, 1998.U dugc dd chay tua bin khi, ndi hoi, nd'u kim loai XAY DUNG TIEU CHI trgng sdtham gia vdo xdc djnh didm tiiu chf cung nhu xdc (Tiep theo trang 20) djnh khoing phdn loai) Tuy nhiln, vile xac djnh theo c i c bd tieu chf van cdn nhflng nhflge didm ein phii khac phuc, dd la vile thiiu hut cic cac thdng tin ljch sfl (do khdng ed quan ly) vd thdng tin khoa hgc liln quan d i n dilu kiln dja hinh, dja chd't vd tiim nang phdt tan chat d nhilm mdi tmdng dat vd nudc ngim, eung nhu phu thudc nhiiu vdo y kiln ehuyin gia (vile dua eae trgng sd tham gia vdo xdc djnh didm tiiu chf eung nhu xdc djnh khoing phdn loai) D i y Id nhflng tdn tai can phii khac phuc dd cd thd phue vu tdt cdng tdc quin ly cdc dja didm ONTL Hiln thdi, ede tdn tai ehinh cDa bd tiiu chi ed thd dugc lilt k l nhu sau: - Khd xdc djnh chi't d nhiem eu the can dilu tra, d i e bilt Id vdi nhdm cae hgp chi't hflu eo b i n vflng, nhdm c i c hgp chi't hflu cd khd phin hiiy chfla Cio; - Chfla cd danh mue va tiiu chuan d i y dD cua Viet Nam cho cac chat d nhilm d i e thu nhu d trin; Thiiu hut cdc thdng tin ljch sfl (do khdng ed quin ly) vd thdng tin khoa hgc liln quan ddn dilu kiln dja hinh dja chd't vd tiim nang phdt tan chat d nhilm mdi trudng dd't vd nudc ngim; - Phu thudc nhiiu vdo y kiln chuyin gia (vile dua cdc V KET LUAN Qua vile tham khio eie tiiu chf dinh g i i nlu trin tfl eie nfldc phdt tridn, cd thd eho thi'y rang vile i p dung cic tiiu chf x i c djnh vd phdn loai hodn toan cd thd thue hiln duge d Viet Nam, nhiln c i n cd thim eie nghiln eflu nham dinh g i i lai mflc v i g i i trj cCia cac tiiu chi ndy cho phii hgp hon vdi dilu kiln thuc t l cung nhu nang lue quin ly, xfl ly vd dilu tra thdng tin d Vilt Nam Tdi iieu tham khio: Criteria for Managing contaminated sites in British Columbia, Waste Management Act, November 1989 Interim Canadian Environmental Quality Criteria forContam natedSites,CanadianCoundlcfMinistersoftheEnvironment(CCME) Paul Nathanail and R PaulBardos Reclamation of Contami nated Land John Wiley and Sons ltd West Sussex, England, 2004 4.CUC Quin ly chat thii vi Cii thiin Mdi trudng - Tong cue Mdi trudng Bio cio ting ket nhiem vu "Dieu tra, dinh gii vi d4 xuat kShoach quin ly', xirly va phuc hoi moi trudng tai cic diem dNTL" Hi Ngi, 2010 So tay Quin ly cic diem ONTL d Viet Nam, Cue Bio ve Moi trudng, Bg Til nguyen vi Moi trudng, 2008.U Tf p chi 11/2011B A O HQ LAO DONG 25 ... chit vit lilu hda, nhiit dd hoi nudc, ap suit van hdnh, cha''t xiic tie, nhiit trj, tdc nhdn khf hda die loai thiet bi hda: thiet bj khf hda ting cd dinh (fixed bed) vd thiet bj hda ting sdi (fluklised... flng thuy phdn, phu thudc vdo vile sfl dung gas cudi eung Cac chit khde (tro hodc kim loai) loai tfl khf hod tdn tai dang xf hoic sin phdm binh kim loai Cic yeu to inh hudng tdi qui trinh hda gdm:... nghiln eflu hda Id rdc thii eiia ngdnh ddy da Phuong phip nghien cflu 2.1 Nguyin lliu Nguyin lilu sfldung nghiln cflu Id rdc thii cua ngdnh gidy da lay tai DN tu nhdn Tdn Phdt Tdi - Biin Hda -Oong