TuyIn tap bio cio Hpi nghj KHCN "30 nim Dau khi Vift Nam Cff hpi mdi, thach thde mdi" 77̂ KHA NANG H A P PHU CAC TAP CHAT CUA M Q T SO LOAI ZEOLIT Sir DVNG TRONG CONG NGHE Xif LY KHI Vo Thj Lien Tdng[.]
TuyIn tap bio cio Hpi nghj KHCN "30 nim Dau Vift Nam: Cff hpi mdi, thach thde mdi" 77^ KHA NANG H A P PHU CAC TAP CHAT CUA M Q T SO LOAI ZEOLIT Sir DVNG TRONG CONG NGHE Xif LY KHI Vo Thj Lien Tdng cdng ty Ddu Viet Nam Le Manh Hiing Cdng ty Dung dich khoan vd Hod phdm Ddu TOM T A T Tir ndm 1954, cdc logi zeolit tdng hap da duac img dung thdnh cdng nhiiu linh vice Dac biet linh vuc xir ly cdc zeolit duac sir dung nhu cdc chdt hdp phu Nhiiu logi zeolit nhu zeolit A, X, P da duac sir dung ldm khd xir ly tdch cdc tgp chdt nhu CO2, H2S, NH}, mercaptan, v.v Cdc qud trinh khdc nhu ldm sgch sdn xudt O2, N2 zeolit cUng duac sic dung nhu cdc chdt hdp phu Bdo cdo giai thieu vi mpt sd zeolit da icng dung cdng nghi xir ly vd dang Id sdn phdm thuang mgi Ddng thdi giai thieu khd ndng hdp phu mpt sd tgp chdt thudng gap cdc ddng DAT V A N D E Xir ly bao gdm cac van de nhu say khd khi, tach va lam sach nham thu dugc ddng cd phan dap ung cae yeu eau cho van chuyen, tang trii, che bien va sir dung Nhirng giai phap de xir ly cac ngudn la: hap thy, hap phy va ngung ty Vdi phuang phap hap phu, cae loai vat lieu thudng dugc sir dyng nhu than boat tinh, nhdm oxit, kem oxit, sat oxit, silicagel va zeolit Hien nay, loai vat lieu hap phy zeolit dugc sir dung rat phd bien, loai vat lieu cd cae uru diem ndi trdi so vdi cac loai vat lieu khae nhu chgn lge hap phu va dung lugng hap phu cao C5 Viet Nam, trir lugng kha ldn, cd lan hoi nude va cac tap chat nhu H2S, NH3, CO2 nen cin phai xir ly trudc van chuyin, tang trir, che bien va sir dung Hien nay, vat lieu zeolit da dugc sir dyng Nha may xir ly Dinh Cd de lam khd Trong nha may dam va nha may Igc dau ciing cd cac ngudn can xir ly nhu cracking, hydro tir reforming, thai, v.v Cac ITnh vue khae nhu xir ly mdi trudng, san xuat cdng nghiep, san xuat cho y te, san xuat thue pham ciing can mdt lugng chat hap phu kha ldn Vi vay, nghien ciiu cae zeolit hap phu va tien tdi san xuat loai vat lieu d nude ta se dap ung dugc cac yeu eau thuc tien dat NHOM c A c ZEOLIT H A P PHU vA PHAM VI iTNG DUNG Hinh 1: Cau true tinh the zeolit A '8 Kha ning hap phu cac tap chat cua mpt so loai zeolit sd dung tr^ng^ L Zeolit hap phu thuoc nhdm zeolit A a Zeolit 3A (KA) La loai aluminosilicat kim loai kiem cd dudng kinh mao quan khoang Angstroms (0,3nm) Vdi kich thudc mao quan nhu vay, zeolit 3A cd kha nang hip phy cac cau tir nhu hoi nude, cdn cac phan tir cd dudng kinh ddng hgc ldn hon bj giir lai Cdng thirc hoa hgc ciia zeolit 3A la: 0.45 K2O 0.55 Na20 AI2O3 2Si02 n HjO LTnh vuc ap dyng cua zeolit 3A: - Tach nude tir cac hydrocarbon chua no nhu etylen, propylen, butadien, v.v - Lam khd thu dugc tir cracking - Siy khd ty nhien nlu yeu cau giam thieu lugng COS tao hoae giam thieu lugng hydrocarbon bj hap phy - Tach nude tir eae hgp chat cd eye nhu metanol, etanol - Lam khd cac tac nhan lanh nhu R22, Rl34a - Lam khd thuy tinh each dien Zeolit 3A dugc tai sinh bang ddng khd cd nhiet dii de say ndng khdi zeolit tang dan len va chi d nhiet 200 - 230 °C thdi gian - 3h Khi diing lam khd ddng chira hydrocarbon olefin, tai sinh zeolit KA d nhiet thap cd the giam thieu lugng polime tao thanh, loai zeolit cd the lam khd ddng xudng dudi 0,1 ppm H2O Cac chat hap phy zeolit 3A cua Cdng ty ZEOCHEM nhu Z3-01 (diing cho lam khd cracking, lam khd dau md), Z3-02 (diing eho loai nude cua etanol, metanol), Z303 (diing cho loai nude ciia ty nhien), Z3-04 3A-8KM (diing cho loai nude ciia tac nhan lanh), IS0M0L3 (diing tach im eho thuy tinh each dien) b Zeolit 4A (NaA) Zeolit 4A cung thudc loai aluminosilicat kim loai kiem cd dudng kinh mao quan khoang Angstrom (0,4nm) Zeolit 4A cd thi hip phu hiu hit cac phan tir ed kich thudc ddng hgc nhd ban 4A*', ngan chan cac phan tir cd kich thude ldn hon Cac loai phan tir cd the hap phu dugc nhu O2, N2, CO2 va hydrocarbon ngoai trir cac hydrocarbon mach nhanh va hydrocarbon thom Cdng thirc hoa hgc eiia zeolit 4A la: Na20 AI2O3 2Si02 n H2O LTnh vyc ap dyng: - Say khd va tach CO2 tir ty nhien, LPG, khdng khi, tro va cac loai khae - Tach cac hydrocarbon, amoniic va methanol tir cac ddng (qua trinh xir ly tdng hgp amoniac) Zeolit 4A duge tai sinh bing ddng ndng, nhiet ciia khdi zeolit duge tang din Tuygn tap bio cio Hpi nghj KHCN "30 nim Dau khf Vift Nam: Cff hpi mdi, thich thde mdi" 79^ len 250 - 300°C va tri thdi gian - 3gid Loai zeolit dugc tai sinh thich hgp cd thi nhiet dilm suong cua ddng xudng - lOOT va ham lugng CO2 xudng dudi 5ppm Cac san phim chit hip phy zeolit 4A ciia UOP nhu: 4A-DG MOLSIV chiem tren 60% lugng cac chit hip phy dugc sir dyng qua trinh lam khd ty nhien tren the gidi, UI-94 MOLSIV dugc sir dung nhilu d Trung Ddng, Bic My, UOP IlK-38 va 4ALNG de tach CO2 va mercaptan cd phan tir khdi thap da dugc sir dyng hon 100 nha may tren the gidi Nhdm cac san pham chira zeolit 4A ciia ZEOCHEM gdm Z4-01 diing qua trinh lam khd cac tro, CO2 hoae khdng khi, Z4-02 diing cdng nghe san xuat LNG, Z4-04 diing qua trinh lam khd ty nhien, 4A-8BL diing cac loai phanh hoi ciia xe bus, xe tai, tau boa de lam khd, 4A-8KM diing lam khd cac tac nhan lanh c ZeoUt 5A (CaA) La loai aluminosilicat kim loai kiem, cau tnic tinh the zeolit 5A cd khoang 70 - 75% ion natri dugc thay the bang ion canxi Dudng kinh mao quan ciia zeolit 5A khoang Angstrom cd the hap phy cac phan tir cd kich thudc ddng hgc nhd hon 5A" Loai zeolit dac biet thich hgp eho cdng nghe hap phu PSA (pressure swing adsorption), d dd chung dugc sir dyng de tach rieng n-paraffin va iso-paraffin (C4, C^), san xuat oxy, nito tinh khiet diing y te Cdng thirc boa bgc ciia zeolit 5A la: 0.7 CaO 0.3 NazO AI2O3 2Si02 n HjO LTnh vyc ap dyng: - Tach nude, CO2, H2S tir ty nhien, giam thieu sy tao COS Loai zeolit cdn cd the hap phy cac mercaptan nhe - Sir dyng eho tach rieng n-paraffin va iso-paraffin - San xuat cac N2, O2, H2 va eae tro khae cd tinh khiet cao Zeolit 5A duge tai sinh bang edng nghe PS (pressure swing) hoae bang ddng sach cd nhiet dii dl lam ndng zeolit len din nhiet 200 - 300 "^C Neu dugc tai sinh thich hgp thi loai zeolit cd the lam giam nhiet diem suong xudng - lOO'^C va ham lugng CO2 hoae H2S xudng dudi 5ppm Cac san phim 5A ciia ZEOCHEM gdm: Z5-01 diing de phan tach isome, Z5-02 diing lam sach ty nhien giam thieu ham lugng COS, Z5-03, Z5-04 diing qua trinh lam giau oxy, Z5-05 diing qua trinh lam sach hydro San pham ciing loai cua UOP nhu COSMIN, MOLSIV, v.v Zeolit thudc nhom zeolit X Hinh 2: Cau triic tinh the zeolit X 80 Kha ning hap ph^ cie tap chat cua mpt so loai zeolit sd dung t£on£:^ a Zeolit lOX Loai zeolit cd dudng kinh mao quan khoang Angstrom (0,8nm), tinh the zeolit lOX cd ciu triic kilu faujasit Trong zeolit lOX khoang 75% ion Na"" dugc thay the bang ion Ca^"^ Zeolit CaX cd the nhan duge tir qua trinh trao ddi cafion ciia zeolit dang NaX Cdng thirc hoa hgc ciia zeolit I OX la: (0.83 ± 0.05) NajO AI2O3 (2.48 ± 0.03)SiO2 n HjO LTnh vyc ap dung: - Lam chit hap phy cac phan tir cd dudng kinh ddng hgc nhd ban kich thudc mao quan (8A°) - Diing lam xuc tac, tach chat Loai zeolit cd tinh chat tuong ty zeolit lOX la Zeolon Na (My), Zeosorb (Ddng Dire), Calsite (Tiep), CaX (Lien Xd cu) b Zeolit 13X Loai zeolit cd dudng kinh ldn hon nhieu so vdi zeolit A Dudng kinh mao quan ciia loai zeolit vao khoang 7,4 angstrom (0,74nm) cho phep hap phy cac phan tir cd dudng kinh ddng hgc nhd hon 9A'' Loai zeolit 13X cd dung lugng hap phy va tdc chuyen khdi cao Zeolit 13X cd the tach cac tap chat cd kich thudc ldn hon nhieu so vdi kich thudc mao quan cua zeolit A Cdng thirc hoa hgc ciia zeolit 13X: Na20 AI2O3 2.5 Si02 n HjO LTnh vuc ap dung - Tach CO2 va am tir khdng - Tach, lam giau oxy tir khdng - Tach mercaptan, H2S tir ty nhien - Tach cac chat oxy boa tir cac hydrocarbon - Tach cac n-paraffin khdi cac chit thom - San xuat oxy tinh khilt diing cho Y tl Cac san pham zeolit 13X nhu ZlO-2 (diing cdng nghe tach rieng hydrocarbon olefin), Zeochem (diing qua trinh tach mercaptan va H2S), Z10-01 (la loai 13X tieu chuin diing lam sach khdng khi), Z10-03 (diing san xuit oxy), Z10-04, ZIO06, v.v ciia Cdng ty ZEOCHEM Ngoai ra, cdn cd Zeosorb 13X (Ddng Diic), Nalcit 13X (Tiep),^ v.v Cdng ty UOP vdi san phim 13XAPG dugc sir dung nhilu nha may san xuit oxy va nito tren thi gidi Loai zeolit 13X dugc tai sinh bing ddng khd cd nhiet cd the nang nhiet ciia khdi zeolit len 250 - 300"C Loai zeolit 13X dugc tai sinh thich hgp cd thi nhiet suong ciia ddng xudng -lOO^C, ham lugng mercaptan va CO2 xudng dudi mirc 2ppm Tuygn tip bio cio Hpi nghj KHCN "30 nim Dau Vift Nam: Cff hpi mdi, thich thde mdi' KHA NANG HAP 81 PHU MOT SO T A C N H A N CO HAI CUA CAC LOAI ZEOLIT HAP PHU Trong diu md, khdng va thai chiia cac tap chat cd hai gay anh hudng tdi mdi trudng va quy trinh cdng nghe nhu cac hgp chat chiia luu huynh, NH3, CO2, hoi nude Tuy theo yeu ciu vl nguyen lieu, san pham va eau true, tinh chat, dung lugng hap phu ddi vdi mdi loai tap chat ciia timg loai zeolit ma cd the lya chgn mdt cac loai zeolit tren sir dyng lam tac nhan hap phy cac qua trinh edng nghe lam sach, tach cac tap chat ed hai dd khdi ddng Kha nang hap phu hoi nirdc ciia cac zeolit hap phu Viee tach hoi nude ddng hay edn ggi la qua trinh lam khd la mdt nhirng cdng doan quan trgng qua trinh san xuat hoa Idng, qua trinh san xuat oxy, nito, qua trinh lam khd cdn, lam khd thuy tinh each dien Hoi nude thudng gay cac tac hai nhu tao hydrat, an mdn dudng dng, lam thay ddi cac dieu kien lam viec binh thudng cua he thdng thiet bj De de dang so sanh dung lugng hap phu hoi nude cua cae loai zeolit hap phu ciing mdt dieu kien xem Hinh Dung lugng hap phy la ham ciia nhieu yeu td nhu nhiet do, ap suat, ban chat chat hap phy, chat bj hap phy vay de so sanh phai dua ve ciing dieu kien hap phu Tir Hinh va Bang I ed the thay zeolit CaX la loai ed dung lugng hap phy ddi vdi hoi nude cao nhat Sau dd la CaA, NaA cdn NaX hap phy hoi nude kem hon Tuy nhien, thyc tien loai zeolit NaA va NaX tdng hgp de hon so vdi cac loai nen mac dii dung lugng hap phy thap hon van dugc sir dyng nhieu Bang 1: Dung lu'ong hap phu hoi niroc cua cac loai zeolit hap phu TT Logi zeolit hdp phu NaA(4A) Dieu kien hdp phu "K mmHg 298 0,025 - 0,1 20 0,025 0,1 20 0,4 20 20 - CaA(5A) 298 - NaX(13X) 298 - CaX(lOX) 300 - Dung luang hdp phu g/g 0,16 0,20 0,25 0,28 0,19 0,22 0,27 0,30 0,24 0,26 0,24 0,31 0,36 82 Khi ning hap phu cie tap chat cua mpt so loai zeolit sir dung tr^ng» ~5i) U 40 35 30 25 20 15 10 _ f=A ri\ ^i - ffllTF ^- — — — i- — — — !- fd d NaA CaA I Li NaX K_ CaX Hinh 3: Dung lu-ong hap phu hoi nu-dc d 298''K, 20 mmHg (C; dung luang h ap ph u) Kha nang hap phu NH3 Trong thai, tir qua trinh van ehuyin, tang trii, che biin rac thai cd chiira mdt lugng dang kl amoniac, tir nha may san xuat dam ciing thoat mdt lugng NH3 Ngoai ra, tu nhien va ddng hanh ddi ham lugng NH3 ciing vugt cac tieu chuin eho phep Zeolit la chat ed kha nang hap phu tdt NH3, vi vay zeolit dugc sir dung lam chat hap phu de loai bd NH3 cac ddng Bang 2: Dung lirong hap phu NH3 cua cac loai zeolit hap phu TT Logi zeolit hdp phu NaA (4A) CaA(5A) Dieu kien hdp phu mmHg 298 0,090 - 10 0,11 - 100 298 10 0,15 0,10 - NaX(13X) CaX(IOX) 0,135 0,175 0,10 0,14 298 100 - 10 - 100 298 0,175 0,10 - 10 0,14 - 100 0,185 - Dung luang hdp phu g/g «K Sd lieu Bang cho thiy dung lugng hip phy NH3 ciia CaX d lOOmmHg cao nhit, ciia CaA, NaX bing va thip hon so vdi CaX mdt chiit Trong ciing mdt dilu kien, dung lugng hip phu NH3 cua CaX bao gid ciing ldn hon ba loai Dilu cang thay rd ban so sanh tren Hinh Tuyen tap bio cio Hpi nghj KHCN "30 nSm Dau Vift Nam: Cff hpi mdi, thich thde mdi" 83 20- p - 10 o U • P=10 • P=100 Hinh 4: So sanh dung lirong hap phu NH3 Kha nikng hap phu CO2 Khi CO2 la mdt cac axit gay tac hai an mdn thilt bi, dudng dng cd mat hoi nude La loai khdng chay, cd mat LPG, LNG se lam giam nhiet chay cua Trong qua trinh san xuat nito, oxy tir khdng khi, qua trinh che bien tu nhien va ddng hanh can phai loai bd axit Cac ngudn dau md d Viet Nam thudng cd ham lugng CO2 kha cao, dac biet la cac md nam d khu vyc mien Bae va miin Trung Ddi vdi CO2, dung lugng hap phu ciia cac loai zeolit cd su thay ddi dang ke Khi ap suat tang, dung lugng hap phu ciing tang, dung lugng hap phu CO2 cua CaX va NaX d ap suat va nhiet nhu Bang cao hon hai loai zeolit A CJ P = 100, ba loai CaX, NaX, CaA cd dung lugng hap phu bang Dieu thay rd hon tren Hinh Bang 3: Dung lu-ong hap phu CO2 ciia cac zeolit hap phu TT Logi zeolit hdp phu NaA (4A) Dieu kier! hdp phu mmHg "K 298 - CaA(5A) 298 - NaX(13X) 298 - CaX(lOX) 298 - 10 100 700 10 100 700 10 100 700 20 100 700 Dung luang hdp phu, g/g 0,070 0,12 0,165 0,20 0,066 0,13 0,20 0,24 0,06 0,10 0,20 0,26 0,125 0,20 0,26 84 Khi ning hap phy cie tap chat ciia mpt so loai zeolit sd dying troiig^ • P=10 o • P=:100 u OP=700 Hinh 5: So sanh dung lu-ong hap phu CO2 Kha nang hap phu H2S - , Cac hgp chit chiia luu huynh nhu H2S, mercaptan, v.v cd mat cac ngudn diu gay tac hai din mdi trudng, gay an mdn thiet bj, dac biet cd mat hoi nude d nhiet va tdc di chuyin cao Day la mdt loai axit thudng cd mat dau md, thai cua cac phan xudng thu hdi luu huynh, ciia qua trinh cracking, v.v nha may lge diu (ddi vdi qua trinh cracking nlu nguyen lieu cang chira nhieu luu huynh thi cracking cang nhilu H2S), tir cae qua trinh xir ly chat thai Khi H2S la loai rit ddc hai cin phai phai loai bd hoae giam thieu trudc sir dyng hay thai mdi trudng Zeolit la vat lieu cd lye vdi loai cho nen cd the sir dyng vat lieu hap phu zeolit cho myc dich lam sach H2S khdi ddng Cac sd lieu Bang cho thiy zeolit NaX cd dung lugng hip phu ddi vdi H2S d nhiet 298°K va ap suit 10, 100, 400mmHg cao hon NaA va CaA Dilu dugc thiy rd hon tren Hinh Bang 4: Dung lirong hap phu H2S ciia cac zeolit hap phu TT Loai zeolit hap phu NaA(4A) CaA(5A) NaX(13X) Dieu kien hap phu mmHg 298 10 0,16 - 100 0,22 - 400 0,24 10 0,21 - 100 0,28 - 400 0,30 298 298 - CaX(lOX) Dung lugng hap phu, g/g °K 298 - 10 0,224 100 400 10 100 400 0,294 0,34 - Tuygn tap bio cio Hpi nghj KHCN "30 nim D5u khf Vift Nam: Cff hpi mdi, thich thuc mdi" 85 ~5o nP=io • P=100 QPMOO Hinh 6: So sanh dung lirgng hap phu H2S KET LUAN Vat lieu hap phu zeolit cd iing dyng rdng rai cdng nghe san xuat ty nhien, dau md hoa Idng, qua trinh lam khd cac cracking va khdng Dac biet, zeolit hap phu cdn dugc diing san xuat eae loai cdng nghiep, oxy eho y te Trong qua trinh lam khd cac chat phan cue manh nhu etanol, metanol, cac tac nhan lanh nhu R22, lam khd nhien lieu phan luc, v.v sir dung loai zeolit 3A (KA) loai zeolit cd dudng kinh mao quan la 3A° nen cd chgn loc hap phu nude rat cao, khdng hap phy cae cau tir khae ed dudng kinh ddng hgc ldn hon 3A°, vi vay tranh dugc sy hap phy cau tir cd ich Trong qua trinh xir ly dau md mac dii zeolit CaX va CaA cd kha nang hap phu hoi nude, H2S, CO2 cao, nhtrng cac ngudn xir ly chira nhieu cau tir cd kich thude ddng hgc rat khae Neu sir dyng cac loai zeolit ed dudng kinh Id xdp ldn se dan den kha nang ddng hap phy cac eau tir cd ich ddng nhu cac hydrocarbon CH4, C2H4, v.v Mat khae, viec san xuat zeolit 5A va lOX phiic tap hon, gia cao hon vay sir dyng loai zeolit NaA va NaX la hgp ly Trong ITnh vuc xir ly mdi trudng, hau het cac ciu tii ddng deu can phai lam sach nen cd the lya chgn loai zeolit cd dudng kinh mao quan ldn vdi dung lugng hap phu eao nhu NaX, CaX, CaA Trong cdng nghe san xuat oxy cd tinh khiet cao tir khdng khi, sir dyng loai zeolit 5A loai zeolit cd kha nang hap phy chgn lge ddi vdi nito, CO2, H2O cao hon nhieu so vdi oxy Tuy nhien, de xet hieu qua eiia qua trinh hap phu edn phai tinh den yeu td gia vat lieu Dac biet edn phy thude vao cac dieu kien cdng nghe nhu nhiet do, ap suat va su cd mat ddng thdi cac tac nhan hap phy canh tranh ddng TAI LIEU THAM K H A O I Salil U Rege, Ralph T Yang, Mack A Buzanowski, 2000 Sorbents for air purification in air separation Chemical Engineering Science 55 86 Khi ning hap phg cie tap chat cua mpt s6 loai zeolit sir dyng tj;ong^ Mark W Ackey, Salil U Rege, Himanshu Saxena, 2003 Application of natural zeolites in the purification and separation of gases Microporous and Mesoporous Material 61 R Szostak, 1992 Handbook of molecular sieves Van Nostrand Reinhold, New York Donald W Breck, 1974 Zeolite molecular sieves: Structure, Chemistry and Use New York Yang R.T., 1997 Gas separation by adsorption process London Imperial College Press Vd Thi Lien, 2004 Mpt sd gidi phdp ngdn ngira su tgo thdnh hydrat qud trinh khai thde, van chuyen vd che bien tie nhien vd ddu md Tap chi Dau khi, Sd Vd Thj Lien, 2004 Uu the cua chdt hdp chua zeolit so vai mpt sd vdt li?u hdp phu rdn khdc cdng nghe xir ly Tap chi Dau khi, So ... COSMIN, MOLSIV, v.v Zeolit thudc nhom zeolit X Hinh 2: Cau triic tinh the zeolit X 80 Kha ning hap ph^ cie tap chat cua mpt so loai zeolit sd dung t£on£:^ a Zeolit lOX Loai zeolit cd dudng kinh... (0,8nm), tinh the zeolit lOX cd ciu triic kilu faujasit Trong zeolit lOX khoang 75% ion Na"" dugc thay the bang ion Ca^"^ Zeolit CaX cd the nhan duge tir qua trinh trao ddi cafion ciia zeolit dang... chat Loai zeolit cd tinh chat tuong ty zeolit lOX la Zeolon Na (My), Zeosorb (Ddng Dire), Calsite (Tiep), CaX (Lien Xd cu) b Zeolit 13X Loai zeolit cd dudng kinh ldn hon nhieu so vdi zeolit A