Li M uTrn th gii nhiu nc tin tin cng nghip ha hc pht trin t rt lu v n chim mt v tr quan trng trong nn kinh t quc dn, n l mt ngnh sng cn cho cc ngnh khc bi v n to ra ngun nguyn liu cho cc ngng khc i su vo sn xut to ra cc n phm c gi tr ln. Cn tai Vit Nam do yu t v lch s nn cng nghip ha hc cn cha pht trin, nhng nm gn y chnh ph v ang u t, i mi v trang thit b ln con ngi nhm thc y cng nghip ha hc pht trin, ui kp cc nc trong khu vc v trn th gii.Cc sn phm ca ngnh cng nghip ha hc ngy cng a dng, c s dng rng ri trong cng nghip v i sng hng ngy bi nhng u im ht sc qu bu ca n m kh c th thay th c nh nh, bn c v nhit, hn na gi thnh sn xut li r hn nhiu v ngun nguyn liu li di do hn so vi cc loi vt liu khc.Anhydrit phtalic l mt trong nhng sn phm trung gian c vai tr quan trong trong ngnh cng nghip ha hc. T anhydrite phtalic chng ta c th sn xut c nhiu sn phm ha hc c gi tr kinh t ln. Anhydrit phtalic c s dng ch yu sn xut cc cht nha do phthalate. Cc ng dng chnh ca anhydrite phtalic bao gm: Nha phthalates (ch yu PVC), nha polyester khng no, nha ankyl, polyol polyester, thuc nhum v bt mu, v cc ng dng khc.Nhu cu ton cu i vi phthalic anhydride l 3.263 ngn tn (7,195 triu bng Anh) vo nm 2005 tc tng trng ton cu tng th cho PAN d kin s l khong 3,5% mi nm trong nm nm tip theo.Bn khu vc chnh, Bc M, Chu u, Trung Quc v Nht Bn, chim 68% (4,864 triu bng) ca nhu cu.Phn cn li ca th gii chim phn cn li bao gm: cc quc gia chu khc, M Latin v cc khu vc khc (bao gm c Nam Phi v Trung ng).Do p lc mi trng nhu cu v anhydrite phtalic tng chm chp chu u v Nht Bn.Nhu cu trong phn cn li ca chu , c bit l Trung Quc li c s tng trng mnh m. Hin ti Vit Nam cha c nh my sn xut anhydrite phtalic, ngun nguyn liu ch yu nhp ngoi t cc nc pht trin. Tuy nhin nhu cu cho sn xut ngy mt tng, hy vng trong tng lai s xy dng nh my sn xut anhydrite cung cp cho th trng trong nc.Trong n ny em c giao v nhn ti Thit k phn xng sn xut anhydrit phtalic. y l mt ti khng mi nhng cng rt kh khn trong qu trnh nghin cu, v vy em mong s gip ca cc thy c trong b mn, c bit l s gip ca PGS.TS: Nguyn Hng Lin cng ton th cc bn n c hon thin hn.

Phn I: Tng QuanChng I: Gii Thiu Chung V Sn Phm Anhydrit Phtalic1. Tnh cht ha hc:Anhydrit phtalic c cng thc phn t: C6H4(CO)2O.C cng thc ha hc l:

Tn gi IUPAC l: 2-benzofuran-1,3-DioneAnhydrit phtalic l mt cht trung gian c tnh cht ha hc phong ph, nh c vng benzen v phn ng nh thc C=O.a. Phn ng thy phn. Anhydrit phtalic b thy phn bi nc to thnh axit ortho phthalit:

y l phn ng thun nghch, khi lm nng axit ln trn 180oC th axit phtalic b bin i to thnh anhydrit phtalic. Tuy nhin axit phtalic d dng b mt nc do to thnh nhm (CO)2O. b. Phn ng vi ancol to thnh este phtalate.Ging nh vi cc anhydrit khc phn ng vi ancol l c s sn xut este phtalate c s dng rng ri trong sn xut cht do, c bit l sn xut PVC. Trong nhng nm 1980, khong 6,5 109kg ca cc este c sn xut hng nm v quy m sn xut gia tng mi nm, tt c t alhydrit phthalic. Qu trnh bt u vi phn ng ca phthalic anhydride vi ru, cho monome este:

Cc este ha th hai kh khn hn v i hi phi loi b cc nc:

Cc diester quan trng nht lbis (2-ethylhexyl) phthalate("DEHP"), c s dng trong sn xutnha polyvinyl clorua.c. Phn ng vi peroxit.y l phn ng m vng do tc dng vi peroxit, sn phm to thnh l axit peroxy.

d. Phn ng kh nc trong hp cht nitro-ancol to thnh cc nitroanken.Cc nitroanken l nhng hp cht ngun tng hp cc polyme c ngha trong cuc sng.

2. Mc ng dng v tiu th.Anhydrid phthalic c s dng ch yu sn xut phthalates dng to hp cht do polyvinyl clorua linh hot trong cuc sng ca con ngi. Phthalic anhydride cng c s dng sn xut polyeste khng no c s dng sn xut nha si thy tinh gia c. Cc cng ty s dng ccnha ch to cc quy hng hoa sen, hoa tng hp, m tm xy dng, tu thuyn v cc phng tin gii tr. Cc cng ty cngs dng alhydrit phthalic lm cho nha alkyd s dng ch yu trongdung mi truyn qua lp ph bo v trong ngnh cng nghip sn. Cc cng tys dng alhydrit phthalic lm cho anhydrit halogen c s dng nhcht chng la; polyol polyester urethane; phthalocyaninesc t; thuc nhum; nc hoa; dc phm; thuc da; dung mi; thuc dit cn trng; v ha hc khc nhautrung gian.S suy gim trong sn xut ca alhydrit phthalic t 1,040 triubng Anh vo nm 1988, ti 935 triu bng nm 1989, l kt qu cai mi sn phm, thay i cng ngh, sn phm xy ra trong ngnh cng nghip t. Tuy nhin, hng tng trng sn lng ca alhydrit phthalic d kin s phc hi vtng 2-3 phn trm mi nm trong tng lai. Ccsn phm ca phthalic anhydride sn xut nha s dng cho gia c trong vn chuyn vxy dng d kin s tng 3-5 phn trm. Ccnhu cu di hn cho cc dung mi da trn lp ph epoxy hoc sn. Ngoi ra, cn s dng cc alhydrit phthalic nhmt trung gian sn xut thuc nhum. Ccnhu cu dioctyl phthalate, cht do nguyn sinh, s gimbi v cc quy nh v mi trng.Nh vy, cc ng dng chnh ca anhydrite phtalic bao gm: Nha phthalates (ch yu PVC), nha polyester khng no, nha ankyl, polyol polyester, thuc nhum v bt mu, v cc ng dng khc.3. Phng php sn xut ra cht.Anhydrit phtalic c sn xut trong cng nghip t naphtalen hoc o-xylen bng cc k thut oxy ha tng t nhau. Naphtalen c ngun gc ha than l ngun nguyn liu duy nht cho n cui i chin th gii th hai, nhng sau dn dn c thay th bng o-xylen vi t lng ln trong cc phn on du m. Tuy nhin ngun naphtalen t du m lm sng li cc cng ngh s dng loi nguyn liu ny. Nm 1965, khong 80% nguyn liu s dng l naphatalen, v mt na trong s c ngun gc t du m. Nhng nhng nm gn y, tnh trng ny b o ngc v o-xylen chim hn 80% qu trnh tng hp anhydrit phtalic. Phn ln cc qu trnh tng hp s dng nguyn liu naphtalen hay o-xylen u tin hnh trong pha hi, ch mt phn nh thc hin trong pha lng. Trong bn n la chn cng ngh i t o-xylen nn ta ch tm hiu v loi nguyn liu ny.4. Ha hc ca phng php.Cc phn ng lin quan ti qu trnh tng hp gm c:i t nguyn liu naphtalen:

Cc phn ng phn hy chnh:

C10H8 + 9O2 + 6CO2 + 3 H2Oi t nguyn liu o-xylen:

Phn ng ph ca ca qu trnh cng l chy hon ton v hnh thnh anhydrit maleic. Tt c cc phn ng trn u ta nhit mnh, xy ra vi s c mt ca xc tc. Xc tc ny c th l c nh trong thit b phn ng ng chm vi 5000 20000 ng. Nhit c tch ra nh s dng lu cht lm lnh hoc l mui nng chy ( nitrat/nitrit ) hoc hn hp owtectic natri/kali lm vic 360-420oC. Xc tc cng c th c s dng dng tng si, c cc h thng lm lnh (ng xon rut g). Nhit sinh ra c s dng sn xut hi p sut cao. Nhit ta ra v l thuyt l 10500 Kj/Kg anhydrit phtalic, nhng thc t gi tr ny ln n 17000Kj/Kg do qu trnh chy hon ton. Cc h xc tc c s dng trn c s oxit V2O5 v TiO2. Tui th ca xc tc ph thuc vo iu kin lm vic, dao ng trong khong 2-3 nm. Qu trnh oxy ha din ra trong khng kh vi t l mol hydrocacbon/khng kh l 60 120 m bo thp hn gii hn bt la (1,7% mol o-xylen/1mol khng kh) trnh s phn hy ca xc tc.5. Cng nh sn xut.Cc qu trnh pha hi c chia thanh hai loi: xc t c nh v xc tc tng si. Trc y, c hai loi xc tc c nh: mt loi c th lm vic nhit dng thp (350-390oC), tc th tch thp, hiu sut cao, mt loi c th lm vic nhit cao (450-550oC), tc th tch cao nhng hiu st li thp hn. S pht trin ca cc th h xc tc mi gip cho qu trnh c th vn hnh 380-400oC, tc th tch cao nhng vn gi c hiu sut cao nh qu trnh lm vic nhit thp. l cc cng ngh ca BASF, Flatital, Japan Catalytic Chemical, Lonza, Mitsu Toatsu, Rhoone-Poulenc, Scientific Design, VebaCc qu trnh cng ngh xc tc tng si ch yu s dng nguyn liu naphtalen c hiu sut thp hn cng ngh xc tc c nh, c bit l khi s dng nguyn liu l o-xylen. Cng ngh in hnh l ca hng Sherwin-Williams/Badger.a. Cng ngh BASF xc tc c nh.C hai dng nguyn liu o-xylen c gia nhit ti 140-150oC v khng kh c lc, nn v gia nhit ti 160oC c dn vo thit b phn ng ng chm cha 15000 ng ng knh 2,5 cm, cao 3,2 m. Nhit c gi 380oC nh tun hon mui nng chy. H thng trao i nhit vi dng lu cht tun hon c s dng sn xut hi p sutt cao (6 Mpa). Xc tc l hn hp ca cc oxy vanadi v titan mang trn cht mang tr khng c cu trc xp. Hiu sut anhydrit phtalic l 74% vi lng o-xylen tiu th 95%.Dng sn phm phn ng trc ht c lm lnh v tn dng nhit sn xut hi p sut thp (1 MPa) v kh d c ra bng nc, sau c thi vo mi trng. Dng sn phm ngng t nhn c s tip tc chuyn ti cc thit b ngng t lm vic gin on, ti sn phm c nng chy 130oC v dn vo b cha. Sn phm th c gia nhit chn khng vi s c mt ca ph gia phn hy cc tp cht khng bay hi (polyme, cc sn phm mu). Sau n c chuyn sang thp chng chn khng th nht (15Kpa) tch anhydrit maleic v cc axit benzoic v toluen nh, ri chuyn sang thp chng chn khng th hai, ti y 99,5% khi lng anhydrit phtalic c thu hi nh.b. Cng ngh Sherwin-Williams/Badger xc tc tng si.S cng ngh ca qu trnh ny, naphtalen tinh khit dng lng (nhit nng chy> 80oC) c a vo pha di lp xc tc cha trong thit b phn ng. Ngay lp tc nguyn liu s b ha hi v phn tn vo mi trng rn, tip xc vi xc tc nng v khng kh c a vo t ghi phn phi pha di ca h thng. Naphtalen bay hi v b oxy ha thnh anhydrit phtalic nhit ng nht 340-385oC nh c s khuy trn mnh ca mi trng phn ng do tc ng ca xc tc tng si. Xc tc c s dng cho qu trnh ny l oxit vanadi mang trn silicagen.Nhit phn ng c tch nh tun hon nc trong cc ng t trong lp xc tc, v c tn dng sn xut hi p sut cao. Cc ht rn cun theo dng kh ra khi thit b phn ng b gi li nh cc li lc s v tr li mi trng phn ng. Anhydrit phtalic to thnh c ngng t trng thi lng v rn. Sau chng c chuyn ti khu vc tinh ch, ti y chng s c x l nhit phn hy cc tp cht khng bay hi gy ra s c mu ca sn phm v chng ct chn khng. Hiu sut anhydrit phtalic theo cng ngh ny l khng cao so vi cng ngh lp xc tc c nh c bit l xc tc tng si. Trong bn n la chn cng ngh i t o-xylen nn ta ch tm hiu v loi nguyn liu ny.Chng II: Gii Thiu Chung V Nguyn Liu O-xylen1. Tnh cht vt l:O-Xylen hay 1,2-dimetyl benzen l mt trong nhng ng phn c nhiu ng dng quan trng trong s cc ng phn ca xylen C6H4-(CH3)2. O-Xylen c s dng trong cng nghip ch yu sn xut polieste v nha PVC c ng dng rng ri trong mi lnh vc i sng x hi.

Ortho-xileneOrtho xylen c khi lng phn t l 106,16 vC, si 139,40C, im nng chy nhit -25.20C, tn ti dng lng khng mu, c mi d chu hay dng tinh th. O-xylen l cht c d bt chy, tan tt trong etanol v t tan trong nc.Bng 1: Mt s c trng k thut.Thng sn vo-xylen

Khi lng phn tvC106,16

T trng 200C0.876

Nhit nng chy0C-25,2

Nhit si0C144,4

Gii hn n trong khng khTrnDi% th tch1,16,4

Nhit chp chy cc kn0C17,2

T trng hi(khng kh=1)2,773,7

Gii hn tip xc (ppm; gi)100;8

Xylene l mt cht lng d chy v c th tr thnh mt hn hp kh n c bit khi cha trong cc thng rng v khng sch. Hi Xylene th khng th nhn thy c nhng nng hn khng kh, c th trn v lan di trn mt t.Tnh in c th sinh ra trong qu trnh vn chuyn (cng nh trong qu trnh bm rt).Khng s dng kh nn ui hoc np, d ti hoc x l Xylene.Xylene gy d ng mnh vi da v mt. Hi Xylene kch thch vi im gy hi cao. Vo lc cao im, hi c th c hp th v gy ra cc tc ng dy chuyn nh lm hi n gan, thn v h thn kinh trung tm.2. Tnh cht ha hc:O-xylen l dn xut ca benzen nn n c y tnh cht ca benzen, nn n tham gia phn ng th, phn ng cng, phn ng oxi ha.2.1. Phn ng th.a. Phn ng halogen ha:Khi c bt st, o-xylen tc dng vi brom khan to thnh dn xut halogen v kh hiro bromua:

b. Phn ng nitro ha:O-xylen tc dng vi hn hp H2SO4 v HNO3 m c to thnh dn xut nitro ca n:

Khi vng benzen c sn nhm ankyl (hay cc nhmOH,NH2,OCH3,...), phn ng th vo vng s d dng hn v u tin xy ra v trorthovpara. Ngc li, nu vng benzen c sn nhmNO2(hoc cc nhmCOOH,SO3H,...) phn ng th vo vng s kh hn v u tin xy ra v tr meta.2.2. Phn ng cng:Khi un nng c xc tcNihocPt, o-xylen cng vi hiro thnh xicloankan.

2.3. Phn ng oxi ha:Cc ankylbenzen khi un nng vi dung dchKMnO4th ch c nhm ankyl b oxi ha.

3. Cc ngun cung cp nguyn liu:3.1. T qu trnh Reforming xc tc.Hn hp xylen ni chung, cng nh o-xylen ni ring ch yu c tch t sn phm ca qu trnh reforming xc tc, vi nguyn liu u l thng l phn on napthta. Trc khi i vo qu trnh th nguyn liu cn phi c x l tp cht c bit l lu hunh, v lu hunh rt nhy cm ti h xc tc Pt Re ca qu trnh reforming. Thnh phn cng ca sn phm reformate cng nh hm lng ca p-xylen ph thuc rt nhiu vo cch tin hnh qu trnh reforming cng nh l loi nguyn liu naphta c s dng. Thnh phn ca phn on naphtha c bit l hm lng naphthen hay cc hydrocacbon thm c nh hng ln nht n n cht lng ca sn phm reformate thu c.Trn thc t naphtha thu c t qu trnh chng du naphtenic th s ph hp nht cho qu trnh reforming sn xut hp cht thm. Tuy nhin phn on naphtha c sn xut t qu trnh hydrocracking thng cng thu c giu hm lng naphthen nn rt ph hp lm nguyn liu u cho qu trnh reforming sn xut cc ng phn xylen. Bn cnh thnh phn, khong nhit si ca naptha nguyn liu cng nh hng n hiu xut thu c xylen. Bng 2: S ph thuc ca thnh phn reformate vo nhit si ca nguyn liu u vo.Khong nhit si ca Naphtha, 0C

60-160107-16090-160

Thnh phn ca nguyn liu, % khi lng

Paraffin69,662,264,2

Naphten19,521,222,2

Hydrocacbon thm10,916,613,6

Thnh phn hydrocacbon thm trong Reformat, % khi lng

Benzen9,31,65,2

Toluen21,719,025,1

Hydrocacbon thm C820,834,326,2

Hydrocacbon thm C9+8,815,211,2

Nh s liu trong bng, khong nhit si thch hp nht ca Naphtha lm nguyn liu Reforming sn xut para xylen l t 106 n 160 0C.3.2. T qu trnh cracking hi nc.Xng nhit phn c thnh phn t C5 tr ln l sn phm ca qu trnh cracking hi nc cc phn on lng. Thnh phn ca xng nhit phn c cha hm lng ln cc hydrocacbon thm, c bit l benzen, v mt lng tng i cc ng phn xylen. Chnh v vy y cng l mt ngun ng gp sn phm c gi tr co cho c cng ngh sn xut xng cng nh cng ngh tng hp hu c ha du. Sn lng xng nhit phn cng nh hm lng cc ng phn xylen trong c quyt nh bi nguyn liu s dng v iu kin tin hnh sn xut.Bng 3: nh hng ca nguyn liu u vo n lng xng nhit phn v lng hydrocacbon thm C8 t cracking hi nc trong iu kin khc nhit vi dng C2, C3 tun hon Nguyn liuSn lng xng nhit phn (C5-2000C), %Sn lng Hydrocacbon thm C8, %Phn hydrocacbon thm C8 trong xng nhit phn, %

Etan1,7

Propan6,6

Butan7,10,45,6

Naphtha c nhit si trung bnh18,71,89,6

Du chng p sut kh quyn18,42,212,0

Du chng p sut chn khng19,31,99,8

Sn phm xylen t xng nhit phn l sn phm ph ca qu trnh sn xut etylen v propen, tuy nhin trong mt s trng hp vic tch cc ng phn xylen li mang li hiu qu v mt kinh t.Vic iu chnh iu kin sn xut tuy khng ti a ha sn lng ca xylen nhng cng c nh hng ng k, c th l nu tng nhit phn ng, gim thi gian lu, gim thi gian lu bng cch tng lng hi vo th s lm gim ng k lng xng nhit phn thu c, tuy nhin hm lng ca xylene trong li tng ln.

Bng 4: nh hng ca iu kin phn ng (thnh phn etylen trong sn phm) ca qu trnh cracking hi nc n nng xut v thnh phn ca xng nhit phn.iu kin (% Etylen)Xylen + Etylbenzen (trong tt c cc sn phm), % khi lngXylen + Etylbenzen trong xng nhit phn, % khi lng

Thp (24,4)0,93,5

Trung binh (28,5)1,67,2

Cao (33,4)1,710,7

3.3. Cc qu trnh chuyn ha Hydrocacbona. Isome ha.V o-xylen l ng phn c gi tr nht xn xut PVC nn bn cnh vic thu nhn n t qu trnh tch hn hp ng phn xylen bng kt tinh phn on hoc hp ph, hiu sut o-xylen cn c tng cng nh qu trnh isome ha p -, m-xylen v c etylbenzen.b. Phn b li Toluen.Qu trnh ny c pht trin thnh quy m cng nghip nhm mc tiu tng sn lng benzen v hn hp xylen trn c s chuyn ha toluen t c gi tr ng dng hn. Bng cch kt hp vi qu trnh phn tch o-xylen theo phng php kt tinh hoc hp ph, hoc kt hp Isome ha, cng ngh ny c th c s dng sn xut lng tng i ln o, p-xylen m khng cn tng lng reformat x l.c. Qu trnh Cyclar.Bn cht qu trnh Cyclar l chuyn ha c xc tc LPG, mt hn hp ca propan v butan, thnh sn phm giu hydrocacbon thm. Giai on u tin c gi thit l phn ng dehydro ha ca propan v butan thnh cc olefin tng ng. Tip , cc olefin ny s oligome ha thnh cc olefin C6, C7 v C8. Phn ng tip theo l dehydro vng ha to thnh cc hydrocacbon thm BTX. Mc d olefin l cc hp cht trung gian ca qu trnh ny nhng sn phm cui cng ca qu trnh c nng olefin rt thp. Ton b qu trnh phn ng l thu nhit do tnh tri ca phn ng dehydro ha v cracking. Metan v etan l cc sn phm ph hnh thnh t phn ng Cracking. Hiu sut hydrocacbon thm t 63-66% ty thuc vo thnh phn nguyn liu. Thnh phn sn phm lng cha ti 92% khi lng BTX, 7-8% hydrocacbon thm C9 v C10, v rt t lng hydrocacbon khng thm. Nu ch s dng propan lm nguyn liu th lng hydrocacbon thm C8 thu c l 17,3% khi lng, cn s dng butan th thu c 19,8% khi lng hydrocacbon thm C8. Lng xylen thu t qu trnh ny t c khong 15% khi lng nguyn liu a vo.3.4. Ngun t than .Du nh, c hnh thnh nh l sn phm ca qu trnh cacbon ha than (cc ha) nhit cao, c cha khong 60% benzen v 12-20 % toluen. Trong iu kin cc ha 10000C, khng c khng kh, s xy ra cc qu trnh chuyn ha su (phn hy nhit v thm ha) phn hu c ca than to thnh cc, cc sn phm lng v kh. Do thanh ngho hydro hn so vi du m nn hiu sut sn phm cc to thnh (70-80%) ln hn rt nhiu so vi sn phm lng (4-5%). Tuy nhin, v qu trnh cc ha din ra nhit cao nn sn phm lng c thm ha hon ton (95-97%), v vy lng hydrocacbon thm l rt ng k. Cc sn phm hydrocacbon thm hnh thnh t qu trnh phn hy nhit v thm ha phn hydrocacbon ca than l benzen, toluen, xylen, thiophen, pyridinCc hydrocacbon thm c th c tch ra nh qu trnh hp th ngc dng bng phn on du m c nhit si cao, khong 300-4000C. Hn hp c chng tch trong thp chng ct li cun hi nc lin tc. Cc hydrocacbon nh c tch ra nh qu trnh chng ct v sn phm th c ra bng dung dch axit sunfuric c loi b hon ton cc hp cht lu hunh, cc hydrocacbon c tip tc chuyn v b cha, trung ha ht phn axit d v ra li bng nc. Qu trnh hydro ha loi b cc cht lu hunh, nit v cc hp cht khng no cn li. Benzen c tch ra t phn on hydrocacbon thm nh qu trnh chng trch ly vi dung mi sunfolan. Cc ng phn xylen c tch ra tng t so vi i t qu trnh Reforming xc tc.Cng ngh sn xut hydrocacbon thm i t sn phm lng ca qu trnh cc ha than trn thc t ch ph bin khi du m cha c bit n v khai thc. Ngy nay cng ngh ny ch cn c s dng trng mt s nh my Nam Phi v Niudilan.4. ng dng:Sn xut sn v nha:- Dng Xylene lm dung mi cho sn b mt v n c tc bay hi chm hn Toluene v kh nng ho tan tt. N c dng trong trng men, sn mi, sn tu bin, cc loi sn bo v khc v dng trong sn xut nha alkyd.Thuc tr su:- Xylene c s dng lm cht mang trong sn xut thuc tr su ho hc.Mc in:- Xylene dng lm dung mi cho mc in v n c ho tan cao.Keo dn:- Xylene c dng trong sn xut keo dn nh keo dn cao su.