I- Gii thiu mn hc Chng 1

Gii thiu chung

Mn ho k thut i cng c nhim v trang b cho sinh vin nhng kin thc c bn, st vi iu kin thc t sn xut Vit Nam ca ng nh cng ngh ho hc ni chung. Trong cng nghip ho cht sn phm rt a dng, vic m t c nhiu cng ngh c th l rt kh. Mt khc trong k thut sn xut li c nhiu im chung. c Nm c bn cht chung c th hiu c nhiu cng ngh sn xut c th v tng qu trnh sn xut c th, mt khc va phi khi qut ho cc vn . Trc khi hc mn ha k thut i cng sinh vin c hc cc mn c bn v c s cn thit, tuy nhin cc kin thc y li tch ri nhau ch cha to t trong iu kin sn xut thc t. gip sinh vin c ci nhn tng qut v k c th t th nh mt h thng. Mn ho k thut i cng c nhim v nhc li cc kin thc y v Nhim v th hai ca mn hc l nghin cu su v qu trnh . II. Nguyn liu trong cng ngh ho hc 2.1 Khi nim Nguyn liu l nhng vt liu t nhin hoc mt s qu trnh gia cng khc c s dng sn xut ra cc sn phm s dng trong i sng v k thut. Nguyn liu nh hng rt ln n kinh t, quy trnh cng ngh v sn phm. Nc v khng kh cng l nhng nguyn liu ph bin v khng th thiu trong cc ngnh cng nghip. 2.2 Nhng phng hng pht trin ngun nguyn liu cht lng

phng hng ci tin cng ngh. Nh vy mt mt va phi nghin cu su v o

thut ho hc khi i v o cc qu trnh c th s khng b b ng v

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Trong cng nghip ngi ta lun mong mun sn xut ra nhng sn phm c cht lng tt, gi thnh thp. thc hin c iu ny khi tm kim ngun nguyn liu cn phi xt n cc vn sau: - S dng loi gnuyn liu c hm lng cao. - Tm kim v s dng loi nguyn liu r tin hn. - S dng phc hp ngun nguyn liu v lin hp cc nh my. - Thay th ngun nguyn liu thc phm bng nguyn liu khng thc phm. 2.3 Mt s phng php lm giu nguyn liu Khi khai thc khng phi lc no nguyn liu cng tho mn cc yu cu ca sn xut m nguyn liu cn phi c lm tng hm lng cht c ch trong nguyn liu. Trong cng nghip ngi ta thng lm giu nguyn liu ngay ti ni khai thc nh vy s gim c nhiu chi ph vn chuyn. 2.3.1 Phng php tn nh Ni dung ca phng php ny l da vo s khc nhau v cng ca cc thnh phn trong nguyn liu. T ngi ta s dng cc qu trnh sy, p nghin, sng phn loi cc thnh phn qung. Ni dung ca phng php ny l da vo s khc nhau v khi lng ring ca cc thnh phn. T ngi ta s dng s dng cc dng lng hoc dng kh phn loi cc thnh phn trong nguyn liu. 2.3.3 Phng php dng nhit Ni dung ca phng php ny l da vo s khc nhau v nhit si v nhit nng chy ca cc thnh phn. T ngi ta s dng phng php chng luyn v phng php lng gn tch cc thnh phn trong nguyn liu. 2.3.4 Phng php ho hc Ni dung ca phng php ny l da vo nhng tnh cht ho hc khc nhau ca cc thnh phn (s dng s ho tan c chn lc hoc cc phn ng c sn phm ho hi, kt ta). 2.3.5 Phng php tuyn ni
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2.3.2 Phng php trng lc

y l phng php hin nay c s dng rt rng ri. C s ca phng php l da vo thm t khc nhau ca cc thnh phn. T ngi ta s dng dung dch tuyn dung dch ny c kh nng thm t c chn lc. Nhng ht k nc s ni ln trn theo dng dch ra ngoi, nhng ht a nc dn dn s lng xung di. Tuy nhin trong thc t s chnh lch v thm t ca cc thnh phn l khng nhiu do ngi ta thng phi s dng thm cc cht gp hoc cht to bt kch thch qu trnh tuyn ni. III. Nng lng trong cng ngh ho hc 3.1 Khi nim Nng lng l i lng c trng cho kh nng sinh cng. Nng lng c s dng vi nhiu mc ch: Vn chuyn, thc hin phn ng, p nghin, nn kh, lc, bm, qut Vic s dng hp l nng lng l mt trong nhng yu t lm gim gi thnh sn phm. Dng nng lng dng ph bin nht l nng lng in v nhit nng. 3.2 Phn loi Nng lng c th c phn thnh hai loi c bn: - Loi nng lng c kh nng phc hi: Thu in, gi, mt tri, a nhit. - Loi nng lng khng c kh nng phc hi: Than, du m, ht nhn 3.3 Nhng hng pht trin nng lng Trn th gii trong nhng nm gn y i su vo cc lnh vc: Nng lng mt tri, gi, a nhit, sng bin, ht nhn. nh hng pht trin ngun nng lng Vit Nam l thu in v cc ngun nng lng khc trong c nng lng ht nhn. Nm 2002 thng qua d n xy dng nh my in ht nhn, d kin nm 2020 t my in ht nhn u tin bt u hot ng. IV. Nc trong cng ngh ho hc 4.1 Vai tr
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Nc c ng dng rng ri trong sinh hot cng nh trong sn xut nh: Dng lm dung mi, cht ti nhit, cht phn ng, lc ra, sinh hot 4.2 Phn loi 4.2.1 Nc trong kh quyn (Tuyt, nc ma) Tp cht l cc kh ho tan nh: O2, CO2, CO, H2S, SO2 Thnh phn v hm lng tp cht tu vo tng vng. 4.2.2 Nc trn b mt (sng h, ao, bin) Ngoi cc tp cht nh nc trong kh quyn nc trn b mt cn c cha cc tp cht l cc mui khong ho tan. Nc trn b mt c chia thnh 2 loi: Nc ngt (<1g NaCl/1 lt nc) v nc mn (>1g NaCl/1 lt nc). Nc ngt c th c phn loi theo hm lng Ion Ca2+, Mg2+: mg lg Ca2+, Mg2+/lt 0-1,5 1,5 3 36 6 10 > 10 Rt mm Nc mm Trung bnh Cng Rt cng cng

4.2.3 Nc ngm (ging, ging khoan, sui ngm) Loi nc ny cha t tp cht hn hai loi nc trn, tuy nhin trong n vn cha cc mui khong ho tan. * Nh vy cc loi nc trn d t hay nhiu u c cha cc tp cht trong n v vy trc khi s dng trong cng nghip v trong sinh hot nc cn phi c x l trc khi s dng. 4.3 K thut x l nc cp Cc cng on chnh ca qu trnh x l:

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- Lng lc cc tp cht c hc - Lm mm nc - Gii kh c v st trng nc 4.3.1 Lng, lc cc tp cht c hc Di tc dng ca trng lc cc tp cht c hc s c lng xung di ri c lc sch. Qu trnh lng nc c thc hin lin tc trong cc b cha b tng. kch thch qu trnh lng ngi ta thng cho vo nc mt lng nh dung dch in ly Al2(SO4)3.FeSO4 (phn chua) v mt s cht ng t khc. Cc cht ny s hp ph cc ht keo t st mang in tch m trung ho v in lm tng tc lng ng thi lm mt mu ca nc lm nc trong hn. Sau khi lng huyn ph c lc khi nc bng phng php lc, ngi ta thng s dng vt li lc dng ht tr nh ct. 4.3.2 Lm mm nc * Phng php sa vi (Ca(OH)2) : phng php ny ch s l cng tm thi ca nc v tch c mui st, CO2 lm mm n 0,7 mglg/1 lt nc Ca(OH)2 + Ca(HCO3)2 = 2CaCO3 + 2H2O Ca(OH)2 + Mg(HCO3)2 = CaCO3 + MgCO3 + 2H2O Ca(OH)2 + Fe2+ = Fe(OH)2 + Ca2+ Ca(OH)2 + CO2 = 2CaCO3 + 2H2O * Phng php dng x a: Phng php ny c hiu qu tng i cao lm mm n 0.3 mglg/l Na2CO3 2Na+ + CO32Ca2+ + CO32- = CaCO3 Mg2+ + CO32- = MgCO3 lm mm trit hn ngi ta cho thm mt lng nh Na3PO4 c th lm mm n < 0,1 mg/ 1 lt nc. Na3(PO4) 3Na+ + PO43-

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2Ca2+ + 3PO43-= Ca3(PO4)2 2Mg2+ + 3PO43-= Mg3(PO4)2 Phng php ny c kh nng lm mm rt cao do mui pht pht ca Canxi v Magie rt t tan. * Phng php trao i ion: Phng php ny tch ion Ca2+ v Mg2+ bng cch dng cc ionit c kh nng trao i vi ion Ca2+ v Mg2+ Na2[K] Na2[K] H2[K] + Ca2+ [K]Ca + Mg2+ [K]Mg + Ca2+ [K]Ca + 2Na+ + 2Na+ + 2H+ + 2H+

H2[K] + Mg2+ [K]Mg Na+...

[K] l gc cationit c th l nha cao phn t c cha nhm hot tnh nh H+ , [An]OH + HCl = [An]Cl + H2O 2[An]OH + H2SO4 = [An]2SO4 + 2H2O [An] l gc ationit c th l nha cao phn t c cha nhm hot tnh nh OH-, HCO3c tnh ca phng php ny l sau khi trao i nha cao phn t sau khi s dng c th ti sinh li khi phc kh nng trao i ion. ti sinh Na- kationit ngi ta ding dung dch mui n. Cc anionit th ti sinh bng kim hoc bicacbonat. S V. Cc quy lut c bn ca cng ngh ho hc 5.1 Phn loi cc qu trnh ho hc 5.1.1 H ng th L h trong tt c cc cht phn ng nm trong cng mt pha(pha kh, pha lng). Trong h ng th phn ng ho hc xy ra nhanh hn, c ch phn ng n gin hn, iu khin d dng hn. V vy trong thc t ngi ta c gng tin n h ng th.

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5.1.2 H d th L h cha 2 hay nhiu pha. H 2 pha: L R, K R, L - R, L L, R R Trong cng nghip thng gp h d th hn h ng th. 5.1.3 Qu trnh xc tc * nh ngha: Cht xc tc l nhng cht c tc dng lm thay i tc ca phn ng m khng lm thay i tnh cht ho hc, khng c trong thnh phn sn phm phn ng. * Vai tr ca cht xc tc l bin qu trnh ho hc mt giai on cn nng lng hot ho E ln thnh nhiu giai on c nng lng hot ho e1, e2 nh hn. V vy nhiu phn ng khi khng c xc tc khng xy ra c nhng khi c cht xc tc li xy ra vi tc ln. C ch: A+B=D cn nng lng E A + Xt = A[Xt] cn nng lng e1 A[Xt] + B = D + Xt cn nng lng e2 e1, e2 < E

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Nng lng hot ho

e1

e2

Hng ca phn ng

Nng lng hot ho ca phn ng c dng cht xc tc

5.2 Cn bng trong qu trnh ho hc C 2 loi qu trnh ho hc: - Qu trnh mt chiu - Qu trnh thun nghch Tt c cc qu trnh ho hc thun nghch u tin ti cn bng, ti tc qu trnh thun bng tc qu trnh nghch. Khi cc iu kin ngoi bin i th cn bng s thay i. 5.2.1 Quy tc Leshatelia Trong mt h nu do tc ng bn ngoi m h lch khi trng thi cn bng th cn bng s chuyn dch v chiu lm gim nhng tc ng khin cho h lch khi cn bng. Tu vo c im ca tong phn ng m ta c s tc ng phn ng chuyn dch theo chiu chng ta mong mun. 5.2.2 Hng s cn bng K Xt phn ng: mA + nB pC + qD Tc phn ng thun:
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r1 = k1.[A]m.[B]n Tc phn ng nghch: r2 = k2.[C]p.[D]q k1, k2 l hng s tc ca phn ng thun v phn ng nghch. [A], [B], [C], [D] l nng mol cc cu t ti thi im xt. Khi cn bng (ti thi im cn bng) tc phn ng thun bng tc phn ng nghch. r1 = r2 hay K=
k1 [C] p [ D]q = k 2 [ A]m [ B]n

k1.[A]m.[B]n = k2.[C]p.[D]q

y [A], [B], [C], [D] l nng mol cc cu t ti thi im cn bng. Hng s cn bng phn ng c chng cho hiu sut phn ng, hng s cn bng thun cng cao th hiu sut phn ng thun cng ln. 5.2.3 Hiu sut qu trnh Hiu suet sn phm l t s gia lng sn phm thc t thu Gtt trn lng sn phm ban u G.
x= Gtt Gd

i vi cc qu trnh hiu suet thng c tnh theo cht u chnh. Cht u chnh l cu t quan trng nht trong hn hp phn ng. Khi phn ng t n trng thi cn bng th lc hiu suet t c l hiu suet cn bng xcb. Vi phn ng 1 chiu phn ng xy ra hon ton th xcb =1 Vi phn ng thun nghch th xcb < 1 5.3 Tc ca cc qu trnh ho hc Trong cng ngh ho hc kch thc, nng sut thit b, lng sn phm ph thuc rt nhiu vo tc phn ng. V vy s hiu bit v tc phn ng l rt cn thit.
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Tc phn ng ng th l lng cht tham gia phn ng hoc to thnh khi phn ng sau mt n v thi gian trong mt n v th tch. Tc phn ng d th l lng cht tham gia hoc to thnh khi phn ng sau mt n v thi gian trn mt n v b mt pha. Cng thc c bn ca tc phn ng vi h ng th:
r= dG = k. .C d

Vi h d th:
r= dG = k.F.C d

Trong :

k: L hng s tc phn ng v: L th tch phn ng

C : L ng lc qu trnh

F: l din tch b mt tip xuc pha. Nh vy tc phn ng s ph thuc vo cc yu t sau: 5.3.1 Hng s tc phn ng k Hng s tc k l i lng phc tp ph thuc vo nhiu yu t: - Ho l tnh ca cc cht tham gia phn ng - C cu ca thit b - Tc ca cc dng phn ng i vi h ng hc k ph thuc vo tc phn ng thun k1, tc phn ng nghch k2, cc phn ng ph kn, ph thuc vo h s khuch tn ca cc cht u D1, D2 v h s khuch tn ca sn phm D1, D2 Nh vy ta c
' k = (k1 , k 2 , k n ,..., D1 , D2 ,..., D1' , D2 ,...)

Khi tnh ton cn xc nh xem yu t no nh hng yu t no khng. * i vi qu trnh ng th khi khuy trn mnh s khuch tn xy ra nhanh nn h s khuch tn khng nh hng n qu trnh:
k = (k1 , k 2 , k n )

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* i vi qu trnh d th th khuch tn nh hng chnh n tc khi h s khuch tn s ng vai tr quyt nh:

' k = ( D1 , D2 ,..., D1' , D2 ,...)

i lng hng s tc phn ng k c th tra cu trong s tay hoc c th t tnh ton. 5.3.2 B mt tip xc pha i vi cc phn ng d th cc phng php tng b mt tip xc pha (tng mn, tng tc khuy, xp m, s dng thp a ) u lm tng tc phn ng. i vi cc h K R, L R b mt tip xc pha s bng b mt tt c cc ht rn c bao b bi kh hay lng. i vi nhng ht xp (cht hp ph, cht xc tc) ngi ta tnh c b mt bn trong ca cc mao qun:
F = S rieng .v

Srieng : B mt ring ca lp m(m2/m3) v : Th tch lp m Trong cc h K L, L- L khi khuy trn mnh th vic xc nh b mt tip xc thc t l rt kh khi ta ch xc nh c b mt tip xc pha tng i. 5.3.3 ng lc ca qu trnh * i vi phn ng mt chiu th ng lc C l tch cc nng ca cc cht tham gia phn ng ti thi im xt. mA + nB = pD
m n .C B ng lc ca qu trnh: C = C A

* i vi phn ng thun nghch: mA + nB pD

* m * n C = (C A C A ) .(CB CB )

* i vi qu trnh chuyn khi:

C = (C C * )

Trong : C: L nng thc ca cu t ti pha cho.

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C* : L nng cn bng ca cu t trn b mt phn chia pha. * i vi dng chy cng chiu, i lu, dng cho nhau th ng lc c tnh theo gi tr trung bnh : - Trung bnh logarit:
Ctb = Cd Cc c 2,3 lg d Cc

(Khi hiu cc yu t nh hng n tc phn ng i vi mi qu trnh c th ta s c cc phng php tng tc ca qu trnh).

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Chng 2

Cng ngh cc cht V C

I. Cng ngh sn xut axit sunfuric 1. Khi nim, tnh cht v ng dng 1.1 Khi nim - Trong ho hc: Axt sunfuric l hp cht ca anhydrit sunfuric( SO3 ) vi nc. Cng thc ho hc H2SO4, khi lng phn t 98,08. - Trong k thut : Hn hp theo t l bt k ca SO3 vi H2O u gi l axt sufuric + T l SO3/H2O < 1 (dung dch axt sunfuric ) + T l SO3/H2O = 1 (dung dch monohydrat hay axit sunfuric 100% ) + T l SO3/H2O > 1 (dung dch oleum hay axt sunfuric bc khi) 1.2. Mt s tnh cht ca axt sunfuric v oleum - Axt sunfuric iu kin thng l cht lng snh v nng. - Axt sunfuric sch khng mu, cn axit k thut v ln nhiu tp cht nn c mu sm. - Axt sunfuric l mt axt mnh v l mt a axt. C th y tt c cc axit khc ra khi mui khi tng nhit . - Axt sunfuric l mt cht rt ho nc. - Khi pha long axt sunfuric to nhit mnh lit. 1.3. Nhng ng dng quan trng. axt sunfuric l mt trong nhng ho cht c bn c sn lng ln nht do phm vi ng dng rt rng ri. Axt sunfuric c s dng chnh trong cc lnh vc sau : - Lng ln nht sn xut phn bn supe phtphat, sunfat amn... - Trong cng nghip luyn kim mu axt sunfuric c dng lm tc nhn phn hu. - Trong lnh vc gia cng kim loi axt sunfuric c dng lm sch b mt trc khi sn.

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- Lm nguyn liu sn xut c qui axit, thuc nhum vi, cht do, sn xut thuc n, ru etylic cng nghip... v l nguyn liu iu ch cc hp cht v c v hu c khc. 2. Nguyn liu sn xut Nguyn liu sn xut axt sunfuric rt phong ph bao gm lu hunh nguyn t v cc hp cht c cha lu hunh nh cc mui sunfua, sunfat, kh thin nhin... Sau y l mt vi dng nguyn liu ph bin sn xut axt sunfuric. 2.1 Qung pyrit (FeS2). Qung pyrit l mt loi nguyn liu ph bin sn xut axt sunfuric v t trc tip qung ta thu c hn hp kh cha SO2. Thnh phn ch yu ca qung pyrit l st sunfua (FeS2) cha 53,44% S v 46,56% Fe Qung pyrit thng gp l mt loi khong mu xm, trong qung c ln nhiu tp cht nh : Cc hp cht ca ng, ch km, niken, bc, vng, coban, asen, selen, cc mui cacbonat, canxi sunfat...V vy hm lng thc t ca lu hunh trong qung dao ng trong khong 30-52%. min bc nc ta c mt s m qung pyrit nhng ni chung hm lng lu hunh thp, tr lng khng ln. 2.2 Lu hunh nguyn t (S). Lu hunh nguyn t l mt trong nhng dng nguyn liu tt nht sn xut axt sunfuric v : - Khi t lu hunh nguyn t ta thu c hn hp kh c hm lng SO2 v O2 cao. - Lu hunh cha rt t tp cht (c bit l tp cht ca asen v selen) nn dy chuyn sn xut n gin i rt nhiu. - Khi sn xut vi qui m ln v xa ngun nguyn liu th lu hunh li l ngun nguyn liu r tin nht 2.3 Thch cao

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y cng l mt ngun nguyn liu phong ph sn xut axt sunfuric v nhiu nc trn th gii c m thch cao(CaSO4.2H2O hoc CaSO4). Ngoi ra trong qu trnh sn xut axt phtphoric, supe phtphat kp, nitrpht- nitrphtka...cng thi ra mt lng ln CaSO4. Thng th t thch cao ngi ta lin hp sn xut c axt sunfuric v xi mng khi ngi ta nung thch cao, t st v than trong l quay khi CaSO4 b kh phn kh cha SO2 axt sunfuric i sn xut axt sunfuric, phn x thm ph gia v nghin mn sn xut xi mng. 2.4 Cc cht thi c cha S a. Kh l luyn kim mu Kh l trong qu trnh t cc qung sunfua kim loi mu nh qung ng, ch thic, km...c cha nhiu SO2. y l mt ngun nguyn liu r tin sn xut axt sunfuric ngoi ra vic thu hi SO2 trong kh l cn trnh gy nhim mi trng. b. Kh hydr sunfua (H2S) Khi cc ho than khong 50% tng lng lu hunh c trong than s i theo kh cc ch yu dng H2S. Vic thu hi kh H2S va c ngha kinh t li m bo v sinh cng nghip. Ngoi ra ngi ta cn tn dng mt s cc loi cht thi cng nghip khc nh : tn dng kh l, tinh ch li axt sunfuric thi cng nghip... 3. Qu trnh sn xut axit sunfuric theo phng php tip xc Qu trnh sn xut c m t theo s tng qut sau: Chun b nguyn liu Sn xut kh sunfur (SO2) Tinh ch kh xi ho SO2 thnh SO3 Hp th SO3 thnh H2SO4

3.1. Chun bi nguyn liu

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 sn xut kh SO2 ta phi thc hin qu trnh t nguyn liu, trc khi t nguyn liu cn phi c gia cng c hc hoc gia cng nhit tu vo tng loi nguyn liu. V d : - Qung pyrit thng thng c kch thc 50 - 200 mm v vy trc khi a vo l t cn phi c sy, p, nghin, sng c m v kch thc thch hp. - i vi lu hunh nguyn t cn phi ho lng, lng tch cn trc khi a vo l t. 3.2 Sn xut khi sunfur Qu trnh sn xut kh sunfur thc cht l qu trnh t chy nguyn liu trong cc l t, vi mi loi nguyn liu ngi ta s dng cc loi l t khc nhau. * Khi t pirit u tin FeS2 b phn hu theo phng trnh sau: 2 FeS2 2 FeS + S2 - 103,9 kJ Hi lu hunh tch ra s chy ging nh qu trnh t lu hunh nguyn t: S2 + 2O2 = 2 SO2 + 724,8 kJ Sau khi tch lu hunh, nguyn liu tr nn xp, to iu kin cho n tip tc chy. FeS cng chy theo phn ng: FeS + 7O2 = Fe2O3 + 4SO2 hoc 3FeS + 5O2 = Fe3O4 + 3SO2

C ch ca phn ng ny cha c xc nh r. D theo c ch no phn ng t chy FeS2 cng xy ra theo phng trnh tng qut nh sau: 4 FeS2 + 11O2 = 2Fe2O3 + 8SO2 + 3415,7 kJ hoc 4 FeS2 + 8O2 = Fe3O4 + 6SO2 + 2438,2 kJ

Qu trnh chy ca qung khng nhng ch xy ra gia pirit v oxi m cn xy ra gia cc pha rn vi nhau:
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FeS2 + 16Fe2O3 = 11Fe3O4 + 2SO2 FeS + 3Fe3O4 = 10FeO + SO2 - Sn phm ca qu trnh t qung pirit gm c: SO2 , SO3, Fe2O3 hoc Fe3O4 , N2 , O2 , H2O , Al2O3 , SiO2 , bi, HF , SiF4. - Qu trnh phn hu FeS2 nm trong vng khng ch ng hc, qu trnh chy FeS nm trong vng khng ch khuych tn. - Khi tng nhit tc phn ng tng, tuy nhin khng th tng nhit qu cao v s lm hng thit b, gy hin tng kt khi trong l. Nhit v vn tc ca qu trnh c biu din bng phng trnh: k = k0. e
E RT

- Qu trnh chy xy ra gia pha rn v pha kh qua nghin cu ta thy tc phn hu FeS2 khng ph thuc vo kch thc ca ht qung. Ngc li khi tng mn ca qung, tc l tng b mt tip xc gia pha kh v pha rn th tc chy ca FeS tng ln kh nhiu. Hng s tc chy xc nh theo phng trnh: k = k0.Fn F: B mt tip xc pha n: H s t l - Tc chy ca qu trnh t qung cn ph thuc vo nng O2 theo quan h:
n k = k0. C O
2

C O 2 : Nng oxi trong kh l

Ngoi ra, tc chy ca qung cn ph thuc vo cu to tinh th, thnh phn ho hc v thnh phn khong ca qung, vo cc tp cht trong qung. * Khi t Lu hunh

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Qu trnh t lu hunh tng i n gin v sn phm ca qu trnh chy ch l kh l cha SO2. S + O2 = SO2 + 297,322 kJ Phn ng nm trong min ng hc (tc phn ng ph thuc vo nhit v nng S v O2). Khi tng nhit tc phn ng tng. Thnh phn kh l ch yu l SO2, O2, N2 * Khi t hydr sunfua H2S + O2 = H2O + SO2 * Khi nung thch cao
t CaO + SO3 CaSO4 t CaSO4 + C CaO + CO + SO2

3.3 Tinh ch kh - y l cng on tch bi v cc tp cht ra khi hn hp kh trc khi a sang cng on xi ho. - Qu trnh tch bi c thc hin trong cc thit b xycln, lc in kh, thp ra. - Qu trnh tch cc tp cht c thc hin trong cc thit b : Thp ra 1, thp ra 2, lc in t 1, lc in t 2, thp sy. Tuy phng php tch cc tp cht ny vi dy chuyn thit b cng knh phc tp v c nhiu mu thun nhng y vn l phng php d thc hin v hiu qu v vy hin nay vn c dng ph bin. 3.4 Cng on xy ho SO2 SO3 3.4.1 Phn ng xi ho SO2 a. Cn bng phn ng Phn ng : SO2 + 1/2O2 SO3 + Q y l phn ng thun nghch, to nhit, gim th tch v c s dng xc tc.
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Hng s cn bng phn ng :

K cb = PSO3 PSO2 . PO 2

(I-5)

PSO 3 , PSO2 , PO2 : p sut ring phn ca cc cu t trng thi cn bng, atm.

Trong khong nhit c th tnh Kcb theo phng trnh sau.

lg K cb = 4905,5 4,6455 T

(I-6)

b. Mc chuyn ho : Mc chuyn ho l t l gia lng SO2 b oxi ho thnh SO3 v tng lng SO2 ban u.
x= PSO3 PSO3 + PSO2

(I-7)

Khi phn ng t trng thi cn bng th mc chuyn ho t gi tr cc i, gi l mc chuyn ho cn bng.

xcb = PSO3 ( cb ) PSO3 ( cb ) + PSO2 ( cb ) PSO3 K p . PO 2

(I-8) thay vo (I-8) ta c

= 1 1+ 1 K p . PO2 = Kp Kp + 1 PO2

T (I-5) ta c

PSO2 =

xcb =

PSO3 ( cb ) PSO3 ( cb ) + PSO2 ( cb )

(I-9)

Gi

P : p sut chung ca hn hp kh 2a, b : nng ban u ca SO2 v O2, % th tch SO2 Ban u : 2a Phn ng : 2axcb + 1/2O2 b axcb SO3 0 2axcb 2axcb

Cn bng : (2a-2axcb) (b-axcb) Coi tng s mol ca hn hp kh u l 100 %

Do hn hp kh ngoi SO2, O2, SO3 cn 1 lng ln cc kh khc nn :

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Tng s mol ca hn hp kh sau khi t cn bng l (100 - axcb) Nh vy Thay vo (I-9)

PO2 =

(b axcb ) .P (100 axcb )

xcb = K cb +

K cb 100 ax cb P(b axcb )

(I-10)

V vy phn ng oxi ho SO2 l phn ng to nhit, gim th tch nn khi gim nhit v tng p sut, mc chuyn ho cn bng s tng. 3.4.2 Cht xc tc oxi ho SO2 a. Xc tc kim loi C rt nhiu kim loi c kh nng xc tc cho phn ng oxi ho SO2. Xc tc kim lai c s dng u tin trong cng nghip axit sunfuric l platin do Philips sng. Xc tc platin c hot tnh rt cao, nhit hot tnh thp (khong 375 4000C) nhng rt b nhim c (c bit i vi hp cht ca asen) v rt t tin. tng hot tnh ca cht xc tc v gim gi thnh, ngi ta em platin (c th thm 20 - 40% paladi) ri trn cc cht mang khc nhau nh amian, mage sunfat silicagel... Cc kim loi khc nhau trong nhm platin cng c kh nng xc tc cho phn ng oxi ho SO2 nhng hot tnh thp hn: Pt > Rh > Ir > Pd Ngoi ra, hp kim ca bc, vng vi platin, molipden... cng c hot tnh cao. b. Xc tc phi kim loi Xc tc oxit kim loi : Loi xc tc oxit kim loi c pht hin sm nht l xc tc st oxit c ch to t x qung. u im ni bt ca n l r tin, d kim v t nhy c vi cc tp cht c trong kh l. Song v xc tc st oxit c nhit hot tnh kh cao (di 6250C n d b chuyn thnh st sunfat km hot ng) nn mc chuyn ho SO2 trn xc tc ny

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khng vt qu 0,5. v vy ch dng cht xc tc st oxit khi khng yu cu mc chuyn ho cao (chuyn ho s b). Xc tc crom oxit c hot tnh ban u tng i cao, nhng sau mt thi gian lm vic, n b chuyn thnh dng crom sunfat nn hot tnh gim. V d : nhit 2500C v tc th tch 750 gi (tc th tch tnh bng th tch hn hp kh iu kin tiu chun khi qua mt n v th tch cht xc tc trong mt n v thi gian) mc chuyn ho ban u t trn 0,90. Nhng sau 26, 50, 100, v 130 gi th mc chuyn ho tng ng ch cn 0,80- 0,40 v 0,27. Cc oxit ca ng, mangan, thic, titan, molipden, xeri, thori ... nhit cao (khong 7000C) cng c hot tnh i vi phn ng oxi ho SO2. Kh nng xc tc cho phn ng oxi ho SO2 ca vanadi oxit c pht hin t nm 1895. Sau nhiu ngi tp chung vo nghin cu cht xc tc ny. Cc cng trnh nghin cu i n mt s kt lun sau. - Vanadi oxit V2O5 nguyn cht c hot tnh khng cao i vi phn ng oxi ho SO2. - Xc tc vanadi c hot tnh cao, ngoi thnh phn chnh l vanadi oxit V2O5, phi cha c hp cht kim loi kim Me2O v silic ioxit SiO2. Tng hp ca ba thnh phn chn l iu kin cn thit ch to cht xc tc vanadi c hot tnh cao. - Silic ioxit SiO2 ( dng t do hoc lin kt vi cc cht khc) chim phn ch yu trong xc tc v quyt nh cu trc bn trong ca ht xc tc ( xp, b mt bn trong ...) 3.4.3 iu kin xi ho SO2 trn xc tc vanadi Qu trnh xi ho SO2 l mt giai on quan trng trong sn xut axit sunfuric. V vy cn phi nghin cu nhng iu kin thch hp t c nng sut, hiu sut cao, gi thnh h. Trc ht ta xt n tc phn ng v n quyt nh n nng sut, lng xc tc cn dng, kch thc thit b...

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Trong iu kin sn xut, p sut v nng kh ban u l khng i th tc phn ng ch ph thuc vo hng s cn bng Kcb v hng s tc phn ng k. M ta bit rng k v Kcb ph thuc vo nhit . Khi tng nhit th hng s tc phn ng k tng cn vi phn ng xi ho SO2 th hng s cn bng Kcb gim. Do ta xem xt n s thay i ca k v Kcb theo nhit . Lc u nhit thp khi tng nhit (t 400-500 oC) Kcb c gim cht t tuy nhin k tng rt nhanh do tc phn ng tng. V sau khi tng tip nhit hng s tc tng khng ng k hoc khng tng trong khi hng s cn bng Kcb gim nhanh do tc phn ng gim. Nh vy mi mt hiu sut phn ng ng cong biu din s ph thuc gia tc phn ng vo nhit s c mt im cc i.
Tc 12 tng i xi ho 8

0 420

460

500

Nhit , oC
540

Hnh

nh hng ca nhit n tc phn ng

a. Nhit thch hp. Nhit thch hp l nhit m ti tc phn ng t cc i ng vi mi mc chuyn ho xc nh. nh ngha ny biu din di dng ton hc:
dx d T
X = COSNT

=0

Ly tch phn trn kt hp vi phng trnh tc phn ng ta c

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Tth = lg

4905,5 x b ax (1 x ). 100 ax

+ 4,937

T biu thc trn ta thy nhit thch hp khng phi l mt hng s m ph thuc vo nng SO2, O2 ban u v ph thuc vo mc chuyn ho x.
Mc chuyn 80 ho (%) 60 40 20 0 400 500 Nhit , oC 600 100 B C

ng cn bng v ng nhit thch hp trn th T-X

Trong

BB : ng cn bng CC : ng nhit thch hp

V trong iu kin sn xut khi nng cc cht u khng i, khi mc chuyn ho tng th nhit thch hp gim. Nh vy mun cho tc xi ho t cc i phi tin hnh phn ng nhit thch hp. Nhng trong qu trnh phn ng mc chuyn ho tng tc l nhit thch hp gim. Do ta ch c th tin hnh sao cho gn vi ng thch hp nht mun lm c iu ngi ta chia qu trnh xi ho SO2 ra thnh nhiu on (hay cn gi l nhiu lp) sau mi lp ta tin hnh lm ngui hn hp kh. Trong thc t ngi ta thng s dng 4 5 lp xc tc. Khi qu trnh xi ho c biu din trn th T-X nh sau : b. Mc chuyn ho Khi tng mc chuyn ho s: - Gim c lng SO2 trong kh thi.

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- Tng c mc s dng lu hunh. Nhng t c mc chuyn ho cao phi kt thc qu trnh xi ho nhit thp m ti iu kin s gn ng cn bng khi tc phn ng chm tc l thi gian phn ng cn thc hin lu, mun ko di thi gian phn ng ta li phi tng lng xc tc nh vy li lm tng gi thnh sn phm. nh hng ca mc chuyn ho vo gi thnh sn phm c biu din trn th.
4

Gi thnh
2

0 0.96 -2

3
0.97 0.98 0.99 1

1 Mc chuyn ho, x

-4

nh hng ca mc chuyn ho n gi thnh axit sunfuric

Trong : 1- Gim gi thnh do tng mc chuyn ho. 2- Tng gi thnh do tng lng xc tc. 3- nh hng chung ca c hai yu t. Nh vy v gi thnh sn phm th ng vi mc chuyn ho x = 0,98 l thch hp nht, nhng v mt v sinh cng nghip th mc chuyn ho ny khng m bo yu cu do kh thi vn cn cha nhiu SO2. c. Nng thch hp. Nng SO2 nh hng n nhiu yu t k thut nh : Qut kh, thp chuyn ho, hp th (tiu hao in nng, lng cht xc tc, ch nhit... ). Nu xt ton b s nh hng trn l rt kh y vn chnh chng ta quan tm n l nh hng ca nng SO2 trong qu trnh xi ho. Khi nng sut v ng knh thit b khng i nu tng nng SO2 th lng xc tc cn dng s tng nhanh khi chiu cao lp xc tc s tng lm tng tr lc
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ca thp. Mt khc nu nng SO2 qu cao nhit lng phn ng to ra ln lm nhit ca lp xc tc tng cao lm xc tc nhanh b mt hot tnh. Tuy nhin nu nng SO2 qu thp th th tch hn hp kh ln iu ny cng dn n vic tng tr lc ca lp xc tc. S nh hng ca nng SO2 n nng sut c biu din bng th. Do vy nng thch hp ca SO2 s tu thuc vo tng loi nguyn liu s dng. Nguyn liu u: Nng SO2 thch hp: SO2100% 14 S 8,5 FeS2 7,0 H2S 6,3

2.4

Nng 2.2 sut thp, 2 n v 1.8 qui c

1.6 1.4 5 6 7 8 9 10

92% 94% 96% 97%

Nng SO2, % nh hng ca nng SO2 ban u n nng sut thp

Theo th trn ta thy khi nng SO2 tng t 6,5 ln 9 % th nng sut thp tip xc ch thay i khong 5%. V vy trong thc t sn xut ngi ta thng s dng nng SO2 cao hn nng thch hp.

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100

B C B C

Mc chuyn ho

80 60 40 20 0 400

450

500

550

600

650

Nhit , oC

Qu trnh xi ho trn th T-X trn thp tip xc 5 lp xc tc S dng trao i nhit trung gian

3.5 Hp th anhydrit sunfuric SO3 C s ho l ca qu trnh hp th SO3 Qu trnh hp th SO3 u tin SO3 ho tan vo dung dch axt sunfuric, sau phn ng vi nc trong : nSO3 + H2O = H2SO4 + (n-1)SO3 Tu theo t l gia lng SO3 v H2O m nng axit thu c s khc nhau: + Khi n >1 sn phm l oleum + Khi n =1 sn phm l monohydrat (axt sunfuric 100%) + Kh n <1 sn phm l dung dch axit long Thng thng, ngi ta c xu hng sn xut ton b sn phm dng oleum bo qun, vn chuyn v s dng thun li hn. Mun vy, cho hn hp kh cha SO3 qua thp c ti oleum (thp oleum). Nh bit, oleum l dung dch axt sunfuric 100% c d SO3 nn p sut hi ring phn ca SO3 trn n kh ln. Do , hp th SO3 l phi a hn hp kh tip tc qua thp hp th th hai ti (monohydrat). n y mi kt thc qu trnh hp th SO3. - S cng on hp th:

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Hn hp kh SO3 5 6 4 S cng on hp th II. Cng ngh tng hp amnic NH3 1. Tnh cht v ng dng

1: Thp hp th olum 2: Thp hp th Mnhydrat 3: ng khi 4: B cha axit 5: Bm axit tun hon

- Amnic iu kin thng l cht kh khng mu, c mi khai xc. - Mang tnh kim - Amnic ho tan tt trong nc. - Bt u b phn hu nhit 300 0C , 600 700 0C phn hu mnh - NH3 c th phn ng vi mt lot cc cht nh : NH3 + H2O = NH4OH 4NH3 + 5O2 = 4NO + 6H2O NH3 + HNO3 = NH4NO3 NH3 + CO2 = (NH2)2CO + H2O NH3 + H3PO4 = NH4H2PO4 NH3 + H3PO4 = (NH2)2HPO4 NH3 + H2SO4 = (NH4)2SO4 Nh vy ta thy NH3 l nguyn liu u sn xut cc hp cht ca nit. 2. Sn xut kh nguyn liu tng hp Amnic
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2.1. Phn ly khng kh lng tch N2 v O2 u tin s tin hnh lm lnh ho lng khng kh sau tin hnh chng luyn tch N2 v O2. Trc khi ha lng khng kh th cn loi b cc kh C2H2, CO2, H2O v cc kh ny c nhit ng bng cao s ng rn lm hng, tc thit b. Phng php ny da vo s trnh lch nhit si khc nhau ca xy (-183,2
o

C) v nit (-198,5 oC). Do nhit si ca 2 cu t l kh gn nhau nn tch 2

cu t ny ngi ta phi s dng phng php chng luyn, trong thc t ngi ta s dng thp chng luyn kp.

S thp chng luyn kp

N2

1 T3 T2

O2 4

T1 3

Khng kh nn

1- Thp trn

2- Thp di

3- y thp di 4- Mng cha Nit lng

T1,T2, T3 : Cc van tit lu

Thp chng luyn trn lm vic p sut 1 1,5 atm v thp chng luyn di lm vic p sut 6 7 atm. Khng kh nn (120at) s i vo pha y thp di v chuyn nhit gin tip cho y thp di dun si y thp di sau kh c a qua van tit lu T1 h p xung cn 7 at ri vo pha gia thp di.

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Trong thp di cu t kh bay hi l oxy s i dn xung pha y thp (y thp l khng kh lng giu oxy 35-40%). Cu t kh bay hi l Nit s i dn ln nh thp, kh ny li chuyn nhit gin tip cho y thp trn un si thp trn v chnh bn thn li b mt nhit nn ho lng ri xung c ngng t mng cha 6. Khng kh lng giu oxy y thp di c a qua van tit lu T2 gim p xung cn p sut 1,5 at ri c a vo gn y thp trn. Nit lng mng cha 6 c a qua van tit lu T3 gim p xung cn 1,5 at v c a dn vo nh thp trn. Trong thp trn cu t d bay hi l N2 s i dn ln pha nh v cu t kh bay hi l O2 s i dn xung pha y. nh l N2 khong 99% v y thp trn nng Oxy khong 96%. 3) Phng php kh ho than (phng php nhit cao) Phng php ny dng cc tc nhn Oxi hoc hi nc phn ng vi than to ra thnh phn ca kh nguyn liu. - Ch dng tc nhn l khng kh th phng php thu c l kh ho than kh (sn phm ch yu CO, N2) - Ch dng tc nhn l hi nc th phng php thu c l kh ho than t (sn phm ch yu CO, H2) - Dng tc nhn l khng kh v hi nc th phng php l kh ho than m (sn phm ch yu CO, N2, H2) Trong ti liu ny ch cp n phng php kh ho than m. Yu cu ca than dng kh ho: o Than phi c bn c bn nhit o C tnh kt dnh thp o Hm lng x c nhit nng chy thp phi nh o C hot tnh cao S kh ho than

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Than

Kh l

H CO2 CO H2 H2O N2

1 2 3 4 5 O2

Hi nc

Khng kh

Nng kh, %

Din bin nng kh theo chiu cao l kh ho

L kh ho c chia lm 5 khu vc
- khu vc 1: khu vc sy, than c sy do tip xc vi kh nng i t di ln - Khu vc 2: Khu vc chng kh, vng ny cc cht hu c trong than b nhit phn thot ra khi than cn than b cc ho. Khu vc 3: khu vc kh chnh. y xy ra phn ng gia hi nc v than. Mt phn CO2 b kh trn than to thnh CO. C + H2O = CO + H2 C + 2H2O = CO2 + 2H2 C + CO2 = 2CO Khu vc 4: khu vc oxy ho. Vng ny phn ng gia than v oxy do cc phn ng to nhit nn nhit tng nhanh chng ti mc gn nhit ho mm ca x. C + 1/2O2 = CO C + O2 = CO2
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CO + 1/2O2 = CO2 Khu vc 5: khu vc x. Khu vc ny cht kh ho tip xc vi kh than nng nng nhit t 60oC ln khong 420oC ng thi x ngui v i ra ngoi. C + O2 = CO2 1) phn ng tng hp NH3 v cc yu t nh hng 1. Cn bng phn ng N2 + 3H2 = 2NH3 + Q - y l phn ng thun nghch, to nhit, gim th tch do nu nhit gim, p sut tng th cn bng chuyn dch v pha phI hiu sut tng hp tng. Hng s cn bng :
KP =
3 p N2 . pH 2

p NH 3

Trong thc t phn ng tin hnh p sut cao cch xa so vi iu kin l tng nn Kp khng ch ph thuc vo nhit m cn ph thuc vo p sut.
lg KP = 2077 ,8 + 2 , 4943 . lg T + .T 1,8564 . 10 7 .T 2 + I T

Trong : I l hng s tch phn

l h s hiu chnh i vi p sut.

I v ph thuc vo p sut theo bng sau. P atm 100 1,256.10-4 - 2,113 300 1,256.10-4 - 2,206 600 1,0856.10-3 - 3,059 1000 2,6833.10-3 - 4,473

* Cc yu t nh hng n cn bng phn ng: a. Nhit v p sut

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100 80 60 40 20 0 0

y*(%)

200 300 400 500 600

200

400

600

800

1000

P(atm)

nh hng ca nhit v p sut n cn bng phn ng

T th trn ta thy: - P = const th nhit cng thp nng NH3 cng cao - T = const th p sut cng cao nng NH3 cng cao * p sut p sut cng ln th hiu sut tng hp cng cao tuy nhin khng th tng p sut mt cch tu m n b gii hn bi iu kin an ton ca dy chuyn v thit b. Trong cng nghip ngi ta chia thnh 3 loi lu trnh : - Lu trnh thp p : P = 100 200 atm. Lu trnh ny t c s dng v hiu sut tng hp thp. - Lu trnh trung p : P = 280- 300 atm. Lu trnh ny c ng dng ph bin nht, tuy hiu sut t c cha cao nhng vic u t cho dy chuyn thit b ban u cn p ng c. - Lu trnh cao p : P = 450- 1000 atm. Ch c p dng cc nc c nn cng nghip pht trin. * Nhit Nhit cng thp th hiu sut tng hp cng cao tuy nhin phn ng ny phi s dng xc tc nn nhit s b gii hn bi nhit hot tnh ca xc tc. Vi xc tc s dng l oxit st t (Fe3O4) th nhit thch hp l 450- 500 oC.

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 p sut P = 300 atm v nhit 500 oC nng NH3 cn bng ch t 26,2%. Trong thc t ch t 15 - 18% b. nh hng ca t l N2/H2
50

40

30

20

10

0 0 1 2 3 4 5 6

nh hng ca t l H2/N2

Qua nghin cu cng mt iu kin nhit v cc p sut khc nhau nng NH3 ln nht khi t l N2/H2 = 1:3 t l ny cng ph hp vi t l tiu hao theo phn ng c. nh hng ca kh tr (CH4+Ar) Kh tr (CH4+Ar) lm gim p sut ring phn ca N2 v H2 lm cn bng phn ng chuyn dch theo chiu nghch v vy trong dy chuyn sau khi phn li NH3 ta phng khng mt lng kh ti im c nng kh tr ln nht m bo nng kh tr t 8-12%. d. nh hng ca NH3 tun hon Khi phn ly khng th phn ly trit NH3 do vy trong hn hp kh tun hon lun c mt lng NH3 lm cn bng phn ng chuyn dch theo chiu nghch gim hiu sut tng hp. Do vy khi phn ly ta phi gim nhit sao cho lng NH3 tun hon < 0,5% 2. S sn xut NH3

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6 9 1 2 3 H2 O 4 7 5 Kh m i 8 8 NH3h

V kho h Hnh Dy chuyn tng hp NH3

Sn xut HNO3
1)Tnh cht v ng dng Tnh cht Tkt = - 42 C0, ts = 83 C0 HNO3 khan khng bn iu kin thng L mt axit rt mnh, oxy ho hu ht cc hp cht hu c v kim loi Hn hp HCl & HNO3 (3:1) l nc cng toan
C 2HNO3 200 2NO2 +
0

1 O2 + H2O 2

ng dng 75% dng sn xut mui Nitrat lm phn khong 15% sn xut lm thuc n Dng sn xut cht mu v lm xc tc

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2) Mt s phng php sn xut H2SO4 + 2NaNO3 = Na2SO4 + 2HNO3

V .0 , 75 A N2 + O2 8000 2NO O Nm 1800 NH3 + O2 Fe NO + H2O
2 3

Nm 1839 s dng xc tc Pt 3) Qu trnh sn xut HNO3 long a) Oxy ho NH3 2NH3 +

5 xt O2 2NO + 3H2O + Q (1) 2

xt N2O + 3H2O + Q (2) 2NH3 + 2O2

2NH3 +

3 xt O2 N2 + 3H2O + Q (3) 2

Vng khng c xc tc 2NO N2 + O2 - Q (4) 3NO +2NH3

5 N2 + 3H2O (5) 2

900 C0 c K1 = 1051, K2 = 1061, K3 = 1067 Cc hng s cn bng rt ln chng t cc phn ng 1,2,3 l cc phn ng mt chiu, - Mun to ra sn phm mong mun chng ta phi s dng tnh chn lc ca xc tc. Trong sn xut s dng xc tc Pt hoc hp kim ca Pt to ra NO - Khi nhit tng kho st cho thy tc phn ng v hiu sut chuyn ho tng ln. Tuy nhin nhit cao s gy n mn thit b v tng tn tht Pt. - Hn ch phn ng ph bng cch hn ch vng khng c xc tc, thng t cc lp xc tc st vi nhau hn ch khong trng - T l O2/NH3 cng thp th hiu xut to NO cng nh nn thng phi tng t l ny bng cch dng d O2 khong 30% l thch hp tc O2/NH3 ~ 1,72,0

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b) Oxy ho NO 2NO2 + O2 = 2NO2 + Q (1) NO + NO2 = N2O3 + Q (2) 2NO2 = N2O4 +Q (3)

Sn xut phi thc y phn ng 1 to nhiu NO2, hp th NO2 s to ra HNO3 - tng hiu xut chuyn ho phn ng 1 th cn gim nhit v tng p sut. nhit nh hn 200 C0 th phn ng 1 xy ra hon ton, trn 700 C0 phn ng 1 khng xy ra. Nhit cng thp th tc phn ng cng nhanh. Hp th NO2 bng H2O to HNO3 long. Hn hp kh sau khi oxy ho bao gm NO, NO2, N2O3, N2O4(NO khng phn ng vi nc). 2NO2 + H2O = HNO3 + HNO2 + Q N2O4 + H2O = HNO3 + HNO2 + Q N2O3 + H2O = 2HNO2 + Q HNO2 phn hu nhanh chng theo phn ng: 3HNO2 = HNO3 + 2NO + H2O - Q NO +
1 O2 = NO2 + Q 2

tng tc hp th th cn phi tng tc phn hu HNO2 vi cc bin php: - khuy trn - Dng dung dch axit long hp th. - Tng nhit (t<40 C0), nhit cao hn th Oxy ho tan t, tc oxy ho NO li gim xung. - Thc hin hp th p sut cao 15-20 at tng hiu sut hp th, tb cng gn hn - Tng nng NO2 th hiu sut hp th cng tng ln.

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S tng hp HNO3

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Chng 3 CNG NGH PHN KHONG IN HA I- Sn xut supe ln n 1.Tnh cht: L phn bn mang tnh axit, c mu xm. khi lng ring 1,5g/cm3 Cung cp cht dinh dng l P Thnh phn ch yu bao gm Ca(H2PO4)2.H2O v CaSO4, ngoi ra cn c nhiu cht khc nh FePO4, AlSO4, SiO2 . Hm lng dinh dng ca phn bn 16-18%.

2.Nguyn liu sn xut - axit H2SO4 - qung pht pht(qung Apatit Ca5F(PO4)3 v Canxi Pht pht Ca3(PO4)2) 3. S khi sn xut
Qung Apatit Axit H2SO4 (98%) Pha long (65%)

Sy nghin (0,16mm)

Lm mt (60 0C)

Trn u

Trung ha Axit du (Vi, NH3...)

Supe thnh phm

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4.C s ho l Khi cho qung tip xc vi axit th xy ra phn ng tng qut sau: 2Ca5F(PO4)3 + 7H2SO4 + 3H2O = 3Ca(H2PO4)2.H2O + 7CaSO4 + 2HF Thc t phn ng phn hu qung xy ra theo hai giai on G1: Ca5F(PO4)3 + 5H2SO4 = 3H3(PO4) + 5CaSO4 + HF G2: Ca5F(PO4)3 + 7H3SO4 + 5H2O = 5Ca(H2PO4)2.H2O + 2HF Giai on 1 xy ra trong khong thi gian 20-40 pht giai on ny kt thc khi aixt H2SO4 phn ng ht. Giai on 2 xy ra trong khong thi gian 6-20 ngy. Giai on ny chm do qung b phn hu bi axt yu hn, cc cht tham gia phn ng kt khi nn khng linh ng, Mng tinh th CaSO4 v Ca(H2PO4)2.H2O bao bc ht qung khng cho Axit tip xc vi qung. 5.Cc yu t nh hng a)Lng axit s dng: Khi tng s dng lng axit trn mt n v khi lng qung th cho thy tc phn hu qung tng v mc phn hu qung tng. Trong sn xut ch dng d t 6-10% axit v: - d nhiu axit lm lng ph nguyn liu - Khi d axit th phi trung ho nn li em tp cht vo sn phm b)nh hng ca nhit t C0 65-75 60-70 55-65 50-60

CH2SO4 % 61- 65 66 67 68

C ng vi mi mt nng axit th c mt nhit thch hp. Nhit ny s to ra tinh th ln lm cho lp mng tinh th s c khe h ln.
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c)nh hng ca nng axit H2SO4 Trn th cho thy mc phn hu qung t gi tr ln nht ti nng khong 30 v 66%(v tr cc cc i ny ph thuc vo loi qung). Mc phn hu nng 30% th cao hn. Trong sn xut trn nng 66% vi mc ch to ra sn phm kh ti xp. d)nh hng ca kch thc ht qung Kch thc nh s tng c din tch tip xc, lp mng tinh th bao bc nh nn axit d thm qua phn hu qung. Nhng nghin qung kch thc qu nh li lm tng chi ph nghin, v tn tht qung. e) nh hng ca khuy trn v thi gian o trn Khuy trn tng c qu trnh khuych tn, trnh hin tng qu bo ho lm kt tinh cc b trn ht qung. Nn lm tng mc v tc phn hu qung. Thi gian o trn cng nhiu th qu trnh khuy trn tt. Tuy nhin thi gian lu s khng c li bi khi phn ng kt khi s lm gy cnh khuy, bn phn ng kh vn chuyn sang cng on khc. Thc t i vi qung Apatit Lo cai thi gian lu t 2-4 pht l thch hp.

1) S cng ngh

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s dy chuyn sn xut supe pht pht n

13 9 10 14 11 12 15 16 17 18 19 20

47 46 45 44 43 42 41 40 39 38 37 36 35 34 33 32

Kho suppe tui My nh tung Bng ti suppe tui Vt ti tr su L sy thuc tr su Thng ho mui Thng cha nc mui Qut ht

Bng ti thuc tr su
My ly tm Thng cha NaCl Thng phn ng

Thng cha H2SiF6

Qut ht kh Flo Bm H2SiF6 Thng cao v cha H2SiF6

12

31 30 29 28

ng phng khng Thp hp th

B hp th Thng cha axit Phng ho thnh Gim tc karusel Thng trn Thng cao v cha nc Thng cao v cha axit Bunke cha bt Appatit Bng ti bt Apatit Lc bi t Xyclon nhm 6 Xyclon n Thit b phn ly c hc My cung cp liu Bunke cha qung sau sy Thit b tch git

1 2

34

21

27 26 25 24 23 22 21 20 19

21 22
Nc lm mt

23 24

26 27 28 2930

31

32 33

36

37

18 17 16 15 14

45
Xung trung ho t 1

25 34 35 4344

38 39

46 47

40 41 42

13 12 11 10 9 8 7 6 5 4 3 2 1 T.T

Lc bi u't
Bng ti qung sau sy Xyclon nhm 4 My sy thng quay

Bun ke cha qung

Qut ht sau nghin My nghin bi Qut ht sau sy My p ba ng c chuyn ng Hp gim tc Qut cp gi Bung t Tn gi

Sn xut phn ln nung chy 1.Gii thiu C hnh dng b ngoi ging thu tinh, khng tan trong nc nhng tan trong dch axit xitric(do r cy tit ra). L phn bn mang tnh kim v chm tan.

2. Nguyn liu sn xut. - Qung apatit loi II (P2O5 22-28%) - Cht tr dung cung cp MgO: lmt([Ca,Mg]CO3), Manhzit MgCO3 , Secpentin 3MgO.2SiO2.2H2O - Cht tr dung cung cp SiO2: Sa thch (SiO2 > 96%) - Ht qung c gia cng ti kch thc d = 11-90 mm

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3) S sn xut
Qung Apatit Loi II p nghin Sn(10-15mm) x vn Sa thch Than

p nghin Sn(10-15mm)

p nghin Sn(10-15mm)

p nghin Sn(10-15mm)

Trn u

L cao (1450 0C)

Lm lnh nhanh (bng nuc)

Vt bn sn phm ro

Sy nghin thnh sn phm

4) Nguyn l sn xut Qung pht pht c trn vi cht tr dung theo mt t l nht nh sau c a vo l nung nhit cao (1450 C0) ho lng hon ton phi liu. Sau lm lnh t ngt phi liu nng chy bng dng nc p lc cao t 3-4 at. Phi liu s ng rn v v vn thnh cc ht nh ging nh thu tinh.

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Lm lnh t ngt gi cho Ca3(PO4)2 dng v nh hnh (cy trng hp th c) Tc lm lnh cng nhanh th chuyn ho thnh dng v nh hnh cng ln. lm lnh nhanh cn s dng nhiu nc lm lnh hoc nung chy qu nhit phi liu ng knh git phi liu nh. Vt liu ht sau lm lnh nhanh c phn ly tch khi nc ri tin hnh sy nghin s to ra sn phm. Nhit sy cng khng nn vt qu 750 C trnh b chuyn cu trc mng Mt s phn ng xy ra khi nung: 2Ca5F(PO4)3 + SiO2 + H2O 3Ca3(PO4)2 + CaSiO3 + 2HF 4Ca5F(PO4)3 + 3SiO2 6Ca3(PO4)2 + 2CaSiO3 2Ca3(PO4)2 + 6SiO2 + 10C 6CaSiO3 + 10CO + P4 5)Vai tr ca cc thnh phn chnh trong phi liu: - P2O5 : y chnh l thnh phn cung cp dinh dng cho cy, hm lng trong sn phm cng cao th cht lng phn bn cng tt. Nhng hm lng ny trong phi liu m ln hn 25% th s lm tng nhit nng chy v tng tc kt tinh. - CaO: hm lng cng nhiu th cng lm tng nhit nng chy ca phi liu, SiO2 c th lm gim c tc hi ny - SiO2 : Khi nng chy s tan ln vo trong mng tinh th Apatit lm suy yu lc lin kt to nn mng. SiO2 c tc dng h thp nhit chuyn mng, nhit nng chy, gim tc kt tinh. Khi nhiu SiO2 s lm tng nhit nng chy ca phi liu v lm tn tht P2O5. - MgO : lm gim nhit nng chy ca phi liu, lm gim nht, tc kt tinh. Tuy nhin nhiu MgO s lm tng nhit nng chy ca phi liu - F,Al2O3 , Fe2O3 : Flo lm tng tc kt tinh MgO,SiO2 li gim tc hi ca Flo Oxyt st v nhm hm lng vt qu 5% s lm tng nhit nng chy ca phi liu. Khng c hai oxyt ny th li gim hiu xut chuyn ho.

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n MgO n P2O5

= 2-3 ;

n MgO nCaO

= 0.5-1 ;

n MgO + nCaO n SiO2

= 1,8 -2,7

III- Tng hp Ur

1)Gii thiu C cu trc tinh th, khng mu, khng mi Nhit nng chy 132 C0 tan nhiu trong nc , ru, NH3. Khi nung nhit cao th b phn hu. c ng dng sn xut dc phm, si nhn to, nha keo nhn to, ty sch du m, v bo gia sc, lm phn bn. 2)S khi sn xut.

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Than, kh t

Kh ha than

N2,CO2,H2

Hp th CO2

Dung dich hp th CO2

Kh N2, H2

Nh hp th, thot kh CO2

Tng hp to NH3

Thc hin tng hp 200 oC, 200 at

Chung c c Ure

Kh N2,H2, CO2 tun hon sn xut

To ht

3)C s ho l sn xut Cho CO2 v NH3 phn ng vi nhau p sut 200at v nhit 200 C0 NH3 + CO2 NH2COONH4 + 68 kcal NH2COONH4 CO(NH2)2 + H2O - 6,8 kcal Phn ng tng qut ca qu trnh NH3 + CO2 CO(NH2)2 + H2O + Q

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Qu trnh tng hp s to ra hai pha Pha kh gm CO2, H2O, NH3 Pha lng gm CO(NH2)2, NH2COONH4, NH3, H2O Ur ch to ra trong pha lng do NH2COONH4 rn phn gii rt chm, cn trng thi lng n phn gii nhanh chng to Ur. Qu trnh tng hp ur c hiu xut khong 60%. nng cao hiu xut tng hp th cn thc hin phn ng nhit cao qu 200 C0 hn ch phn ng ph, ng thi cn tun hon li nguyn liu cha phn ng. 4) Cc yu t nh hng a) nh hng ca p sut Kho st cho thy hiu sut cng cao th hiu xut chuyn ho v tc phn ng cng cao. Tc to thnh NH2COONH4 t l bnh phng so vi p sut. p sut cao hn ch c cc phn ng ph. Nhc im nu p sut cng cao th chi ph vn hnh s tng vt. b) nh hng ca nhit nng chy NH2COONH4 Ur ch to ra khi NH2COONH4 trng thi chy lng. NH2COONH4 tinh khit c nhit nng chy 152 C0 , phn ng c nhiu cht mi s lm gim c nhit nng chy ca NH2COONH4 (v to ra cc im etecty) hn hp 50% Ur v 50% NH2COONH4 c nhit nng chy 98 C0. c)nh hng ca H2O Nc ban u c tc dng thc y tng tc phn ng do lm xut hin pha lng. Nhng khi nhiu nc li lm gim hiu xut chun ho do phn ng tng hp thun nghch v to ra nc. d) nh hng ca CO2 d CO2 d khng nh hng ti phn ng tng hp do phn ng tng hp trong pha lng cn CO2 d pha kh. CO2 d lm tng chi ph thu hi nguyn liu, tng p sut ca thit b. Sn xut khng dng d CO2. e) nh hng ca NH3 d

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C tc dng lm gim tc n mn thit b, hn ch cc phn ng ph, tng hiu xut chuyn ho, lin kt vi nc lm gim tc hi ca nc i vi phn ng tng hp. Khi d nhiu NH3 s lm tng chi ph thu hi do vy thc t dng t l NH3/CO2 = 4 . CO(NH2)2 NH2CONHCONH2 + NH3 f) nh hng ca nhit v thi gian un nng Khi tng nhit th tc phn ng v hiu xut phn ng u tng. Nhng th cho thy l nhit ln hn 180 C0 nu un nng lu s lm gim hiu xut chuyn ho do xy ra cc phn ng ph. Nh my m h bc thc hin phn ng 200 C0 vi thi gian un nng l 30 ph. IV) in phn dung dch sn xut NaOH, Cl2, H2 1)iu kin thc hin qu trnh in phn in phn mt cht no th phi t vo bn ngoi mt in th ln hn in th phn hu ca cht . Ep > Eh = ( Ea - Ek ) + (a + k ) + IR Trong : ( Ea - Ek ) in th phn cc (a + k ) qu th IR in th ri 2)Thit b in phn s dng catt rn 3)Yu cu dung dch NaCl NaOH Na2CO3 T 310 g/l 0,2-0,3 g/l 0,2 0,5 g/l 60- 70C0

Dung dch trong sut, trung tnh 4) Qu trnh in phn trn Catt rn (Fe) Dung dch mui c qu trnh phn ly nh sau: NaCL Na+ + Cl-

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H2O H+ + OHDi tc dng ca dng in mt chiu bn ngoi t vo cc ion m s di chuyn v cc dng, cc ion dng di chuyn v cc m. Trn Catt (Cc m) S tp trung Ion H+ ,Na+ 0 Na+/Na = -2,7 (V) 0 H+/H2 = 0 (V) Trong dung dch mui trung tnh gi tr th Oxy ho kh ca Na+/Na ~ -2,66 (V) H+/H2 ~ - 0,41 (V) S liu trn cho thy th oxy ho kh ca Natri rt b so vi hydro, ng thi qu th ca n trn in cc rn cng rt ln. Do vy in th phn hu ca Natri rt ln nn natri khng tham gia phn ng in cc. Ch c ion H+ v H2O tham gia H+ + e H H2O + e H + OH2H H2 Trn Ant (Cc dng): Tp trung ion CL-, OH0 Cl2/2Cl- = 1,36 (V) 0 O2/4OH- = 0,41 (V) Trong dung dch mui bo ho th oxy ho kh ca Clo v Oxy c gi tr xp x Cl2/2Cl- ~ 1,32 (V) O2/4OH- ~ 0,82 (V) Gi tr in th ca chng xp x nhau do vy khi in phn c Clo v Oxy c th thot ra ng thi. khng ch cho Clo thot ra trc chng ta cn tng in th phn hu ca Oxy bng cch tng qu th thot oxy. Cch tng qu th s dng cc in cc c bit nh Pt, Ti , Ti-Pt. ng thi dng dung dch mui c nng cao gim th oxy ho kh ca Clo, nhit dung dch cao cho Clo thot ra d rng(gim c qu th ca Clo)
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Phn ng ti Ant 2Cl- - 2e Cl2 Tm li qu trnh in phn xy ra nh sau: 2NaCl + 2H2O

dpdd 2NaOH + H2 + Cl2

5) qu trnh in phn s dng Catt lng (Hg) Qu trnh Ant cng tng t nh trn Trn Catt lng do Na to Hn hng vi Hg nn in th phng in ca Na dch v pha dng hn v dng hn c so vi Hyr. Ni cch khc in th phn hu ca Na b hn so vi Hyr do vy khi in phn Na thot ra trc. Na + nHg NaHgn NaHgn + H2O NaOH + 0.5H2 + nHg . V- Sn xut Pin kh Mn-Zn

a)Cu to

2 3 4
1. Cc than 2. Bao than 3. Giy 4. V Km

Cu to Pin

V lm bng Zn ng vai tr lm cc m(Ant). Cc dng (Katt) : ch to t bt MnO2, bt Graphit, mui than, NH4Cl, ZnCL2, H2O c trn u sau nhi p thnh khi theo v, khi ny gi l bao than v gia bao than c cc than dn in gia.
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Gia cc dng v cc m l in dch NH4Cl, in dch ny c tm vo giy, thm h tinh bt chuyn dch sang dng kh hn. b)C ch phng in - Trn cc dng: Khi phng in Ion H+ t in dch chui qua lp in tch kp v chuyn vo MnO2, H+ b trung ho bi in t t do ng thi Mn b kh xung s Oxy ha thp. MnO2 + e + H+ MnOOH

Khi phng in s giu MnOOH th Mn c th tn ti theo cc dng sau MnOOH + e + H+ Mn(OH)2 MnOOH + e + 3H+ Mn2+ + 2H2O

- Trn cc m: Zn phng in Zn - 2e Zn2+ Zn + 2H2O - 2e Zn(OH)2 + 2H+ Zn + H2O - 2e ZnO + 2H+ c)Tnh nng ca pin - sc in ng: c gi tr t 1,5-1,9 V , sdd ny ph thuc vo nng in dch v bn cht MnO2. - Dung lng ca Pin ph thuc vo kch thc ca Pin, nhit mi trng v thi gian bo qun. pin cng ln dung lng cng ln. Nhit thp dung lng cao do in tr pin ln, nhit cao dung lng ca pin thp do t phng in. P t phng Zn + O2 + H2O Zn(OH)2 MnO2 + H2O MnOOH + O2. VI.Sn xut c quy 1)Gii thiu (mi trng trung tnh v kim)

(Mi trng axit yu)

2)Cu to: (+)PbO2/H2SO4/Pb(-)

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S xp xp l cc

Cc dng: gm sn cc v bt cc. Sn cc c vai tr gi bt cc, bt c ch to t bt Pb, PbO2, H2SO4, H2O, si ha hc Cc m: gm c sn cc,bt cc. Bt c ch to t bt Pb, PbO2, H2SO4, H2O, si ha hc, BaSO4, NH4SO4, ph gia

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L cch: c vai tr ko cho chp cc dng v cc m, gi cho bt cc ko b ri. c th c lm t si thy tinh, giy, nha Polyme xp ( cho cht phng in i qua) in dch: dng axit H2SO4 c nng 30% (d~1,22) v nng ny dung dch c in tr thp.

3) C ch phng np Khi np in th trn cc m s kh PbSO4 thnh Pb, cc dng oxy ha PbSO4 thnh PbO2 (-) PbSO4 2e = Pb + SO22 (+) PbSO4 + 2H2O +2e = PbO2 + H2SO4 + 2H+ Khi phng in th xy ra qu trnh ngc li vi qu trnh np Cc m xy ra qu trnh oxy ha Pb thnh PbSO4, cc dng kh PbO2 thnh PbSO4 (-) Pb + SO22 -2e = PbSO4 (+)PbO2 + H2SO4 + 2H+ +2e = PbSO4 Phn ng phng np in tng qut:
n, p 2PbSO4 + 2H2O Pb + PbO2 + H2SO4

Khi c quy s dng thi gian di th PbSO4 thay i cu trc nn ko tham gia phn ng phng in. Khi phng in s lm nng H2SO4 gim , khi np th nng axit ny li tng. qu trnh s dng s bay hi nc(i vi c quy h) nn chng ta phi b xung thm nc ct nh k. 3) Tnh nng ca c quy - Sc in ng ca c quy:

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E = a - k +

RT ln aH2SO4 . sc in ng ph thuc vo nhit mi trng , F

hot ca axit v bn cht Pb, PbO2 - in th ca c quy Vn = E + Epc/n + Inrn Vp= E - Epc/p + Iprp Trong Vn, Vp l in th khi np v khi phng Epc/n, Epc/p l sc in ng phn cc khi np v khi phng Inrn, Iprp l in th ri ~ 0 (v) - in tr trong ca c quy rn, rp nh khng ng k - Dung lng ca c quy ph thuc vo cu to l cc, nng axit, nhit . L cc cng dy xp th dung lng cng tng, dung lng ln nht khi nng axit khong 30%. Nhit cao c quy s t phng in, thp th in tr ln.

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Chng IV CNG NGH CC CHT HU C

I-Du m v ch bin du m 1. Khi nim: l hn hp phc tp ca cc cht hu c c mu t nu n en, c nht ln. Thnh phn chnh l cc hydrocacbon, ngoi ra cn cha nhiu hp cht hu c khc, mui khong v oxyt 2. Chun b ch bin du m gia cng a)Tch kh v n nh du Du m thng su trong lng t hoc y bin do nn p sut rt cao nn ha tan nhiu kh. Chng ta phi tch cc kh ny trc khi ch bin chng nu khng cc kh ny s gy p sut cao trong cc ng ng dn v thit bi, lm ri lon ch lm vic, bay ra ngoi gy lng ph, lm chy n. Do vy chng ta cn tch kh ra khi du. Tch kh bng cch l gim p sut hoc gia nhit nh (100- 130 0C) Sau khi tch kh cn mt lng xng nh, ta tip tc tch xng nh bng cch chng luyn nhit thp. b) Lm sch du Trong du m thng cha nhiu nc v mui v cc oxyt vv.. Cc tp cht ny gy n mn thit b, lm gim nhit tr ca du, lm qu trnh chy khng u. Tch cc tp cht c hc bng cch lng lc nhiu ln Tch mui bng cch ha tan mui bng nc nng ri lng trong thit b in Tch nc dng nh tng ra khi du bng cch un nng 40-50 0C ri lng trong 24h, Dng phng php in trng, thm vo cht chng nh tng 3) Cc phng php gia cng ch bin du m a) Phng php ch bin gi nguyn cu to

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da vo tch cht khc nhau ca cc thnh phn trong du m nh ha tan, nhit si tch cc thnh phn ra khi nhau.. cch thng dng nht l phng php chng ct. Phng php ny n gin , nhanh nhng nhc im l ch ly c nhng sn phm c sn trong du m nn hiu xut s dung nguyn liu khng cao. S chng ct du m:

b) Phng php ch bin thay i cu to Dng nhit v xc tc b gy mch , ni mch , thay i cu trc mch to ra sn phm cc phng php s dng: - Carackinh nhit : dung nhit b gy mch cc phn t to ra sn phm mi. Nguyn liu s dng l cc hydrocacbon mch di (mazut, gazoin ..) sn phm cui l kh v xng.
t CnH2n + CmH2m+2 CxHy

Trong phng php ny th nhit nh hng nhiu n tc phn ng, p sut t nh hng n tc nhng li nh hng nhiu ti v tr ct mch. p

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sut cng cao th v tr ct mch s cng vo gia nhng li t to ra sn phm xng. p sut tin hnh thng 40-50 at - Crackinh xc tc: tin hnh ct mch di tc dng ca xc tc. nh hng c v tr ct mch nn cho hiu xut , cht lng sn phm cao hn. Phng php ny hin l phng php gia cng c bn du m. Tc phng php ny ln hn nhiu so vi phng php nhit. Thng thc hin p sut thng. Nhng xc tc d b mui than che lp. II- Sn xut cc hp cht hu c c bn. 1. Sn xut C2H2 1.1 Tnh cht: l cht kh khng mu, mi t nh, khi chy ta nhit mnh ng dng: dng d hn ct kim loi, sn xut ru etylic, axit axetic, butadien, nha tng hp, cao su. 1.2 sn xut t canxi cacbua (CaC2)
C CaC2 + CO CaO + 3C 2000

CaC2 + 2H2O = C2H2 + Ca(OH)2 Phng php ny n gin . Thit b cng knh, tiu hao nhiu nhit nng, b thi nhiu S 1.3 Sn xut C2H2 t Ankan Phng php ny mang tnh kinh t hn. thc hin bng cch nung ankan v ng ng ca n trong iu kin thiu oxy nhit ~ 1500 C
C2H2 + 3H2 381kj 2CH4

C2H6 C2H2 + 2H2 330 kj iu kin tin hnh l tng nhit v gim p sut Quan h gia nhit v p sut
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T(0C) % C2H2

500 0

1000 1,53

1200 11,8

1400 46,2

1800 96,5

2200 99,68

Kt qu s liu thy rng nhit cng cao th hiu xut to C2H2 cng ln. Nhng nhit 1400 1500 0C th C2H2 li khng bn, d phn hy
2C + H2 C2 H 2 2CO + 3H2 C2H2 + 2H2O 4CO + H2 C2H2 + 2CO2

nng cao hiu xut th thc hin phn ng nhit cao (t>1400 0C) nhng thi gian rt ngn 1/1000 giy sau lm lnh khng cho C2H2 b phn hy

2. Sn xut ru Metylic t CO v H2 2.1 gii thiu L cht lng khng mu, c nhit si 680C, rt c, tan v hn trong nc. ng dng dng lm dung mi, sn xut foocmanhit, metyl axetat, metyl amin, este 2.2 Sn xut Cho CO phn ng vi H2 nhit , p sut cao v c mt ca xc tc CO + 2H2 CH3OH + Q t0 : 350 400 C p : 200 300 at xt: Cr2O3 + ZnO H2/CO : 48 Cc phn ng ph CO + H2 HCHO CH3OH + CH3OH CH3OCH3 + H2O

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CH3OH + H2 CH4 + H2O CO + 3H2 CH4 + H2O 2CO + 2H2 CH4 + CO2 tng hiu xut phn ng cn gim nhit v tng p sut 3. Sn xut ru etylic C2H5OH 3.1 ng dng To ra butadien sn xut cao su Sn xut thuc tr su Ch to etylaxetat, este, dc phm, hng liu, dung mi 3.2 Phng php sn xut Qu trnh c 4 cng on - hp th etylen bng axit Sunfurich - thy phn este to ru - chng ct tch axit - c c axit v tun hon li sn xut. a) Hp th etylen C2H4 + H2SO4 C2H5OSO3H C2H5OSO3H + C2H4 Cc yu t nh hng - thi gian hp th tng th hiu xut hp th tng - nng axit tng hiu xut hp th tng - p sut C2H4 tng th hiu xut hp th tng b) Thy phn este to ru (C2H5O)2SO2 (C2H5O)2SO2 + C2H4 2 C2H5OSO3H

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C2H5OSO3H + H2O C2H5OH + H2SO4 (C2H5O)2SO2 + 2H2O 2 C2H5OH + H2SO4 Phn ng ph khi thy phn (C2H5O)2SO2 + H2O C2H5OC2H5 + H2SO4 C2H5OSO3H + C2H5OH C2H5OC2H5 + H2SO4 hn ch phn ng ph cn phi tch ngay ru IV. Sn xut cc hp cht hu c trung gian 1. Khi nim: hp cht hu c trung gian l hp cht dng iu ch ra cc hp cht hu c khc 2.Phng php sn xut bng cch th vo nhn thm 2.1 Qu trnh Sunfor ha a) Khi nim: l qu trnh th mt hay nhiu nguyn t Hir nhn thm bng nhm Sunfor (SO3H) b) Tc nhn: thng dng l axit H2SO4 hoc Oleum Ar-H + H2SO4 ArSO3H + H2O + Q Phn ng iu ch thun nghch v to ra nc do vy tng hiu xut phn ng cn tng nng axit (thng s dng oleum). c) Cc yu t nh hng - nh hng ca nng tc nhn: Nng tc nhn lm thay i tc phn ng, v d kh Sunfor ha naptalen nu nng axit tng 9% th tc phn ng tng 39 ln.

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SO3H

H2SO4
SO3H

- nh hng ca nhit : lm thay i tc phn ng v v tr nhm th

OH 20 oC OH SO3H OH 100 oC

H2SO4

SO3H

- nh hng ca xc tc: lm thay i tc phn ng v v tr nhm th.

O H2SO4 O
Xt

SO3H

O O
SO3H khong Xt

2.2 Qu trnh Nitro ha a) N: l qu trnh thay th mt hay nhiu nguyn t hir nhn thm bng nguyn t nhm Nitro b) Tc nhn: thng dng l axit HNO3 nng t 6595 % Ar-H + HNO3 ArNO2 + H2O + Q c im phn ng l ta nhiu nhit v mt chiu. c) Cc yu t nh hng

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- nh hng ca nhit : lm thay i tc phn ng v v tr nhm th. Phn ng thng ta nhiu nhit nn thng khng ch nhit 40 60 C trnh to sn phm ph - nh hng ca xc tc: lm thay i tc phn ng v v tr nhm th, thng s dng Thy ngn v mui ca thy ngn lm xc tc. - nh hng ca nhm th c sn trong nhn thm: khi trong nhn thm c nhm ht in t th s lm gim kh nng th, ngc li khi c nhm y in t th lm tng kh nng th. Sp xp theo th t tng dn ca cc nhm lm tng kh nng th: NO2- < SO3H- < COOH- < Cl- < CH3- < CH3O- < C2H5O- < OH

2.3 Qu trnh Halozen ha a) n: l qu trnh thay th mt hay nhiu nguyn t Hir nhn thm bng nguyn t nhm Halozen b) Tc nhn: thng s dng Clo v hp cht ca Clo (Cl2, NaCLO, HCl) Ar-H + Cl2 ArCl + HCl c)Cc yu t nh hng: - nhit : lm thay i tc phn ng v v tr nhm th - Xc tc: lm thay i tc phn ng v v tr nhm th, thng s dng St v Mui St lm xc tc. 2.4 Sn xut Phenol a) Phng php sn xut i t dn xut Sunfor

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V. Sn xut cc hp cht cao phn t 5.1 n: Hp cht cao phn t l nhng hp cht c cha nhiu nguyn t cho nn c khi lng v kch thc rt ln 5.2 Qu trnh ch to 5.2.1 qu trnh trng hp a) nh ngha : l qu trnh cng hp nhiu n phn t ging nhau to ra polyme n(CH2=CH2) (-CH2-CH2-)n b) c im mnme : trong phn t phi c t nht mt lin kt i c) Din bin qu trnh trng hp u tin cc mnme do b kch ng (nh sng, nhit , xc tc, p sut) nn chuyn sang trng thi hot ng sau chng dn kt hp vi nhau to polyme vi c ch c th minh ha nh sau:
Xt A A

A + A A2 A2+ A A3 A3+ A A4 Al+ Am An (polyme)

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d) Cc phng php trng hp - Trng hp khi: cc mnme dng tinh khit v thm mt s xc tc tin hnh trng hp. Phng php ny to ra sn phm tinh khit tuy nhin th nht khi phn ng cao nn kh thot bt kh cng nh khng ch nhit phn ng. - Trng hp trong dung dch: tin hnh ha tan cc mnme vo trong dung dch , tin hnh kch ng ri trng hp, phng php ny d khng ch nhit khi phn ng, sn phm cha t bt kh nhng li d ln dung mi ha tan. - Trng hp dng nh tng: Tin hnh ha tan mnme dng nh tng sau kch ng ri trng hp. u im c tc phn ng cao, phn t to ra ln ng u. Nhc im l sn phm d ln cc tp cht. 5.2.2 Qu trnh trng ngng a) n: l qu trnh cng hp nhiu n phn t to ra polyme nhng c gii phng ra nhiu phn t nh nh ROH, H2O, NH3 nNH2-CH2-NH2 2nH2O b) c im ca monome: Trong polyme thng t nht c hai nhm chc. Cc nhm chc ny c th ging hoc khc nhau. Vd: HOOC-CH2-COOH, NH2-CH2-COOH c) c im Polyme: Polyme c nhiu tnh cht khc bit so vi monome do trong polyme c nhiu lin kt mi xut hin. cu trc polyme cng a dng mch thng, mch vng, khng gian. d) Phng php trng ngng - trng ngng khi nng chy: nu chy monome ri trng ngng. C u im l sn phm t tp cht nhng ch thch hp cho monome bn nhit.
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nHOOC-CH2-COOH

(NH-CH2-NHCO-CH2-CO-)n +

- trng ngng trong dung dch: ha tan monome trong dung dch trng ngng, phng php ny thng thc hin nhit thp v sn phm thng ln cc tp cht(dung mi). 5.3 Sn xut mt s hp cht cao phm t a) Nha PVC cho C2H2 tc dng vi HCl s dng xc tc l mui thy ngn (HgCl2) C2H2 + HCl C2H3Cl Sau ha lng vinylclorua ri trng hp
t ,P (-CH2- CHCl- )n n(C2H3Cl)

Phng php c hiu xut cao nhng s dng xc tc l thy ngn nn c.

b) Sn xut si visco Nghin bt g vi dung dch NaOH khng ch nhit 20 C 50 C trong khong thi gian 10 60 pht: [C6H7O2(OH)3]n + nNaOH [C6H7O2(OH)3.nNaOH]n Lm lnh dung dch phn ng xung 20 22C ri cho Sunfua cac bon [C6H7O2(OH)3.nNaOH]n + nCS 2 [C6H9O4-O-CS2-Na]n + nH2O

Dung dch iu ch c a i phun qua dung dich axit H2SO4 long to si [C6H9O4-O-CS2-Na]n + nH2SO4 (C6H10O5)n + nCS2 + nNaSO4

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c) Sn xut si axetat [C6H7O2(OH)3]n + 3n(CH3CO)2O [C6H7O2(OOCCH3)3]n + 3nCH3COOH em ha tan cht phn ng vo dung dch 85% axeton v 15% ru metylic sau bay hi to si.

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Chng V : CNG NGH HA SILICAT A-Sn xut cht kt dnh I-gii thiu chung 1) Vai tr 2) Phn loi: chia lm hai loi - cht kt dnh thy lc: ng rn v gi bn trong nc - cht kt dnh khng kh: ng rn v gi bn trong khng kh II- Sn xut cht kt dnh khng kh 1) Nguyn liu: vi (CaCO3) Phn ng khi nung
C CaCO3 950 CaO + CO2
0

Nung nhit 950 C th s cho vi hot tnh d ti nhit 1200 1400 C th li cho vi gi chm phn ng. Phn ng khi ti CaO + H2O Ca(OH)2 + Q Phn ng ti vi ta nhiu nhit nn cn ch an ton khi ti tng tnh do ca vi cn vi trong nc 10 12 ngy m cho CaO hydrat hon ton Bo qun vi phi ngn cch vi vi khng kh (nc hoc ct) trnh vi b ha 2) Thch Cao CaSO4.2H2O Qu trnh nung
140 C CaSO4.2H2O 100 CaSO4.1,5H2O + 0,5H2O
o

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CaSO4.1,5H2O tn ti hai dng th hnh l ,. Dng to thnh khi tch nc th lng c cu trc tinh th hnh kim, ng rn nhanh khi gp nc. Dng to thnh khi tch nc th kh, ng rn khi gp nc nhng cho bn km hn dng
450 C CaSO4.2H2O 300 CaSO4 + 2H2O
o

CaSO4 to t nhit ny gi l Anhidrit ha tan, dng ny ng rn khi gp nc nhng cho bn thp. Nu nung n nhit 600 700 C th to ra Anhidrit khng ha tan v dng ny khng ng rn.
1000 C CaO + SO3 CaSO4 900
o

III- Sn xut cc cht kt dnh thy lc 1) Vi thy c ch to bng cch nung vi vi t st hoc hn hp vi vi t st nung. Hm lng t st t 617% Tnh cht: ng rn nhanh khi gp nc, cho bn thp ch xy dng nhng cng trnh nh. Gi thnh t 2) Xi mng La M Nguyn liu sn xut l vi v t st nung nhng cha n nhit kt khi Khi nung th cc Oxyt CaO phn ng to cc khong. Nhit nung 800 900 C nu phi liu nhiu Oxyt MgO, v 1000 1100 C nu t MgO Tnh cht: ng rn nhanh khi gp nc, cho bn thp nn ch thch hp xy dng cng trnh nh chu ti b. 3) Sn xut Xi mng Pooclng a) Nguyn liu sn xut - vi: CaCO3 . c th c ln tp cht nh t st hoc MgCO3

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- Qung st -t st: thnh phn gm c cc khong chnh Khong Caolinit: Al2O3.2SiO2.2H2O Monmoriolit: Al2O3.4SiO2.nH2O Bentonit: - Cc ph gia Ph gia thy: cho vo tng tnh bn nc ca ximng, thng s dng SiO2, Al2O3 hot tnh Ph gia khong ha: c vai tr thc y qu trnh to khong, thnh phn c th NaCl, CaF2, P2O5, B2O3. Ph gia y: cho vo tng thm lng ximng ng thi h gi thnh sn phm. Thng s dng l ct hoc bt vi b) Phi liu T l cc oxyt trong qu trnh hinh thnh Clanhke thng m bo cc thng s sau CaO 6467% Quan h v t l
%CaO = 1,92,4 %( SiO2 + Al 2 O3 + Fe2 O3 )
% SiO2 = 1,73,5 %( Al 2 O3 + Fe2 O3 ) % Al 2 O3 = 1,0 3,0 % Fe2 O3
CaO 1,65 Al 2 O3 0,35 Fe2 O3 = 0,8 0,95 2,8SiO2

Al2O3. SiO2.5H2O

SiO2 2127%

Al2O3 47%

Fe2O3 24%

MgO 23%

M un kim: m = M un silicat: n =

M un Alumin : p = H s bo ha : KH =

c) Cc phng php sn xut xi mng

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C hai phng php l phng php l ng v phng php l quay, trong phng php l quay li c phng php t v phng php kh - Phng php l quay-t: c u im l phi liu c nghin mn trn u nh c nc nn cht lng sn phm tt. Nhc im do nguyn liu nhiu nc nn s lm tn nhin liu, l nung di lm tng chi ph thit b, mt bng, chi ph vn hnh - Phng php l quay-kh: u im tiu hao t nhin liu, l kch thc ngn hn, nng xut l cao hn. Nhc im tiu hao nhiu in v s dng nhiu nhn cng lao ng - Phng php l ng: u im l vn u t khng ln, mt bng sn xut b, in nng tiu hao t. Nhc im cht lng xi mng khng cao, nng xut thp, tiu hao nhiu nhin liu

d) Qu trnh ha l khi nung xi mng - Khi nung nguyn liu n nhit 200 C xy ra qu trnh thot nc l hc - Nung n nhit 500 C Xy ra qu trnh thot nc ha hc v t chy cc cht hu c - Nung n nhit 900 C bt u phn hy cc khong cacbonat v c mt s phn ng gia cc oxyt - n nhit 1200 C th phn ng gia cc khong xy ra mnh nhng xy ra ch yu trong pha rn. - n 1400 1450 C th phn ng xy ra mnh lit do hnh thnh pha lng, ng thi hnh thnh tt c cc khong chnh ca xi mng (C3S, C2S, C3A,C4AF) e) Cc yu t nh hng ti cht lng ca xi mng
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- Kch thc cc ht xi mng - Lng nc khi trn vi xi mng - Hm lng vi t do trong xi mng phi nh - Mc xi mng phi t chun d) S sn xut xi mng theo phng php kh

1 Nguyn liu 3.ng phng khng 5. L quay

2. Thit b trn 4. Thit b trao i nhit Xyclon 6. Thit b lm lnh

S khi nh my xi mng Hong Thch

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B- Sn xut thy tinh

1) Tnh cht, thnh phn, phn loi a) Tnh cht - dn nhit nh, c tnh cch nhit - H s dn n nhit khng ng k - bn ha - c tnh cht in mi cao, cch in - C ch s quang hc tt b) thnh phn Me2O.RO.SiO2 Me: l kim loi kim nh Na, K, Li RO: C th l cc oxyt CaO, MgO, BaO, ZnO, PbO - SiO2: ng vai tr lm khung ca thy tinh, lm tng bn ha, bn c. bn nhit. Nu nhiu Th li lm tng nhit nng chy. - Na2O: C tc dng h thp nhit nng chy ca thy tinh, lm gim nht ca thy tinh. - K2O: lm thy tinh trong sut, d gia cng, sc thi p hn, lm gim khuynh hng kt tinh ca thy tinh. - PbO: h thp nhit nu thy tinh, thy tinh d gia cng hn(mi , ct) dng nhiu trong thy tinh quang hc - ZnO, B2O3 lm thy tinh bn ha, bn nhit nn ng dng nhiu trong sn xut thit b th nghim. c) Phn loi thy tinh - Thy tinh dng tm: vd knh ca, knh t.. - Thy tinh hnh th rng: chai l, phch nc, bng n - Thy tinh khi c nh gch, tng
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- Thy tinh dng bng si - Thy tinh c bit: knh an ton, knh t ngoi, hng ngoi 2) Nguyn liu sn xut thy tinh a) Nhm nguyn liu chnh( Nhm ny cung c p cc oxyt SiO2,K2O,Na2O,CaO,MgO, B2O3) Cung cp SiO2 thng dng ct thch anh Cung cp Na2O c th dng Na2CO3, Na2SO4 CaO c ly t vi MgO thng ly t qung lmit [Mg,Ca]CO3 B2O3 ly t nguyn liu axit boric H3BO3 hoc hn the Na2B4O7.10H2O Trong cc oxyt trn th SiO2 thng chim 6075%, Na2O thng chim 1725 % b) Nhm nguyn liu ph - Cht kh bt: dng kh bt khi nu thy tinh. Cc cht thng dng As2O3, NaNO3, NH4Cl. Nhng cht ny khi nu cng thy tinh s phn gii thot kh mnh nn ko cc bt kh trong khi thy tinh bay ra ngoi, ng thi o trn thy tinh c ng u - Cht oxy ha kh: dng phn gii cc dng Sunfat v kh mu ca thy tinh. Thng dng Than ci, than cc Mg, Al, Sn(thic). Na2SO4 + 2C Na2S + 2CO2 2MnO2 + 2FeO Mn2O3 + Fe2O3 en Xanh Tm Vng Mu tm + vng = Khng mu - Cc cht nhum mu: chia thnh hai loi cht nhum mu phn t v cht nhum mu khuych tn keo Cht nhum mu phn t l cht mu khi nu thy tinh s to vi thy tinh dung dch thc, tc cht ny phn tn u. Qu trnh nu th hin mu ngay. Cc
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cht mu thng dng Cr2O3 cho mu xanh lc, NiO cho mu xanh nc bin, FeO cho mu xanh, Fe2O3 cho mu t vng n nu, Oxyt CoO cho mu xanh l cy Cht nhum mu khuych tn keo: Khi nu cng thy tinh n tn ti dng khuych tn keo, khng th hin mu ngay m phi gia nhit ln th hai. Cc cht mu c th l Au, Ag, Cd, .. qu trnh nu i hi k thut cao, dng cc nguyn t qu him nn t tin. - Cht gy m c thy tinh: Khi nu cc cht ny s trong thy tinh dng vi tinh th lm thay i hng i ca nh sng theo nhiu hng nn thy tinh mt trong sut(m c).Cc cht gy m c c th l 3NaF.AlF3, Na2SiF6, CaF2, Ca3(PO4), ZnO 3) Cc phn ng khi nu thy tinh
600 c MgO + CO2 MgCO3 300
c MgCO3 + Na2CO3 300 Na2Mg(CO3)2

Na2Mg(CO3)2 + 2SiO2

650 c 350

Na2SiO3 + MgSiO3 + 2CO2

700 c MgCO3 + SiO2 450 MgSiO3 + CO2

1200 c MgSiO3 MgO + SiO2 900

915 c CaCO3 420 CaO + CO2
c CaCO3 + Na2CO3 400 NaCa(CO3)2 900 c Na2Ca(CO3)2 + 2SiO2 600 Na2SiO3 + CaSiO3 + 2CO2

900 c CaCO3 + SiO2 600 CaSiO3 + CO2 900 c CaO + SiO2 600 CaSiO3
1200 c CaSiO3 + MgSiO3 600 CaMg(SiO3)2 900 c Na2CO3 + SiO2 700 Na2SiO3 + CO2

c) cc giai on khi nu thy tinh

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- khi nung ti nhit 1200 C th bt u nng chy cc ht quc (SiO2) v cc khong khc. tuy nhin phi liu lc ny c nht ln nn thy tinh khng ng u v nhiu bt. - T 1400 -1450 C thy tinh nng chy qu nhit, nht nh nn qu trnh khuych tn nhanh lm thy tinh ng u v thot ra nhiu bt kh. - lm ngui thy tinh xung nhit 1200-1300 C tng nht thy tinh ri tin hnh to bt. 4) S sn xut C-Sn xut Gm s 1) Cc cng on sn xut - p v sy kh, nghin mn nguyn liu ban u - Thit lp t l phi liu - Trn vi nc to nguyn liu do - To hnh sn phm - Sy nung sn phm trc khi nung - Lm ngui sn phm 2) Phn loi - Cn c vo tnh cht xng ca sn phm ngi ta chia lm hai loi: Sn phm c xng xp c kh nng ht m: vd gch, ngi Sn phm c xng kt khi , st c, khng ht m: snh. s - Cn c vo cu trc xng chia lm hai loi: Xng ng nht Xng khng ng nht 3) Nguyn liu a) Vt liu do - t st & Cao lanh, hot thch Thnh phn ch yu t st v cao lanh l cc oxit nhm, oxit Silic, oxit St
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Khong chnh l caolinit Al2O3.2SiO2.2H2O Cc khong khc: monmoriolit Al2O3.4SiO2.3H2O, Quc (SiO2), FeS2, TiO2.. lng cc cht thay i trong gii hn rng. Hot thch: 3MgO.4SiO2.H2O; 4MgO.5SiO2.H2O - Tnh cht ca t st 1. do: tnh do lm cho qu trnh to hnh khng b ph hy, gi hnh dng khi sy v khi nung. do ph thuc vo kch thc ca nguyn liu, kch thc cng nh th do cng ln (thng d<0,005mm). tng tnh do th c th gi m lu, thm keo hu c hoc cht in gii. 2. co: khi t st nung n 200C s sy ra qu trnh mt nc lm cho th tch b co, qu trnh ny gi l co khng kh. Khi nung n 700 C th mt s cu t nng chy lm th tch vt th b co, qu trnh ny gi l co la. t st cng do th co cng ln, do c th iu chnh c bng vt liu gy. 3. chu la: L kh nng khng b nng chy, bin dng khi nung nhit cao hay s thay i nhit nhanh. chu la cao c th ln n 1600 C b) Vt liu gy Nguyn liu ny cha nhiu khong SiO2 v khong Cacbonat b.1 Nguyn liu cha SiO2 gm c thch anh, ct thch anh, Quc Nhng nguyn liu ny c hm lng SiO2 khong 98%, Quc l qung gm nhng tinh th thch anh b c lin kt st c li vi nhau bng cht kt dnh. b.2 Khong Cacbonat - vi: cha ch yu l khong Canxit CaCO3, ngoi ra c nhiu cc tp cht nh alumosilicat, cc hp cht St, axit silicic. Ni chung hm lng tp cht thay i trong gii hn rng. Thng dng lm men trong sn xut gm s.

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- Qung manhezit: gm ch yu MgCO3, c tp cht l cc oxit nhm, st, silic, canxi. Hm lng MgO cao c th ln ti 46%. Qung dng sn xut vt liu chu la v cch in. - lmt: thnh phn ch yu CaCO3, MgCO3, hm lng MgO c th ln n 20%. Trong qung c th c cc tp cht nh oxit st, nhm, silic lm cho nguyn liu d nng chy nhng li lm gim chu la. ng dng dng sn xut vt liu chu la, men, xng s. c) Cht tr dung: L nhng cht c nhit nng chy thp, khi nng chy s lp y vo khe trng gia cc cu t nn lm sn phm st c, rn chc, bn c, bn ha. Cc cht tr dung thng dng: Fenspatkali: K2OAl2O3.6SiO2 FenspatNatri: Na2OAl2O3.6SiO2 FenspatCanxi: CaO.Al2O3.2SiO2 Trong Fenspat Kali c nhit nng chy thp nht (tt nht) d) Men: l dng thy tinh silicat, khi trng s lm cho b mt sn phm st c nhn bng, bn ha, bn c, bn nhit v lm p cho sn phm. - cch trng men c th thc hin trc khi nung, hoc trng sau khi nung nhng cch ny phi gia nhit li. - khi trng c th nhng sn phm mc vo huyn ph men, dng chi qut, phun - Tiu ch chn men Men c h s dn n nhit tng ng vi xng Nhit nng chy ca men phi tng ng vi nhit nung ca xng e) Cc cht mu - Dng trang tr b mt sn phm, thnh phn ch yu l cc oxit v mui ca kim loi. Cc oxit thng dng : Oxit st cho mu t vng ti nu
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Oxit Crom cho mu xanh lc Hn hp oxit st, crm cho mu nu Hn hp oxit Crm v oxit thic cho mu hng Oxit Mangan cho mu nu sm Oxit Coban cho mu xanh l cy, khi thm Ch v Natri th cho mu tm. 4) S sn xut

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