I.

GII THIU S LC V NH MY M PH M

II. TNG QUAN V QU TRNH KH LU HUNH V SN XUT KH TNG HP

III. M PHNG QUY TRNH CNG NGH KH LU HUNH V REFORMING HI NC KH T NHIN TRONG NH MY M PH M

IV . KT LUN

I. S LC V NH MY M PH M

S LC V NH MY M PH M
Ch u t: Tng cng ty Du kh Vit Nam Nh thu: Technip Italia v Samsung Egineering Hn quc

Tng vn u t : 450 triu USD

Cng ngh: an mch v Italia Khi cng xy dng nh my: 3/2001 Ngy nhn kh vo nh my: 24/12/2003 Ngy ra sn phm ammonia u tin: 4/2004

Ngy ra sn phm ur u tin: 4/06/2004

Ngy bn giao sn xut cho ch u t: 21/9/2004 Ngy khnh thnh nh my: 15/12/2004

NGUYN LIU CHNH DNG CHO NH MY

Kh thin nhin: CH4, C2H6, C3H8, C4H10 Kh ng hnh m Bch H, Kh thin nhin t bn trng Nam

Cn Sn v cc b khc thuc thm lc a pha Nam.

Lng kh tiu th: 450 x 106 Nm3/nm. c tnh v thnh phn kh: Nhit : 18-36 0C. p sut: 40 Bar Trng lng phn t: 18,68 g/mol Nhit tr: 42,85 MJ/m3 hay 40613,4 BTU/m3 Thnh phn: C1=83,31%. C2=14,56%. C3=1,59%. iC4=0,107%.

nC4=0,109%.

S LC V NH MY M PH M

in Nc tun hon Kh CO2

Sng Th Vi

Nc lm mt Nc thi

Xng ph tr

Hi nc

Xng Amnic

Amnic Hi nc

Xng Ur

Ur ht 2200 t/ngy

Xng sn phm

Nc lm mt
Kh t nhin

SN PHM CHNH CA NH MY

NH3: 1,350 tn NH3 /ngy (Cng ngh Haldor Topsoe - an mch)

UREA: 2,200 tn Urea /ngy (Cng ngh SnamProgetti - Italia) IN: 21MWH

II. TNG QUAN V QU TRNH KH LU HUNH V SN XUT KH TNG HP.

Khng kh ( t) Hi nc

Chuyn ha Kh t nhin Kh Lu hunh

Primary Reformer

Secondary
Reformer

Chuyn ho CO Nhit cao

CO

Nhit thp

H2

S khi qu trnh sn xut kh tng hp ca nh my m PH M

Kh t nhin

CNG ON I: KH LU HUNH

10-K-4011 H2 Recycle Thp Hyr ha 10-R-2001 Thp hp th Lu hunh 10-R-2002 A/B

Kh sch ti l Reforming (S 0,05ppm)

Mc ch ca cng on:ng trong 10-R-2001: Phng trnh phn kh lu hunh khi dng kh cng ngh v lu380 C t = hunh gy ng c R-S-H RH + H2S xc Reforming. + H2 Xt : Co-MoS Mc ch ca thit b Hydro ho: chuyn ho Phng trnh phn ng cc hp cht ca lu hunhtrong 10-R-2002 A/B: dng hu c sang t = 400 C ZnO + H S dng v c H2S 2v xc tc ZnO ZnS + H2Oth ch hp c lu hunh dng v c
o o

CNG ON II: REFORMING

Kh nhin liu (Kh t) Khng kh

Hi nc Kh cng ngh

L Reforming s cp 10-H-2001

CH4 : 14%

L Reforming th cp 10-R-2003

Chuyn ha CO

CH4 : 0,6%

Phng trnh phn ng trong 10-H-2001:

Xt Nhng yu t nh hng n hiu: Ni-Mg ca phn ng: sut phn ng Reforming bng hi nc. Nhit Cn-1H nhit lng cung nH2n+2 + H (2,9-3) Phn ngCReforming 2l phn ng thu nhit,2n + CO + 3H2 Q cp cho phn T l Steam/Cacbon O Hot ti thit b Reforming s xc t qu trnh t kh Fuel gas gian di ng tnh ca xc tc. Khi cp tc hot ng sau mt thi t / Xt hot tnh gim, m O CO + H2 bo hiu sut phn 2 + Q cao th phi tng CO2 + H ng Nhit lng cung cp cho phn ng trong thit b Reforming th cp t nhit hoc tng t l Steam/Cacbon.
o

Mc ch ca cng on:2O t = 650/780 khCO + 3H2 thnh CO, CO2 v H2 qua CH4 + H Chuyn ho C t nhin - Q
o

phn ng chy trc tip gia khng kh c nn t my nn khng kh v T = 160 kh t nhin, H2

CH4 + 2O2
o

Phng trnh phn ng trong 10-R-2003 : CO2 + 2H2O ( Khng kh c 21% O2 v 79% N2 )

CNG ON II: REFORMING

NH HNG CA NHIT :

Khi nhit tng t 800 1100oK th hiu sut chuyn ha CH4

tng, cn hiu sut

chuyn ha CO gim Nu qu trnh chuyn ha CH4 v CO trong cng mt thit b th nhit cao nng CO cn li cao, do khng th tng nng H2. Khi nhit chuyn ha thp (800oK) mt lng ln CH4 cha phn ng. Do : thu c nng H2 cao phi chuyn ha hai giai on

CNG ON II: REFORMING

NH HNG CA T L HI NC/ NGUYN LIU

chuyn ha ca CH4 khi thay i t l S/C v nhit , kho st p sut l 1 bar

CNG ON II: REFORMING

Kh nhin liu (Kh t) Khng kh

Hi nc Kh cng ngh

CH4 : 14%

Chuyn ha CO

CH4 : 0,6%

Xc tc ca thit b Reforming s cp gm 3 lp xc tc: RK211, RK201 v R-67-7H tui th d kin t 3 n 5 nm. Xc tc ca thit b Reforming th cp RKS-2-7H.Tui th d kin > 5 nm.

CNG ON III: CHUYN HA CO THNH CO2 v H2

Kh Reforming

CO : 3,23%.

Thp chuyn ha CO nhit cao

Thp chuyn ha CO nhit thp

Kh chuyn ho ( co : 0,23%)

10-R-2004

10-R-2005

o Mc ch ca qu trnh : chuyn ha CO thnh CO2 v H2 o Phn ng chuyntrnh phnthnh 10-R-2004 : ng to nhit, Phng ha CO ng CO2 l phn nhit cao tc phn ng ln nhng hiu sut chuyn ha C CO + cng t = 360 430 chia thnh 2 thit thp. V vy H2O on nyCu CO2 + H2 + Q b chuyn ha Xt : Fe, Cr, o Thp chuyn ha CO nhit cao chuyn ha phn ln CO CO2. Phng trnh 10-R-2005. o Thp chuyn ha = 195 220 C t nhit thp chuyn ha CO CO2 CO + H2O CO2 + H2 + Q hn. Xt : Cu, Zn, Al
o o

CNG ON II: CHUYN HA CO THNH CO2 v H2

Kh Reforming

CO : 3,23%.

XT : Fe; Cr; Cu

XT: Cu; Zn ; Al

Kh chuyn ho ( co : 0,23%)

Xc tc 10-R-2004: SK-201-2, thi gian bo hnh 3 nm, tui th d kin 5 nm. Xc tc 10-R-2005 : gm 2 lp: LSK v LK-821-2, thi gian bo hnh 2 nm, tui th d kin 3 nm.

PHN III: M PHNG QU TRNH CNG NGH KH LU HUNH V SN XUT KH TNG HP TRONG NH MY M PH M

3.1.

Thit lp thng s c bn cho qu trnh m phng

3.1.1.Thit lp cc cu t cn thit cho qu trnh - La chn cc cu t sau: Oxygen, Hydrogen, Nitrogen,CO, CO2, Argon, Methane, Ethane, Propane, i-Butane, n-Butane, n-Hexane, H2O, M-Mercaptan, E-Mercaptan, ZnO, H2S, ZnS. - Lp cu t gi: Cu t Khi lng phn t T khi (Kg/m3) - H ng hc: Peng-Robinson. 5650.03 7133.02 ZnO 81 ZnS 97

3.1.

Thit lp thng s c bn cho qu trnh m phng

3.1.2.Thit lp cc phn ng cho qu trnh

Phn ng cho qu trnh hydro ha Phn ng cho qu trnh kh lu hunh Phn ng cho qu trnh Reforming s cp Phn ng cho qu trnh Refoming th cp Phn ng cho qu trnh chuyn ha CO -> CO2

3.1.

Thit lp thng s c bn cho qu trnh m phng

1. Qu trnh hydro ha Add Reaction: Conversion Name Stoichiometry/Component Hidro hoa 1 M-Mercaptan Hydrogen Methane H2S -1 -1 1 1 VapourPhase 100 Hidro hoa 2 E-Mercaptan Hydrogen Ethane H2S -1 -1 1 1 VapourPhase 100

Stoichiometry/Stoich Coeff Basis/Rxn Phase Basis/Co

3.1.

Thit lp thng s c bn cho qu trnh m phng

1. Qu trnh hydro ha

3.1.

Thit lp thng s c bn cho qu trnh m phng

2. Qu trnh kh lu hunh

Add Reaction: Conversion

Name Khu S ZnO H2S ZnS H2O -1 -1 1 1 100

Stoichiometry/Component

Stoichiometry/Stoich Coeff

Basis/Co

3.1.

Thit lp thng s c bn cho qu trnh m phng

2. Qu trnh kh lu hunh

3.1.

Thit lp thng s c bn cho qu trnh m phng

3. Qu trnh Reforming s cp Add Reaction: Conversion Name Refor_SC1 Methane H2O CO H2 -1 -1 1 3 Basis/Rxn Phase Basis/Co VapourPhase 55 Refor_SC3 Ethane H2O Methane CO Hydrogen Hydrogen -1 -1 -1 -1 1 1 1 1 2 VapourPhase VapourPhase 35 100 Refor_SC2 CO H2O CO2

Stoichiometry/Component

Stoichiometry/Stoich Coeff

3.1.

Thit lp thng s c bn cho qu trnh m phng

3. Qu trnh Reforming s cp

Name Stoichiometry/ Component

Stoichiometry/S toich Coeff Basis/Rxn Phase Basis/Co

Refor_SC4 Propane H2O Ethane CO Hydrogen -1 -1 1 1 2 VapourPhase

100

Refor_SC5 i-Butane H2O Propane CO Hydrogen -1 -1 1 1 2

Refor_SC6 n-Butane H2O Propane CO Hydrogen -1 -1 1 1 2

Refor_SC7 n-Hexane H2O Methane CO Hydrogen -1 -5 1 5 10

VapourPhase VapourPhase VapourPhase

100 100 100

3.1.

Thit lp thng s c bn cho qu trnh m phng

3. Qu trnh Reforming s cp

3.1.

Thit lp thng s c bn cho qu trnh m phng

4. Qu trnh Reforming th cp

Add Reaction: Conversion

Name Stoichiometry/ Component Refor_TC1 Methane H2O CO Hydrogen -1 -1 1 3 VapourPhase 70 Refor_TC2 Methane Oxygen CO2 H2O -1 -2 1 2 VapourPhase 100 Refor_TC3 CO H2O CO2 Hydrogen -1 -1 1 1 VapourPhase 5

Stoichiometry/ Stoich Coeff Basis/Rxn Phase Basis/Co

3.1.

Thit lp thng s c bn cho qu trnh m phng

5. Qu trnh chuyn ha CO -> CO2 Gm hai giai on: giai on chuyn ha nhit thp v nhit cao. i vi qu trnh ny th trong Hysys tch hp sn cho chng ta phn ng trong library v c tnh ton theo hng s cn bng. Nn ta chn loi phn ng Add Reaction: Equilibrium v vo trong Library chn phn ng: CO + H2O -> CO2 + H2 Vi mc Reaction Set Name Hidro Hoa Khu S Refor_SC Active List Hidro hoa 1, Hidro hoa 2 Khu S Refor_SC1, Refor_SC2, Refor_SC3, Refor_SC4, Refor_SC5, Refor_SC6, Refor_SC7

Refor_TC CO -> CO2 Tcao CO -> CO2 Tthap

Refor_TC1, Refor_TC2, Refor_TC3 CO -> CO2 CO -> CO2

3.1.

Thit lp thng s c bn cho qu trnh m phng

Cui cng ta phi add ton b cc Reaction Set ny vo trong h nhit ng chn.

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3.2.1. Thit lp cc dng nguyn liu cho qu trnh 1. Dng kh t nhin 2. Dng km oxit Nhit 36oC, p sut 24.5 bar_g Nhit 250oC, p sut 38.2 bar_g lng mole l 31476 Nm3/h (gas) mass flow: 290 Kg/h
Cu t N2 CO2 CH4 C2H6 Thnh phn (% mole) 0.26 0.01 83.31 14.57 Cu t ZnO Thnh phn (% mole) 1.0

C3H8
n-C4H10 i-C4H10

1.60
0.11 0.11

n-Hexane

0.03

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

2. Dng Recycle H2 Nhit 370oC, p sut 38 bar_g v lu lng mole l 1.083x105 Nm3/h (gas)
Cu t Thnh phn (% mole)

Hydrogen
CO2 H2O

0.01%
0.06% 99.93%

3. Dng khng kh nng Nhit 550oC, p sut 31.5 bar_g, lu lng dng mole 5.353x104 Nm3/h (gas) Cu t Thnh phn (% mole) Oxygen Nitrogen CO CO2 Ar H2O

20%

76%

1%

1%

1%

1%

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3.2.2. Thit lp cc thit b c trong qu trnh 1. Thit lp my nn K-100 My nn K-100 c nhim v nn kh t nhin t 24.5 bar_g ln 39.2 bar_g Name Connection Inlet Outlet Energy Worksheet Pressure, Gas to E1 (bar_g) K-100 Khi Tu Nhien Gas to E1 Q-K100 39.2

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

2. Thit lp thit b un nng E-1

Name Connection Inlet Outlet Energy Parameters Duty Delta P

E-1 Gas to E1 Gas to Mix1 Q-E1 2.037x107 kJ/h 49.81 kPa

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3. Thit lp Mix 1
Name Connection Inlet Outlet Mix 1 Gas to Mix1 Recycle H2 Gas to E2

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

4. Thit lp E-2

Name Connection Inlet Outlet Energy Worksheet Pressure, Gas to Hydro Hoa (bar_g) Temperature, Gas to Hydro Hoa (C)

E-2
Gas to E2 Gas to Hydro Hoa Q-E2

38.2
400

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

5. Thit lp Hydro Hoa (Conversion)

Name Connection Inlet Vapour Outlet Liquid Outlet Energy Reaction Details, Reaction Set Worksheet Temperature, To khu S (C)

Hydro Hoa
Gas to Hydro Hoa To khu S Hydro Liq Q-hydro hoa

Hydro Hoa
380

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

6. Thit lp Khu S (Conversion) Name Connection Inlet Vapour Outlet Liquid Outlet Energy Reaction Details, Reaction Set Worksheet Temperature, To Mix 2 (C) Khu S To khu S Km oxit To Mix 2 Khu S Liq Q Khu S 390 7. Thit lp Mix 2

Name Connection
Inlet Outlet

Mix 2
To Mix 2 Hoi Nuoc To E3

8. Thit lp E-3 (Heater Name E-3 Connection Inlet To E3 Outlet To Refor_SC Energy Q-E3 Worksheet Pressure, To 34.8 Refor_SC (bar_g) Temperature, To 535 Refor_SC (C)

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

9. Thit lp Refor_SC (Conversion) Name Refor_SC Connection Inlet To Refor_SC Vapour Outlet To Mix 3 Liquid Outlet Refor_SC Liq Energy Refor_SC Q Reaction Details, Reaction Set Refor_SC Worksheet Presure, To Mix 3 30.90 (bar_g) Temperature, To Mix 783 3 (C)
Name Connection Inlet Outlet

11.Thit lp Refor_TC (Conversion) Name Connection Inlet Vapour Outlet Liquid Outlet Energy Parameter Delta P Reaction Details, Reaction Set Worksheet Temperature, Vap To E4 (C)
Mix 3 To Mix 3 Khong khi Nong To Refor_TC

Refor_TC To Refor_TC Vap to E4 Refor_TC Liq Refor_TC Q 50 kPa Refor_TC 958

10. Thit lp Mix 3

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

12. Thit lp E-4 (Cooler) 13. Thit lp CO -> CO2 Tcao (Equilibrium)

Name Connection Inlet Outlet Energy Parameters Delta P Worksheet Temperature, To CO -> CO2 Cao(C)

E-4 Vap To E4 To CO -> CO2 Cao E4-Q 20 kPa 340

Name Connection Inlet Vapour Outlet Liquid Outlet Energy Reaction Details, Reaction Set Worksheet Temperature, To E5 (C)

CO-CO2 Tcao To CO -> CO2 Cao To E5 Liq Tcao Q1 CO -> CO2 Tcao

360

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

15. Thit lp E-5 (Cooler) 16. Thit lp CO -> CO2 Tthp (Equilibrium) CO-CO2 Tthap To CO -> CO2 Tthap Vap Product Liq Product Q2 CO -> CO2 Tthap 190

Name Connection Inlet Outlet Energy Parameters Delta P Worksheet Temperature, To CO -> CO2 Tthap(C)

E-5 To E5 To CO -> CO2 Tthap E5-Q 90 kPa 170

Name Connection Inlet Vapour Outlet Liquid Outlet Energy Reaction Details, Reaction Set Worksheet Temperature, To E5 (C)

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

3.2.

Thit lp m phng qu trnh kh S v qu trnh Reforming hi nc trong nh my m Ph M

S PFD trn Hysys qu trnh kh lu hunh v Reforming hi nc trong nh my m Ph M

3.3.

Kt qu m phng

3.3.1.So snh kt qu m phng vi s liu t nh my m Ph M

Bng 3.1. Thnh phn dng sn phm ca l Reforming s cp v th cp

3.3.

Kt qu m phng

3.3.1.So snh kt qu m phng vi s liu t nh my m Ph M

Bng 3.1. Thnh phn dng sn phm ca l Reforming s cp v th cp

3.3.1

So snh kt qu m phng vi s liu t nh my m Ph M

Bng 3.2. S liu v dng sn phm thit b chuyn ha CO -> CO2 nhit cao v nhit thp Nhn xt: Kt qu gia qu trnh m phng v thc t l tng i st vi nhau, thnh phn sn phm kh ca m phng c sai lch nhng khng ng k.

3.3.2

Kho st s nh hng ca t l hi nc trn hydrocacbon n qu trnh Reforming hi nc.

S dng Set trong Hysys ci t gi tr ca t l dng lu lng mole gia hi nc v kh t nhin. Tin hnh kho st s nh hng ca qu trnh Reforming khi m t l hi nc trn kh t nhin thay i, ta kho st s thay i thng qua s thay i ca lu lng mole ca kh H2 v CO c trong dng kh sn phm (Vap Product). Thit lp Set cho t l hi nc v kh t nhin nh sau: Name Connection Target Variable, Object Target Variable, Variable Source, Object Parameters Multiplier SET-1 Hoi Nuoc Molar Flow Khi Tu Nhien 3.4403 S dng Case study kho st s nh hng ca lu lng mole hi nc n qu trnh Reforming.

3.3.2 3.3.

Kho st s nh hng ca t l hi nc trn hydrocacbon n qu trnh Reforming hi nc.

Hnh 3.2. th nh hng ca t l hi nc trn kh t nhin n qu trnh reforming thng qua vic kho st s thay i ca lu lng mole ca H2 v CO.

3.3.2

Kho st s nh hng ca t l hi nc trn hydrocacbon n qu trnh Reforming hi nc.

T th ta thy rng: Khi tng t l hi nc trn kh t nhin th qu trnh reforming cho chng ta c nhiu Hydro hn v lng CO thu c gim dn, do n thun li cho qu trnh mun thu nhiu hydro. Mt khc ta cng nhn thy rng, khi t l hi nc trn kh t nhin tng n mt gi tr no trong khong > 3.5 th lu lng dng ca kh hydro tng khng ng k. Do vi t l 3.4403 ca nh my nh ti u v ph hp vi thng s kho st trn Case Study.

KT LUN
M phng thnh cng qu trnh kh S v qu trnh Reforming So snh c kt qu ca qu trnh trong m phng v trn thc t.

Kho st s nh hng ca t l hi nc trn kh t nhin n qu trnh Reforming

XIN CHN THNH CM N THY V CC BN THEO DI