Trng i Hc M a Cht

Khoa Du Kh B Mn: Lc Ha Du

TI: TI U HA QU TRNH REFORMING ETANOL SN XUT H2 S DNG XC TC Ni/Al2O3 TRN PHN MM HYSYS

HN: 2011

SINH VIN THAM GIA TI:

Lng Vn Sn Ng Th Hnh Nguyn Th Thanh Mai
Gio Vin Hng Dn:
KS. on Vn Hun

MC CH V NGHA CA TI
Mc ch: Sn xut hydro t etanol mt ngun nguyn liu biomass Ti u ha qu trnh nhm thu c ti a H2 gim lng CO2 thot ra mi trng da vo m phng trn phn mm Hysys Tng hp xc tc cho phn ng v nghin cu ng hc ca phn ng trn xc tc Ni/Al2O3 ngha:

- Sn xut H2 nhm thay th ngun nhin liu ha thch ang dn cn kit, ng thi gip gim nhim mi trng do nhin liu ha thch gy ra.
- Sn xut H2 l mt hng i mi, phng php ny c nhiu u im hn cc phng php khc n c tnh ng dng cao, n gin v ph hp vi iu kin ngun nguyn liu biomass sn c nh Vit Nam.

NI DUNG NGHIN CU
Gii thiu ngun nhin liu H2 M phng qu trnh reforming etanol sn xut H2 - M phng qu trnh - Ti u ha qu trnh M phng phn ng reforming trn xc tc Ni/Al2O3 - Nghin cu ng hc ca phn ng - Tng hp xc tc Ni/Al2O3 (c trng bng phng php XRay + BET) - M phng phn ng trn Hysys, nh gi cc yu t nh hng n tc phn ng Kt lun v kin ngh

CC NGUN NNG LNG HIN NAY

Nng lng mt tri

Nng lng ha thch: du m, than

Nng lng sinh khi

Ht nhn

S sn xut etanol t sinh khi

X l ngun biomass Sn xut enzim

Etanol

X l s b

Thy phn xenluloz

Ln men glucoz

Thu hi etanol

Ln men pentoz

Tn dng licnin

Vi mc ch lm nhin liu, H2 c nhiu u im hn so vi nhin liu ha thch

L nhin liu sch, gn nh khng pht kh thi. L ngun nng lng c th ti sinh. Thay th kh thin nhin cung cp nng lng cho nhu cu dn dng. Lm pin nhin liu cho ng c, chy rt m, khng gy n.

ng dng ca ngun H2

Cng ngh ha du

Ngun H2

Cng ngh lc du

Luyn kim, cht bn dn

Nhin liu cho ng c

Ti sao li dng etanol sn xut H2 ?

D reforming hn hydrocacbon

Tit kim nng lng v chi ph

Do khng cn etanol tinh khit nn b qua cc cng on sy kh, chng ct, hp ph . Do khng dng lu hunh, mt xc tc c nh trong reforming hydrocacbon v s dng ngun etanol sinh khi.

Trnh vn nhim mi trng

Ti sao li dng xc tc Ni/Al2 O3 ?

Xc tc c cc u im:

chn lc H2 cao
To ra hiu sut cao, > 90% D tng hp.

M PHNG QU TRNH SN XUT H2 T ETANOL

M phng qu trnh reforming etanol sn xut hydro.
etanol Thit b WGS 100oC

Air
Water S khi

Thit b ATR 100oC

Thit b PROX 70oC Khng kh H2(pin nhin liu)

S dng m phng

Dng nguyn liu

n v

Dng
Name Nhit

Dng 1

Dng 2

Dng 3
etanol 100

Condition water Air 100 100 150

101.3

OC

Lu Lng
p Sut

550
101.3

100
101.3

kmol/h
kPa

THIT LP PHN NG
Trong thit b ATR
CH3CH2OH + 3H2O 6H2 + 2CO2 CH3CH2OH + 3H2O 4H2 + 2CO CH3CH2OH + 0.5 O2 CH3CHO + H2O CH3CH2OH C2H4O + H2 CH3CH2OH C2H4 CH3CH2OH 0.5 CO2 + 1.5 CH4 CH3CH2OH CO + CH4 + H2 C2H4O + H2O 2CO + 3H2 CH4 + 2O2 CO2 + 2H2O CH4 + 2O2 CO + 2H2 CH4 + 2O2 CO2 + 2H2 C2H4 + H2 C2H6 C2H4 2C + 2H2 (Ho =174kJmol-1) (Ho = 256 kJmol-1) (Ho = -175 kJmol-1) (Ho = 68 kJmol-1) (Ho= 45 kJmol-1) (Ho= -74 kJmol-1) (Ho= 49 kJmol-1) (Ho= 180 kJmol-1) (Ho= -800 kJmol-1) (Ho= -36 kJmol-1) (Ho= -320 kJmol-1) (Ho= -140 kJmol-1) (Ho= -52 kJmol-1)

7CH3CH2OH + 5.5O2 + 2H2O 6CO2 + 8CO + 23H2 (HO= -825 kJmol-1)

THIT LP PHN NG

Trong thit b HTS, MTS & LTS (WGS) CO + H2O CO2 + H2 (Ho= -42 kJmol-1) Trong thit b PROX (mc ch l gim nng CO n mc cho php) CO+O2 CO2 v O2 + H2 = H2O.

S dng m phng

Kt Qu M Phng
Kt qu cc dng ra khi thit b ATR v LTS

Thnh phn
CO H2

Dng hi ra khi thit b ATR

0.033193 0.626474

Dng hi ra khi thit b LTS

0.005956 0.658713

TI U HA QU TRNH

Nng ca CO v H2 ph thuc lu lng dng khng kh

Nhit dng hi ra khi thit b ATR thay i theo lu lng mol khng kh

TI U HA QU TRNH

S thay i nng ca CO v H2 dng ra khi thay i lu lng nc.

Nhit dng hi ra khi thit b ATR khi thay i lu lng dng nc

TI U HA QU TRNH

Nng CO ca dng hi ra khi thit b PROX khi thay i lu lng dng PROX air.

TI U HA QU TRNH

Thnh phn

Dng kh ra khi thit b ATR 845 kmol/h

Dng kh ra khi thit b LTS 70 kmol/h

CO
H2

0.0337
0.6355

0.0049
0.6644

Nng CO gim 1.527% 17.73% v H2 tng ln 1.44% 0.86% sau khi ti u

KT QU TI U Worksheet/conditions Name Nhit p sut Tc dng Worksheet/composition H2 O PROX vap out 126 oC 81.32 KPa 2601 kgmole/h Phn mol 0.003453

CO
CO2 H2 N2 O2 AcetAldehyde Methane ethylene

0.000005
0.067303 0.656456 0.267014 0.000014 0.002564 0.001915 0.001276

ng hc qu trnh reforming etanol trn xc tc Ni/Al2O3

C2H6O + 3H2O
1.Hp th etanol Ln b mt xc tc 2.Tng tc gia etanol Hp th vi v tr l Trng lin k

Da trn c ch Eley Rideal.

2CO2 + 6H2 (HO=174kJmol-1)

C2H6O + (a) C2H6O(a)

C2H6O(a) + (a) CH4O*(a) + CH2*(a)

3.Phn ng b mt CH4*(a) + H2O(g) CO2 + 3H2 + (a). Hp ph & gii hp ph CH*2(a) + 2H2O(g) CO2 + 3H3 + (a).

Tng Hp Xc Tc Ni/Al2O3
Trong nghin cu ny, chng ti tng hp xc tc Ni/Al2O3 da trn 2 phng php:
- Phng php ng kt ta (coprecipitation)

Dd Na2CO3
Ni(NO3).6H2O
Al2(NO3)3.9H2O

Dung dch A 40oC

Khuy

Lc kt ta Nung 600oC Mu CP

Sy kh

- Phng php kt ta ha hc (Precipitation)

Ni(NO3)2.6H2O

Khuy 24h

Lc kt ta
Dung dch B (Na2CO3 + Al2O3)

Sy kh

Nung 600oC

Mu PT

Cc mu xc tc tng hp

Mu xc tc
CP10 CP15 CP20 PT10 PT15 PT20

Ni (% KL) (M=58,69)
10 15 20 10 15 20

Al (%kl) (M=27)
47,63 44,98 42,34 47,63 44,98 42,34

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau CP5

700

600

d=2.421

500

d=2.803

d=1.997

Lin (Cps)

400

300

200

100

0 20 30 40 50 60 70

2-Theta - Scale

File: Son DH mo mau CP5.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 20.000 - Theta: 10.000 - Chi 00-004-0858 (D) - Aluminum Oxide - gamma-Al2O3 - Y: 86.62 % - d x by: 1. - WL: 1.5406 -

d=1.562

d=1.413

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau PT15

1500

1400

Kt qu o XRD
d=2.089 d=1.603

1300

1200

1000

900

800

700

d=2.555

1100

300

d=2.421

200

d=1.513

d=1.548

d=1.481

d=1.277

d=1.240 d=1.236

400

d=2.386

d=1.405

500

d=3.490

600

d=1.743

d=1.375

100

0 20 30 40 50 60 70

d=1.965

d=1.206

2-Theta - Scale
File: Son DH mo mau PT15.raw - Type: Locked Coupled - Start: 20.000 - End: 80.000 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 19 s - 2-Theta: 20.000 - Theta: 10.000 - Chi 01-071-1123 (C) - Corundum - Al2O3 - Y: 42.51 % - d x by: 1. - WL: 1.5406 - Rhombo.H.axes - a 4.76170 - b 4.76170 - c 12.99470 - alpha 90.000 - beta 90.000 - gamma 120.000 - Primitive - R-3c (167) - 6 01-089-5881 (C) - Nickel Oxide - NiO - Y: 3.80 % - d x by: 1. - WL: 1.5406 - Cubic - a 8.35320 - b 8.35320 - c 8.35320 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fm-3m (225) - 32 - 582.

Kt Qu BET
Kt qu o BET ca mu xc tc CP15.

BET Surface Area:

204.0826 0.6923 m/g

M phng phn ng reforming trn xc tc Ni/Al2O3

Name Nhit

etanol 78.81 oC

Hi nc 100oC

p sut
Source: [http://en.wikipedia.org/wiki/Plug_flow_reactor_model]

101.3Kpa

101.3Kpa
150 kmol/h

Tc dng 100 kmol/h

Thit b PFR

M phng phn ng reforming trn xc tc Ni/Al2O3

Cc thng s ca Thit b PFR
Kinetic reaction
Total volume [m3] Length [m] Catalyst Data. 2.355 3

Particle Diameter [mm]

Solid density [kg/m3]

0.6
2500

M phng phn ng reforming trn xc tc Ni/Al2O3

Dng sn phm ca qu trnh phn ng

Worksheet
H2 CO2

Khng c xc tc C xc tc
0.5581 0.1860 0.6469 0.2156

etanol
H2O

0.1569
0.0989

0.1092
0.0283

Cc yu t nh hng n phn ng reforming

nh hng ca nhit n chuyn ha etanol v phn mol ca H2

Xu hng to COx v CH4 tng khi p sut tng

Cc yu t nh hng n phn ng reforming

Xu hng to cc c th gim bng cch tng nhit

Xu hng to cc c th gim bng cch tng t l hi nc so vi etanol (S/C)

KT LUN
m phng thnh cng qu trnh reforming etanol sn xut hydro trn phn mm Hysys. Kt qu thu c dng sn phm H2 t tinh khit cao. ti u ha c qu trnh vi mc ch tng hm lng H2 v gim hm lng kh CO da vo s thay i lu lng dng nc v kh. tng hp thnh cng 2 mu xc tc PT15 v CP15. Kt qu sau khi o XRD v BET cho thy c 2 mu xc tc trn u c kch thc mao qun trung bnh. nghin cu v m phng phn ng reforming etanol trn xc tc Ni/Al2O3 bng phn mm Hysys.

KIN NGH

Cn phn tch c trng cc mu xc tc vi hm lng Ni khc c tng hp chn ra xc tc ti u nht Nghin cu trn cc xc tc khc nh CeO2-ZrO2

Tin hnh thc nghim phn ng trn thc t so snh vi kt qu m phng trn Hysys nhm nh gi mc tin cy ca phn mm.