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GV: Hunh Quyn

1. Nguyn Ngc Khoa 61001544


2. Nguyn Vn Hng 61001403
3. H Huy Hng 61001177
4. Nguyn Thanh Tng 61003478
5. Nguyn Vn Ngha 61002120
6. ng Quang Anh 61000038

Ni dung
I. LCH S HNH THNH
III.CC PHNG PHP TI CH
IV. CC XC TC NG DNG
V.. SN XUT XC TC
VI. PHNG HNG
II. TNG QUAN
Lch s hnh thnh cng ngh:
Gii thiu v du nhn:
Du gc:
Du thc vt
Du khong
Du tng hp
Ph gia:
Ph gia tang ch s nht
Ph gia ty ra
Ph gia phn tn
Ph gia c ch n mn
Ph gia c ch g
Ph gia bin tnh, gim ma st
Ph gia h im ng c
Ph gia c ch bt
Du Diesel sinh hc:
Ngun gc: Du chin, du thi(du gc
thc vt) v du cha s dng.
u im:
L nng lng xanh, thn thin mi trng.
L nng lng bn vng, nguyn liu di
do v n nh.
S dng rng ri, p ng tiu chun quc
t v s dng.
Khng thuc vo phm tr sn phm nguy
him, d dng vn chuyn v lu tr.
Sn lng du diesel sinh hc khng chu s
kim sot ca OPEC (T chc cc nc xu
t khu du m), iu ny s gip n nh th
trng du m th gii.

I. TNG QUAN:
Du nhn thi l g ?
Du nhn thi l du c thnh phn tng t nh du
nhn v mt s hp cht b bin i t du nhn
trong qu trnh s dng
1. Nguyn nhn hnh thnh du nhn
thi
Qu trnh oxy ha du nhn.
Qu trnh polymer ha du nhn.
Qu trnh phn hy du theo nhit
S phn hy cc ph gia trong du nhn
Cn bn thi trong du nhn
Qu trnh oxy ha du:
Hu ht cc thnh phn ca du u b oxi ha

Kh nng bn oxy ha ca cc hp cht
hydrocacbon :
Hydrocacbon khng no < hp cht d
nguyn t < hydrocacbon thn < naphten <
parafin
Tc oxy ha du chu nh hng ca
cc yu t:
Bn cht ca du gc
Nhit
S khuy trn
Nng oxy trong du

Qu trnh polymer ha:
Polymer ha cc hp cht trung gian cha lin
kt bi to ra nha, asphalen, cn bn
S phn hy cc ph gia:
To ra cc axit hu c hoc v c gy nguy
hi cho thit b
Qu trnh phn hy du theo nhit :
Xy ra c nhit thp v nhit cao
nhit thp hnh thnh cc sn phm
nh peoxit, ru, andehyt,xeton v nc
nhit cao: qu trnh oxy ha du
xy ra nhanh. Du b oxy ha s lm tng
nht v kh nng bay hi, to cn bn
v du vecni
Cn bn thi trong du nhn:

Bn ngoi ng c: ch yu l cc loi bi bn
trong khng kh, hi m, nc... xm nhp vo
ng c.
Bn trong ng c: do s mi mn ca cc chi
tit ng c, cn sinh ra do qu trnh chy ca
du, ca nhin liu, lp bong trc sn vecni ca
cc chi tit my...
Du nhn thi c thnh phn ch yu nh sau:
Hp cht bn nh cc parafin dng mch thng,
mch nhnh.
Cc naphten c t nht 2 vng chim khong 73%
- 76%.
Cc olefin chim khong 5 - 7%.
Hm lng aromatic chim khong t 10 15%.
Hm lng cn bn, cc hp cht peoxit ...
Tc hi i vi ng c:
Gy n mn thit b khi hot
ng, ph v thit b ng c
sau mt thi gian s dng.
Cc cn rn c nh hng ti
qu trnh chy ca nhin liu
2. Tc hi ca du nhn thi:
Tc hi i vi mi
trng:
Tc hi i vi ngun
t : khi t b nhim
du, t s b bin
cht, khng cn canh
tc hoc gi tr s dng
c na.

Tc hi i vi ngun
nc: gy nhim
ngun nc, ngn
khng cho oxi khng
kh tip xc hoc trao
i vi mi trng bn
ngoi
Tc hi i vi con ngi: Nu
ngi ht phi khng kh nhim
hi du hoc thng xuyn lm
vic vi mi trng c hm
lng hi du cao s dn n mt
s bnh v h hp, tim mch,
mu, thn kinh...
3. Tnh hnh thu gom v ti ch du nhn thi:
Thu gom du nht thi:
Thu gom cn th cng, ch thu gom
dc mt lng rt nh
Qu trnh s dng du nht thi
Du nht thi c dng t l, trng
khun

Ti ch du nhn thi thnh nhin liu diesel,
song cht lng ti ch nhn chung cha t
c cc phm cht, cht lng cn thit v cc
c s ny ch yu ti ch theo phng php kinh
nghim hoc cng ngh n gin.
Mt s phng php ti sinh du nhn thi
1. X l bng t st v cao lanh.

Du thi
c lc v
loi nc,
cc mnh v
kim loi.
Cho axit
sunfuaric
c vo.
Du c tnh
axit nh c
trn vi cao
lanh.
Trung ha v
chng ct
Sn phm nh l du c ti ch,
cao lanh c ly ra y nh thit
b lc.
u im.
n gin trong thit k, v hot ng ph thuc vo
iu kin hot ng v nguyn liu.
Qu trnh x l ny sinh ra du c cht lng tt, c n
khong 70% kim loi c loi b.
1. X l bng t st v cao lanh.

Nhc im
Gi thnh cao v kh khn trong vic loi b thnh phn ln cn
axit v cao lanh thi. Cn axit c cc cht bt chy, ch, cc
hydrocacbon cha kim loai, sunfonat, v cc cht gy ung th.
t st thi cha hm lng du cao t 20% n 30%. C cn axit
v t st thi u t ra vn loi b. Thm vo , qu trnh x
l axit t st ch c tc dng tt vi du thi c hm lng ph
gia cao.
Vn khc ca qu trnh x l bng t st axit l mi thot ra
t bn cha, thit b x l, h thng x l nc thi v cn, du.
1. X l bng t st v cao lanh.
2.Cng ngh ti sinh du ca Phillip (PROP)
u im
Hiu sut cao, hn 90%
Thnh phm du bi trn c cht lng cao, hm lng kim
loi t.
B lc sinh ra trong qu trnh l phophat trung tnh, nn d lc
mt cch an ton.
Trong qu trnh sinh ra nhng sn phm ph c li nh
hydrocacbon nh v ng nng c th lm nhin liu.
Nhc im
Gi thnh sn phm cao.
Cng ngh phc tp v km linh ng.
2.Cng ngh ti sinh du ca Phillip (PROP)
Qu trnh B.V (KTI) gm c qu trnh chng ct v
hydrotreating loi b hu ht cc cht bn trong du thi.
3. Qu trnh B.V (Cng ngh KTI)
Thp chng u
tin loi nc
v tch cc
hydrocacbon nh
c th dng lm
phn on ca
du bi trn.
Du cn li thc
hin qu trnh
hydrotreating
Tripping bng hi
nc hoc chng
ct phn on
u im :
dng sn phm ph khng ln
cht lng sn phm cao; hiu sut cao (82%), linh
ng;
kh nng cc chp nhn cc vt liu c hi v PCBs.

Nhc im: ch yu l nhy ca xc tc
hydrotreating theo loi cht bn
3. Qu trnh B.V (Cng ngh KTI)
Theo vin du m Php (IFP), s dng propan l cht chn lc
chit loi b ph gia v tp cht cha trong du thi.
4. Cng ngh chit bng propan

Chng ct
Trn vi propan
vi t l 15-20:1
Tch chit propan
X l bng axit v
t st
Lc
5. Cng ngh ca tng cng ty xng
du Vit Nam
http://moitruongphucloi.com/cong-nghe-tai-che-dau-thai/
Hin nay xu hng nghin cu sn xut diesel t
cracking t cc du nhn thi, cao su thi nhng m
cha c ng dng rng do hm lng cn cacbon,
hm lng lu hunh v hm lng nc nhu hn cho
php.
6. Cracking sn xut diesel
4. Qu trnh cracking du thi:

QU TRNH CRACKING
DU THI
QU TRNH
CRACKING NHIT
QU TRNH
CRACKING DNG
XC TC
1, Qu trnh cracking nhit:

C ch gc t do theo Rice:
V d minh ha:
Nhit : (450-530)
0

C
p sut cao t gia mch nhiu sn
phm lng
4.1. Qu trnh cracking du thi dng NaOH
Vai tr ca NaOH:
Tng tc ca qu trnh cracking
Trung ha cc sn phm sinh ra mang tnh acid sinh ra trong
qu trnh phn hy cc hp cht ca du nhn thi
iu kin vn hnh:
1. S dng 0.4% NaOH 98%.
2. Thi gian phn ng l 1 gi 45 pht
i vi h xc tc acid
C ch hnh thnh carbocation: ph thuc bn cht hydrocarbon v tnh acid
ca xc tc.
C ch 1: phn t khng no (olefin) nhn proton t xc tc hnh
thnh alkylcarbenium.
R
1
-CH=CH-R
2
+ H-Z R
1
-C
+
H-CH
2
-R
2
+ Z
-

C ch 2: phn t no (paraffin) nhn proton t xc tc hnh thnh
alkylcarbonium. Alkylcarbonium khng bn, c th c chuyn thnh
alkylcarbenium.
R
1
-CH
2
-CH
2
-R
2
+ H-Z R
1
-C
+
H
3
-CH
2
-R
2
+ Z
-


H
2
+ R
1
-C
+
H-CH
2
-R
2
+ Z
-


C ch 1 v 2 xy ra trn tm acid Bronsted, trong c ch 1 xy ra nhanh hn v
nhit thp hn.
C ch 3: tm acid Lewis tch lai H
-
t phn t trung ha hnh thnh
alkylcarbenium.
R
1
-CH
2
-CH
2
-R
2
+ Z R
1
-C
+
H-CH
2
-R
2
+ ZH
-

C ch 4: khi tm acid b hp ph bi mt phn t hnh thnh nn tertiary
alkylcarbenium, qu trnh alkyl ha xy ra gia tertiary alkylcarbenium v phn t
olefin to nn alkylcarbenium vi kch thc ln hn.
Z- R
1
+ + R
2
-CH=CH-R
3
Z
-
+ R
2
-C
+
R
1
-CH
2
-R
3

4.2 Qu trnh cracking du thi dng xc tc H
2
SO4:
iu kin vn hnh:
H
2
SO4 (93-98)%
Lng acid s dng l 0.5% th tch
u im:
th hin hot tnh acid tt trong mi trng du nhn thi
c nhiu hp cht d nguyn t, cn bn d gy ng c xc
tc
Nhc im:
n mn thit b
Kh khn trong vic tch chit sn phm
Ti sinh xc tc kh khn
u tin pht trin cng ngh s dng xc tc d th.
Nghin cu ch to v ng dng xc
tc a mao qun th h mi vo qu
trnh cracking cn du thu nhin liu.
Xc tc a mao
qun th h mi
Al2O3


zeolite HY


Zeolite Meso-HY


zeolite Meso-HZSM-5
c im:

Xc tc d th c tnh axit mnh

C hot tnh cao, va bn trong cc iu kin
c nhiu cht c kh nng c ch hot ng xc
tc


Nguyn nhn:

Cc hp phn c mao qun trung bnh v mao qun ln nh -Al2O3,
hay cc zeolite c mao qun trung bnh Cc hp phn ny c cu trc mao
qun rng v thng thong, ph hp vi kch thc cc phn t cng
knh trong cn du, li c tnh acid nn s thc y tt qu trnh cracking
s cp to ra cc sn phm mch ngn hn

Cc hp phn c cc vi mao qun nh: HY, meso-HY, meso-ZSM-5, ph
hp cho qu trnh cracking th cp to ra cc sn phm cui cng. Cc
hp phn vi mao qun c tnh acid mnh nn kh nng cracking su kt
hp vi cc mao qun nh nn c xu hng to nhiu kh nu s dng
hm lng ln. Do , nhm nghin cu tm ra hm lng cc hp
phn cn thit cho qu trnh cracking

Cc hp phn cu thnh xc tc u c bn nhit, thy nhit ln nn
hon ton p ng c cc iu kin phn ng ca qu trnh cracking
pha lng
i vi axit sunfuric:
H2SO4 92-93% c dng loi kim loi trong du thi
ng vai tr xc tc trong qu trnh cracking xc tc.[1]
i vi natri hydroxit:
Loi lu hunh trong du nhn thi.[2]
ng vai tr cht ng t.
Tham gia vo qu trnh cracking nhit vi vai tr cht trung ha axit.
Xc tc trong qu trnh cracking xc tc.[3]
i vi Zeolit: xc tc tm axit, tng t nh trong qu trnh FCC x l
trong cng ngh lc du.
i vi Xc tc a mao qun th h mi: l xc tc Zeolit trn c s
Al2O3, zeolite HY, zeolite Meso-HY, zeolite Meso-HZSM-5.


Vai tr ca H2SO4, NaOH, Zeolit
Bn cht ha hc:
H
2
S + NaOH NaSH + H
2
O
NaSH + NaOH Na
2
S + H
2
O
RSH + NaOH RSNa + H2O

Thng s cng ngh nh sau:
Tc nhn kim : dd NaOH 20% + 10% kl Methanol
Hm lng tc nhn kim: 10% kl du thi
Nhit phn ng: 60
0
C
Thi gian phn ng: 20 pht
Tc khuy: 120 v/pht


[TS inh Vn Kha, Vin ha hc cng nghip Vit Nam,Nghin cu kho st mt s yu t nh
hng ti qu trnh loi lu hunh trong du nhn thi bng phng php ra kim]
Loi lu hunh trong du nhn thi
Sn xut v thu hi xc tc Zeolit

Phng php
sn xut
Ring l
i t khong
st
Cc bc sn
xut ring l
Tng hp , trao
i ion
Phi trn Zeolit
vi pha nn
Sy phun hn
hp xc tc
Sn xut v thu hi xc tc Zeolit
Sn xut v thu hi xc tc Zeolit
Quy trnh sn xut xc tc t khong st
Sn xut v thu hi xc tc Zeolit


Qu trnh ti sinh xc tc

Qu trnh ti sinh xc tc
Qu trnh ti sinh xc tc
1. Tng hp -Al2O3
2. Tng hp HY
3. Tng hp HY c mao qun trung bnh (Meso-HY)
4. Tng hp HZSM-5 dng mao qun trung bnh (Meso-
HZSM-5)
[Theo Nghin cu ng dng v ch to xc tc a mao qun th h mi vo qu trnh
cracking cn du thu nhin liu, nhm tc gi Vin du kh Vit Nam ]

Sn xut Xc tc a mao qun th h mi
Cracking xc tc du thi
to nhin liu l mt
hng i mi trong vic s
l du nhn thi. Hin nay
cha c mt quy trnh cng
ngh chnh thc c ng
dng quy m thng
mi. Quy trnh ny hin vn
ang c nghin cu,
kho st, ng dng
nhng m hnh nh.
Mt s hng nghin cu trong quy trnh sn
xut diesel t du nhn thi
Dy chuyn thit b cracking xc tc du nhn
thi ti CT CP C in Mi trng Lilama (Khu
kinh t Dung Qut, Qung Ngi) , 4m
3
/m)
Mt s hng nghin nghin cu trong quy
trnh
Trong vn tin x l trc khi a vo cracking xc
tc
C th x l lu hunh trong du nhn thi bng nhiu phng php, trong
ra kim l phng php n gin cho hiu qu cao (y cng l phng
php c s dng ph bin trong cng nghip lc ha du lm sch cc
hp cht cha lu hunh ), ngoi ra kim cn ng vai tr cht ng t c th
loi b cc hp cht axit, asphaten, cc hp cht khc.
y nghin cu v nh hng cc loi tc nhn kim ti hiu qu x l
nh NaOH, KOH, hn hp NaOH iso propylic, NaOH metanol, NaOH
cresylic. Vi mi loi tc nhn, kho st cc lng (% khi lng) v mc
nng khc nhau. i vi cc loi tc nhn hn hp (NaOH iso propylic,
NaOH metanol..) th kho st s thay i ca lng tc nhn ph (iso
propylic, metanol..) ti hiu qu x l.
Mt s hng nghin nghin cu trong quy
trnh
Zeolite Y l xc tc truyn thng trong qu trnh cracking xc tc du m.
Nghin cu tng hp xc tc zeolite Y t cao lanh thay v tng hp t
ha cht tinh khit s c ngha thc tin cao hn.

Nghin cu kho st cc yu t nh hng n qu trnh cracking xc tc
du nhn thi nh nhit , thi gian, hm lng xc tc t tm
ra cc iu kin ti u cho hiu sut thu diesel cao nht.

Trong vn tng hp xc tc v cc yu t nh hng n qu trnh
cracking xc tc du thi
Mt s hng nghin nghin cu trong quy
trnh
y l mt qu trnh quan trng, v diesel (thu c t cracking du
thi) s dng c trn th trng th buc phi p ng c cc yu
cu nh i diesel thng phm .Diesel thu c t cracking du nhn
thi cn cha nhiu cc hp cht khng bn, d b oxi ha, cc hp cht d
vng, c mi.


Vn t ra l nghin cu kho st cc loi cht hp th m bo
diesel c c tnh mu, mi, nht, n nh t yu cu. Thng tin
hnh nghin cu vi cc loi nh st trng Malaysia, silicagel, cao lanh
hot ha xc nh hm lng, t l s dng thch hp.


Trong vn tinh ch phn on diesel t qu trnh cracking xc tc du
nhn thi

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