Chng 3:

Lm kh kh

Chng 3: Lm kh kh
3.1. Gii thiu chung
Nc l tp cht ph bin nht ln trong cc hydrocarbon
Nc ln trong kh thin nhin trong qu trnh khoan, khai
thc, v qu trnh lm ngt kh (tch loi cc kh chua H 2S,
CO2) vv
Nc gy ra cc vn sau:

To thnh hyrt gy tc nghn van, u vi, trong

qu trnh vn chuyn

Gy n mn ng ng, cc thit b

Gy ra cc phn ng ph hoc lm mt hot tnh xc

tc trong cc qu trnh ch bin tip theo
2

Chng 3: Lm kh kh
Hm lng hi nc trong kh ty thuc vo p
sut, nhit , v thnh phn ha hc ca kh.
m bo ha l m ng vi trng thi bo
ha hi nc ca kh.
m tuyt i l khi lng nc cha trong 1
n v th tch hoc 1 n v khi lng kh.
m tng i l t l gia khi lng hi nc
cha trong kh v khi lng hi nc cc i cha
trong th tch kh xc nh iu kin bo ha.
3

Chng 3: Lm kh kh
=p/P
vi: : m tng i
p: p sut ring phn hi nc trong kh
P: p sut hi nc bo ha

Chng 3: Lm kh kh
m cn bng ca kh thin nhin ph thuc
vo thnh phn kh v hm lng mui:
Tng t trng kh v hm lng mui, hm lng nc
ca kh gim.
Khi c H2S, CO2 th m ca kh tng.
Khi c N2 th m kh gim.

Chng 3: Lm kh kh
Hydrat l hp cht dng tinh th tn ti trng
thi bn vng trong iu kin xc nh.
iu kin to hydrat:
Nhit , p sut kh.
Thnh phn kh: C1, C2, C3, i-C4, N2, H2S, CO2, Ar c th
to hydrat, nhng n-C4 khng to hydrat. Nhit bt
u to hydrat ca C1 gim khi trong kh c cha C3+.
Nng mui: tng nng mui, nhit bt u to
hydrat gim.

Chng 3: Lm kh kh
3.2. Lm kh kh bng phng php c ch
Lm kh kh nhm ly hi nc ra khi kh v h
im sng xung thp hn nhit vn chuyn
v ch bin.
Hm lng nc ti a cho php trong dng kh
sn phm thng thng l 100 mg H2O/ 1 Sm3 kh.
Cc phng php lm kh kh:
Dng cht c ch hn ch to hydrat.
Hp th hi nc bng cht lng ho nc.
Hp ph hi m bng cht lm kh rn hat ha.
Ngng t hi m nh nn hoc lm lnh kh.

Chng 3: Lm kh kh

Hm lng nc trong kh thin nhin cn phi

c tnh ton, d on qua xy dng c
phng n lm kh kh ti u.
Hm lng nc bo ho trong kh ngt ph
thuc vo P, T, v thnh phn kh (t trng tng
i : SGg = Mg / Mkk = Mg / 28.97)
Kh chua (c cha H2S v CO2) s c hm lng
nc cao hn. Cn phi hiu chnh hm lng
nc khi nng H2S v/hoc CO2 trong dng kh
ln hn 5%
8

Chng 3: Lm kh kh
Phng php tnh ton, d on

Xc nh t th:
Gin McKetta v Wehe (1958): kh ngt
Gin Campbell: kh chua
Gin Robinson: kh chua

n v: [mg/Sm3]; [lb/MMscf]

Sm3 : mt khi chun; o ti iu kin chun ISO 2533

101.35 kPa; 15oC
MMscf : triu feet khi chun, o ti 14.7 psi (101.35kPa);
60 oF (15.56 oC)
1 lb = 0.454 kg
9

Chng 3: Lm kh kh
Hm lng nc trong kh ngt
Gin McKetta v Wehe
?
01

A
01

Xc nh hm lng nc bo ho cho dng kh

hydrocacbon ngt c SGg 0.9; nhit 70 oC v
p sut 6000 kPa.
- T Hnh 1: W = 4500 mg/Sm3
- H s hiu chnh cho SGg 0.9: CG = 0.98
->Hm lng nc: W = 0.98 x 4500 = 4410
mg/Sm3
10

Chng 3: Lm kh kh
Hm lng nc trong kh chua
?
02

Tnh hm lng nc cho dng kh: 80% C1, 10% H2S v

A
02

a) p dng cng thc:

W = yHCWHC + yH2SWH2S + yCO2WCO2

10% CO2, ti 70 oC v 6000 kPa.

mg/Sm3

= 0.8x4500 + 0.1x6000 + 0.1x4700 = 4670

c WHC, WH2S, WCO2 t cc gin

b) Dng gin Campbell vi nng H2S tng ng:
yH2S* = yH2S + 0.75 x yCO2 = 0.175 = 17.5%
c hm lng nc t gin : W = 4500 mg/Sm3
11
(6900 kPa); 12000 mg/Sm3 (2100 kPa) -> ti 6000 kPa:

Chng 3: Lm kh kh
Xc nh iu kin P, T to thnh hydrat:

S dng SG

Phng php Katz

Phng php Baile

Xc nh iu kin to thnh hydrat trong qu

trnh gin n kh (gim p)

12

Chng 3: Lm kh kh
Cho dng kh:

?
04

C1

0.784

C2

0.060

C3

0.036

C4

0.024

N2

0.094

CO2

0.002

a) Xc nh P to thnh hydrat ti 10oC.

b) Dng kh trn c gin n t 10000
kPa xung 3400 kPa. Xc nh T ti
thiu khng c s to thnh hydrat
trong qu trnh gin n.
c) Dng kh trn ti 15000 kPa, 40oC c
th gin n n p sut no m
khng b to thnh hydrat?
13

Chng 3: Lm kh kh

A
04

a) SGg = 0.693
c t gin : P = 2200 kPa
b) T gin , tm im ni gia ng p sut
u 10000kPa v p sut sau 3400 kPa. c T
tng ng (~450C).
c) T gin , tm im ni gia ng p sut
u 15000kPa v nhit 400C, c p sut
sau (~ 8000 kPa)
14

Chng 3: Lm kh kh
Phng php Katz

Chnh xc hn phng php s dng SG

Chn mt gi tr T ti P cho trc (hoc P ti T

cho trc)

S dng cc gin xc nh hng s cn

bng kh-rn Kv-s cho mi hydrocarbon.

Xt tng (yi/Ki,v-s)

Lp li 3 bc trn cho n khi (yi/Ki,v-s) = 1

15

Chng 3: Lm kh kh
Cho dng kh:

?
05

C1

0.784

C2

0.060

C3

0.036

C4

0.024

N2

0.094

CO2

0.002

Xc nh P to thnh hydrat ti
2000 kPa theo phng php Katz.
?
So snh vi kt qu ca04

16

Chng 3: Lm kh kh

A
05

Xt T = 10oC

Kv-s

y/Kv-s

C1

0.784

2.05

0.382

C2

0.060

0.82

0.073

C3

0.036

0.12

0.3

C4

0.024

0.045

0.533

y/Kv-s = 1.288 > 1

Xt T = 12oC

Kv-s

y/Kv-s

C1

0.784

2.12

0.3698

C2

0.060

1.1

0.0545

C3

0.036

0.23

0.1565

C4

0.024

0.084

0.2857

y/Kv-s = 0.8665 < 1

Xt ti 11oC, thu c y/Kv-s = 1.0417 ~ 1,
c th kt lun y l nhit to hydrt ca dng kh ti 2000 kPa
17

Chng 3: Lm kh kh

i vi dng kh chua c nng H2S, CO2 cao:

Khng s dng c phng php Katz !!!

S dng phng php Baille-Wichert: hiu

chnh nhit to hydrat thng qua % C3

18

Chng 3: Lm kh kh

?
06

Cho dng kh:

C1

0.843

C2

0.031

C3

0.007

C4

0.004

N2

0.003

CO2

0.070

H2S

0.042

a) Xc nh T to thnh hydrat
ti 4200 kPa ?

19

Chng 3: Lm kh kh

Dng phng php Baille-Wichert

a) SGg = 0.682
b) Gin Hnh 12: 4200 kPa -> 4.2 %H2S -> SGg = 0.682
c) Theo dc phn di ca gin xc nh c T to
hydrat tng ng l 17.5oC.
d) Hiu chnh theo %C3
T gin hiu chnh trong Hnh 12, tm im ni gia
%H2S v %C3. Dng thng xung ng P = 4200kPa.
c nhit hiu chnh: -1.5oC.
e) Vy T to hydrat ca dng kh ny l 16oC
20

Chng 3: Lm kh kh

3.2.1. Phng php c ch to hydrate

Bn cht ca phng php c ch l a vo
dng kh m cht c ch ha tan trong nc t do
v do lm gim p sut hi nc v nhit to
hydrat.
Cc cht c ch thng s dng: methanol,
glycol,
Trc y, cht c ch l NH3 v mui.
La chn cht c ch glycol: ph thuc nhit
to hydrat, nht, mc h nhit , s ha tan
21
trong hydrocarbon, nhit tch chit, thnh phn

Chng 3: Lm kh kh
Methanol vs. Glycol
Methanol

Glycol

Khng phn ng vi HC
Tan v hn trong nc
Kh thu hi v hon nguyn
D bay hi di iu kin vn
hnh
S dng khi yu cu nhit <250C
Ha tan mt phn hidrat

Thu hi v ti s dng c
Khng bay hi
S dng n - 250C
Khng ha tan hidrat

Nu lng MeOH cn dung vt qu 30 gal/hrs dng glycol

22

Chng 3: Lm kh kh
Nn xem xt s dng phng php gy c ch khi:
+ vic to thnh hyrat c th din ra trong thi gian
ngn
+ nhit hot ng ca h thng ch thp hn vi
so vi nhit to hyrat ca dng kh
Cc cht c ch thng s dng: glycols (EG, DEG, TEG),
methanol,
Cc cht c ch thng c phun thng vo dng kh

23

Chng thnh to Hydrat bng cc cht c

ch

24

Chng thnh to Hydrat bng cc cht c

ch
Lng cht c ch cn s dng

Tnh theo phng trnh Hammerschmidt

T = K x I / [ (100 I) x MI ]
T :
K:
I:
MI :

gim nhit to thnh hyrt (oF)

hng s cho mi cht c ch
nng ti thiu ca cht c ch trong nc t do wt%
khi lng phn t cht c ch

Cht c ch

Methanol

32

2335

EG

62

2200

PG

76

3590

DEG

106

4370
25

Chng 3: Lm kh kh
Phng trnh Hammerschmidt :
t = 0,556 K I / [MI(100-I)]
t: lng gim nhit hydrat ha p sut xc nh (0C).
W: hm lng cht c ch (%).
M: phn t lng cht c ch.
K: hng s (K = 2335 cho methanol, = 4000 cho glycol).

26

Chng 3: Lm kh kh
Chi ph cht c ch (kg/1000 m3 kh) lai tr
hnh thnh hydrat:
q = (W1 W2) C2/(C1 C2)
W1, W2: hm lng m trong kh trc v sau khi a cht c
ch vo (kg/1000 m3 kh).
C1, C2: nng khi lng cht c ch trc v sau khi s
dng.

27

Chng thnh to Hydrat bng cc cht c

ch
?
09

Dng kh: 2 MMscfd, SGg = 0.6 ti 1000 psi v 100oF

Vn chuyn vo b ti 800 psi v 40oF.
Tnh lu lng MeOH cn bm vo c ch s to
thnh hyrat.

28

Chng thnh to Hydrat bng cc cht c

ch
A
09

1. Hm lng nc ca dng kh:

T Hnh 1b : 1000 psi ; 1000F : 60 lb/MMscf
800 psi ; 40 oF : 10.5 lb/MMscf
-> Lng nc t do: (60 10.5)lb/MMscf x 2 MMscfd
= 99 lb/ngy
2. Nhit to thnh hydrt:
T Hnh 5-b: 800psi, 0.6 SGg : Thydrat = 57.50F
-> T = 17.5 0F
3. Theo pt Hammerschmidt : K = 2335; M = 32 -> I =
19.4%
-> Lng MeOH cn cho 99 lb nc/ngy l 99 x 19.4 /
(100 -19.4)= 23.83 lb MeOH/ngy
29

Chng thnh to Hydrat bng cc cht c

ch
Hnh 5-b

30

A
09

Chng thnh to Hydrat bng cc cht c

ch
4. Lng methanol bc hi vo pha kh:
T Hnh 23
nng MeOH trong pha kh [lb MeOH / MMscf]
C=
nng MeOH trong pha nc [wt%]
Ti 800 psi, 40oF, C = 1.1
-> nng MeOH trong pha kh = 1.1 x 19.4 = 21.34
lb/MMscf
Lng MeOH trong pha kh = 21.34 x 2 = 42.68 lb
MeOH/ngy
5. Tng lng MeOH cn dng l:
23.83 + 42.68 = 66.51 lb MeOH/ngy

31

Chng thnh to Hydrat bng cc cht c

ch

32

Chng 3: Lm kh kh

3.2.2. Lm kh bng phng php hp th

Da trn s chnh lch p sut hi nc trong kh
v cht hp th.
Cc cht hp th thng s dng: mono-, di-, trietylen glycol.

33

Chng 3: Lm kh kh
Qu trnh hp th

L qu trnh truyn khi t pha kh sang pha lng

y l qu trnh tng tc vt l gia hi nc v dung mi

Hai nh lut chi phi qu trnh hp th:

Raoult: Pi = Pi* x Xi

P*i / Ptotal = Yi / Xi

Dalton: Pi = Ptotal x Yi

trong :

Pi : p sut ring phn ca cu t i

Pi* : p sut hi ca cu t i nguyn cht

Ptotal : p sut tng ca dng kh

Xi : % cu t i trong pha lng

Yi : % cu t i trong pha kh

Din ra hiu qu hn T thp v Ptotal cao

34

Chng 3: Lm kh kh

Yu cu ca dung mi:

C i lc vi nc mnh, v vi HC thp

C bay hi thp ti nhit hp th

C nht thp

C bn nhit tt

Kh nng gy n mn thp

Nhit si khc nhit si ca nc.

Triethylene glycol (TEG) l dung mi ph bin nht

35

Chng 3: Lm kh kh

u im

Nhc im
DEG

ho nc cao, bn
Mt mt do b li cun cao
cao khi c hp cht lu hynh, hn so vi TEG.
oxy v CO2 nhit cao.
Khi han nguyn, kh nhn
Dung dch m c khng c dung dch vi hm lng
DEG cao hn 95%.
ng bng.
Gim nhit im sng t
ha tan HC thp.
Hay dng p sut cao v c hn so vi s dng TEG.
Gi thnh cao.
chn lc cao.
Hon nguyn p sut chn
khng
36

Chng 3: Lm kh kh

u im

Nhc im
TEG

Ha tan hydrocarbon
ho nc cao.
trong TEG cao hn trong
To kh nng gim im sng cao
DEG cao hn DEG 25hn, bn tt khi c hn hp lu
30%).
hynh.
Han nguyn d dng n nng .
dung dch 99%.
Dung dch m c khng ng bng.
p sut hi thp hn bay hi ca
TEG thp hn DEG.
u t c bn v chi ph vn hnh
thp hn.
Khng qu nht nhit trn 70oF
Hon nguyn p sut kh quyn
37

Chng 3: Lm kh kh

u im

Nhc im

Dung dch 10-30% MEA, 60-80% DEG, 5-10% nc

Cht hp th c nc, CO2,
Mt mt do b cun ra cao
hn so vi TEG.
H2S.
Ch ng dng lm kh v
lm sch kh chua.
Cht hp th n mn kim
lai nhit han nguyn.
Gim nhit im sng
t.

38

Chng 3: Lm kh kh
Gii hn nhit lm vic ca qu trnh lm kh
kh bng phng php hp th:
Tmax = 380C
Tmin = 100C

39

Chng 3: Lm kh kh
Khi tng nng glycol, lng gim im sng
tng nhiu hn so vi khi tng chi ph ring cht
hp th.
Nhit phn hy ca DEG l 164,40C; TEG l
206,70C
TEG: c s dng ch yu c ch to hidrat
trong kh ngt v kh chua. gim im sng:
40-150oF vi nhit kh u vo: 50-160oF, p
sut 75-2500 psi.

40

41

Chng 3: Lm kh kh

42

- Inlet separator: tch tp cht lng v rn (nc t do,

du ha tan (aromatic, asphaltic), mui, ph gia, ct,
g). Gn 50% s c lin quan n qu trnh c ch
to hirat bng hp th l do cng on ny. Nn
c thit k chu c lu lng max 125% lu
lng kh vo.
- Reboiler: hi nc t reboiler li cun nc (v
hidrocarbon nh nu c) trong dung dch vi glycol.

43

44

Chng 3: Lm kh kh

3.2.3. Lm khan bng phng php hp ph

Da trn kh nng ht m t kh ca cht rn c
cu trc xc nh nhit thp v gii hp chng
nhit cao.
L qu trnh vt l, hiu qu ty thuc vo nhit
, p sut v bn cht chp hp ph.
ng dng lm kh su kh n -85 -1000C.

45

Chng 3: Lm kh kh
Cc cht hp ph thng s dng:
Al2O3
Silica gel
Ry phn t (zeolite): khi cn h im sng n -85
-1000C.

46

Chng 3: Lm kh kh

Ch s
Hnh dng
Kch thc, mm
L xp ni, %
T trng nn, kg/m3
ng knh trung bnh l xp, nm
B mt hp ph hat ng, m2/g
Nhit dung, kJ/kg 0C
dn nhit, kJ/kg 0C
Nhit hp ph cc i, kJ/kg nc

Al2O3

Silica gel

Zeolite

Tr, vin, cu,

bt
0,6-6,0
25-40
480-850
6,0-20,0
100-300
1,005-1,047
795-1172
4787

Cu, bt
2,4-4,0
30-40
400-770
3,5-14,0
200-900
0,921
795
4187

Tr, cu, bt
1,6-3,2
30-35
480-800
0,3-1,0
500-800
0,837
4187

47

Chng 3: Lm kh kh

c im ca phng php hp ph
- Hiu qu hn qu trnh hp th bng TEG
- C th lm kh n thp hn 0.1 ppm H2O
- Hiu qu kinh t v mi trng tt
- Thng c s dng cng vi mt qu trnh hp th bng TEG:
+ Thp hp th bng TEG lm kh n khong 60 ppm
+ Thp hp ph tip tc lm kh n 0.1 ~ 1 ppm

48

Chng 3: Lm kh kh
Qu trnh hp ph ta nhit nhit cht hp
ph tng ln trong qu trnh hp ph.
Trong s hp ph chu k, c t 2-3 thp lm
cc nhim v: hp ph, gii hp, lm lnh cht hp
ph.
Nhit han nguyn cht hp ph: 176-2040C
(Al2O3, silica gel); 316-3700C (zeolite).
Nhit han nguyn c nh hng n kh
nng hp ph v lng gim nhit im sng
ca cht hp ph.
Thi gian lm vic ca cht hp ph: 2-5 nm.

49

Chng 3: Lm kh kh
La chn cht hp ph:
Silica gel: lm kh n im sng -53 -570C.
t st: lm kh n im sng -550C.
Al2O3: lm kh n im sng -610C.
Zeolite NaA: lm kh n im sng -70 -750C.

50

Chng 3: Lm kh kh
Yu cu v c tnh ca cht hp
ph
- Kh
nng hp ph cao ti trng thi cn bng
+ gim th tch cht hp ph cn thit, gim chi ph v nng lng qu
trnh gii hp
- chn la cao
+ gim mt mt cc kh
- D gii hp
+ Nhit gii hp thp, gim chi ph nng lng
- gim p nh
- Tnh cht c hc tt
- R, tr v mt ho hc, khi lng ring ln v khng thay i th tch nhiu
trong qu trnh hp ph
- Din tch b mt, kch thc mao qun
51

Chng 3: Lm kh kh

Silica gel
- R
- D gii hp
- Kh nng hp ph cao: c th hp ph lng nc bng 45% khi lng ca n
- Thi gian s dng lu
- Hp ph n 5-10 ppm nc

52

Chng 3: Lm kh kh

Alumina
- C tnh cht c hc tt nht
- Hp ph c kh chua (H2S, CO2)
- D gii hp nht
- Hp ph n 10-20 ppm nc

53

Chng 3: Lm kh kh
Ry phn t (Zeolite)
- Hp ph n 0.1 ppm nc
- C cu trc mao qun kch thc u v c th iu khin c
- C kh nng hp ph kh chua
- t nht trong cc cht hp ph
- Nhit gii hp cao nht
- Chi ph cho qu trnh hp ph vi zeolite l cao nht

54

Chng 3: Lm kh kh
t im sng ca kh thp v lng gim
im sng cao:
Lm kh hn hp 2 giai an: giai an 1 dng phng
php hp th, giai an 2 dng phng php hp ph.
Lm kh bng hp ph tng hp: bc 1 hp ph trn
silica gel hoc Al2O3, bc 2 hp ph trn zeolite. Phng
php ny cho php lai vt nc ra khi dng kh v kh
c im sng thp.

55

Chng 3: Lm kh kh

u, nhc im ca phng php lm kh bng hp

ph
u im

Nhc im

Khang bin thin thng s

u t ln.
cng ngh rng.
Chi ph vn hnh cao.
Cho php nhn c im
Khng c cc qu trnh lm
sng thp v gim im vic lin tc trong tng cng
sng cao.
an hp ph, gii hp, lm
n gin, tin cy cao.
ngui.
Hiu qu hp ph gim dn
do b u c bi cc cht c
ch n mn v cc hp cht
ha hc khc dn n phi
thay mi.
56

Chng 3: Lm kh kh

Mt s im cn lu khi hat ng thit b kh nc bng

cht hp ph ry phn t:

S thay i p sut ti lp cht hp ph khng nn vt

qu 50 psi/ph (6 kPa/s).

ng knh lp hp ph khng nn qu ln.

Khi kh nng hp ph gim v gim p sut tng

mnh, cht hp ph nn c thay mi. Thng thng,
cht hp ph ry phn t mt 35% hat tnh sau thi
gian hat ng 1-3 nm; hoc mt 50% hat tnh sau
1600 ln ti sinh.
57

Chng 3: Lm kh kh

Thng thng, cht hp ph ry phn t 4A c kh nng

hp ph 20 lb nc/100 lb ht i vi ht mi, v 13 lb
nc/100 lb ht i vi ht s dng iu kin 75 oF
(24oC).

58

Chng 3: Lm kh kh

59

Chng 3: Lm kh kh
Bng chuyn i n
v
F = 0C x 1.8 + 32
0
R (Rankine Temperature) = oF + 460
0

1 psi = 0.068 bar = 6.8 kPa

1 lb = 0.454 kg
1 ft = 0.305 m
1 inch = 0.0254 m
MMscfd ~ milion standard cubic feet per day
60

Chng 3: Lm kh kh

Bng iu kin
chun
H
SI
Universal scientific
Nat. gas industry
American
engineering

273.15K

0oC
60oF
32oF

P
101.325
kPa

V
22.415
m3/kmol
22.415 L/mol

760 mm Hg
14.7 psi
1 atm

379.4 ft3/lb
mol
359.05 ft3/lb
mol
61