I HC QUC GIA H NI

TRNG I HC KHOA HC T NHIN

_______________________

Nguyn Th Thu H

NGHIN CU CH TO MT S

H NH TNG SINH NHIT X L,

NGN NGA PARAFIN LNG NG

TRONG NG NG DN DU TH

VIT NAM

Chuyn ngnh: Ha du

M s : 62440115

(D THO)TM TT LUN N TIN S HA HC

H Ni - 2015

Cng trnh c hon thnh ti:

Trng i hc Khoa hc T nhin HQGHN

Ngi hng dn khoa hc:

1. PGS.TS HOA HU THU

2. TS NGUYN TN HOA

Phn bin 1:

Phn bin 2:

Phn bin 3:

Lun n s c bo v trc Hi ng cp i hc Quc

gia chm lun n tin s hp ti..........

Vo hi .. gi ngy .. thng .. nm 20..

C th tm hiu lun n ti:

- Th vin Quc gia Vit Nam

- Trung tm Thng tin - Th vin, i hc Quc gia HN

1

M U

1. Tnh cp thit ca ti

Lng ng parafin (LPA) l mt trong nhng thch thc ln

nht v an ton dng chy du, vn chuyn du, tng tr du, khai

thc du cn (ng) khai thc, c bit khi khai thc du vng bin

ngoi khi c su ln. Khi LPA xy ra phi dng qu trnh khai

thc x l cc LPA ny.

ngn nga tc ng dn du, LPA cn c loi b nh

k v iu ny v cng tn km. V d, x l LPA trn ng ng

dn du th trn bin, su 100m cn tiu tn 200.000 USD, nu

su 400m cn 1.000.000 USD v gi thnh cng tng khi su

cng ln.

C nhiu phng php x l khc nhau bao gm x l bng

c hc, nhit, ha hc...

Bn cnh vic x l LPA, trong thc t cn cn phi c ch

LPA nguyn pht v y l bin php ngn nga trc cc hin

tng LPA. C nhiu phng php c a ra ngn nga

LPA: thm cc ph gia ha hc nh cc cht h im ng c

(PPD), cc cht km hm s kt tinh ca parafin, cc cht bin i

tinh th parafin hay cc cht ci thin dng lnh. y l cc phng

php thc t nht, kinh t nht v c dng nhiu nht trong cng

nghip khai thc, vn chuyn du th gii quyt vn LPA.

Du th Vit Nam rt giu parafin. cc ging khai thc theo

cng ngh khai thc gaslif, hin tng LPA cn xy ra gp nhiu

ln so vi cc cng ngh khai thc khc.

Chnh v th, trong lun n ny, chng ti nghin cu ch to

mt s h nh tng sinh nhit x l, ngn nga LPA trong ng

khai thc du th Vit Nam. Thc cht y l phng php nhit

2

kt hp vi dung mi, mt trong ba phng php ph bin x l

LPA, ng thi kt hp vi vic s dng cc cht h im ng

c (PPD) nng cao hiu qu loi b v ngn nga LPA nhm

ko di thi gian lm vic ca cc ng khai thc trong iu kin Vit

Nam, trnh cc ch tc do LPA, nh vy nng cao hiu qu kinh t

trong khai thc v c th vn dng cho vn chuyn du th trong

cng nghip du kh, nhng iu kin a hnh, nhit mi

trng khc nhau, vt c nhng thch thc ca hin tng

LPA trong cng nghip khai thc, vn chuyn du th.

2. i tng v phm vi nghin cu

2.1. i tng nghin cu

- Nghin cu, ch to cc h nh tng sinh nhit d trn cc phn

ng sinh nhit c bn: phn ng oxi ha kh v phn ng axit

baz v tm iu kin ti u khi s dng cc h nh ny cho x l

LPA trong ng khai thc;

- Ch to mt h cht h im ng c (PPD) kt hp vi h cc

cht activator c ch qu trnh LPA nguyn pht trong va hoc

vng cn y ging khai thc.

2.2. Phm vi nghin cu

Cc h ha phm sau khi ch to c p dng x l LPA trong

ng khai thc v c ch LPA trong m hnh va.

3. Nhng ng gp mi ca lun n

1. Nghin cu c h thng mt s h nh tng sinh nhit trn c s

ca cc phn ng ha hc nh phn ng oxi ha kh, trung ha

gia cc axit baz hu c nhm mc ch x l lng ng parafin

trong ng ng khai thc cc ging khai thc gaslift Vit Nam;

2. tm c cc iu kin to thnh vi nh nc trong du W/O

ca cc h dung dch nc NH4Cl+CH3COOH/Du, dung dch nc

3

NaNO2/Du c bn vng tha mn yu cu cng ngh x l

LPA ng khai thc gaslift:

3. nghin cu ch to thnh cng v tm c cc iu kin ti u

cho s hnh thnh cc h nh tng: cht hu c phn cc ( l cc

axit hu c hay cc baz hu c) x l LPA trong ng khai thc

m khai thc gaslift.C hai h nh tng ny u c bn nh

cao, d dng vn chuyn t ni ch to n ni x l LPA vi kh

nng x l cao do t c nhit Tmax ln. Tc dng loi b

LPA quy m phng th nghim.: vi h ha phm oxi ha kh,

kh nng loi b LPA l 77% v vi h ha phm axit baz, kh

nng loi b LPA l >88%;

4. a ra phng php s dng cht h im ng c PPD c

ch s lng ng parafin, l PPD Sepaflux ES-3363 kt hp vi

mt h activator c tc dng khng km activator nhp ngoi trong

vic ngn nga LPA. H activator ny l h ha phm VCA-12 bao

gm 60% n-butanol v 40% iso-butanol.

4. B cc ca lun n

Ton b ni dung Lun n c trnh by 152 trang, gm cc phn: M

u (2 trang), Chng 1. Tng quan l thuyt ( 50 trang), Chng

2. Thc nghim (12 trang), Chng 3. Kt qu v tho lun (55 trang),

Kt lun (2 trang). Trong lun n c 26 bng biu, 58 hnh v, 139

ti liu tham kho. Phn ln kt qu ca Lun n c cng b

trong 5 bi bo trn cc tp ch khoa hc uy tn trong nc.

NI DUNG CHNH CA LUN N

CHNG 1: TNG QUAN

1.1. Cc vn lin quan n h nh tng nc/du

Tng quan mt s l thuyt v: khi nim nh tng, phn loi

nh tng, phng php ch to nh tng; nh tng nc trong

4

du v cc yu t nh hng n n nh ca nh tng; cc tc

nhn to nh v phn loi;

1.2. Cc vn lin quan n s lng ng parafin

Tng quan v: nh ngha LPA; cc tnh cht ca LPA (

cng, rn, nhit nng chy, t trng, ha tan); cc yu t nh

hng n LPA (nhit , thnh phn ca du th, p sut, nhng

yu t nh hng khc); c ch LPA (cc c ch LPA, nghin

cu c ch LPA trong cng nghip du kh);

1.3. LPA trong cng nghip khai thc du kh

Xt cc lng ng parafin trong cc qu trnh cng nghip khai thc,

vn chuyn, tng tr v bo qun du th.

1.4. Cc phng php x l LPA

Bao gm cc phng php c hc, vt l, ha hc v ha l

1.5. Tnh hnh nghin cu, ng dng nhng cng ngh x l v

ngn nga LPA trn th gii v Vit Nam

CHNG 2: THC NGHIM V CC PHNG PHP

NGHIN CU

Cc mu LPA c ly t cc ging du khai thc gaslift ti X

nghip Lin doanh Vietsovpetro;

Xc nh lng nhit sinh ra ca cc phn ng hc sinh ra trong

cc h vi nh bng phng php nhit lng k;

Xc nh ha tan LPA bng h nh tng sinh nhit bng

phng php mt khi lng;

Xc nh nht bng phng php o nht ng hc;

Xc nh tnh cht, thnh phn, hnh thi ca LPA bng phng

php sc k kh nhit cao; phng php o nhit ng c;

phng php o nhit nng chy, phng php chp nh hin vi

in t qut.

5

Xc nh tc dng c ch LPA ca PPD bng phng php o

nhit ng c

Xc nh mi trng lm vic ca h nh sau khi ch to bng

phng php o pH

S thit b phng th nghim m phng x l LPA trong ng

khai thc bng cc h vi nh tng sinh nhit

Hnh 2.5: S th nghim x l LPA theo phng php s dng vi

nh tng sinh nhit kt hp vi dung mi *

Thi gian dng ha phm t n cc v tr 20, 30, 40m trong

ng ng (1) c xc nh theo cng thc:

t =d2. l. 60

4.

Cch tin hnh th nghim: LPA c ly t ging khai thc ca

XNLD VietsovPetro

+ Chun b mu LPA: Lm nng chy LPA v trng vo cc ng

mu. Cn chnh xc lng LPA a vo ng v l lng

LPA g0. Lp cc ng mu vo cc v tr 20, 30, 40m trn ng th

nghim 50m.

+ Tnh ton thi gian bm vi cc lu lng khc nhau, sau bm

h ha phm t thng (4) vo ng ng v lc ny nhit ca h

ha phm t c ti mt gi tr xc nh T0 ngay u vo ca

ng ng. Trong thi gian cht lng chy trong ng ng, nhit

s tng dn do phn ng ha hc sinh nhit tng dn theo chiu di

6

ca ng. Ti cc v tr 20, 30 v 40m nhit ca dng cht lng t

c cc gi tr T1, T

2, T

3 (c c trn cc ng h 3). Ghi nhit

v thi gian o c ti cc im ny.

+ Khi ton b lng ha phm (60 lt) chy ht qua ng ng, tho

cc ng mu, cn lng LPA cn li trong ng mu. Ghi li cc gi

tr ny tnh hiu qu x l, H.

CHNG 3: KT QU V THO LUN

3.1. Kt qu xc nh tnh cht ha l ca cc mu LPA mt

s ging khai thc Vit Nam

3.1.1. Thnh phn v nhit nng chy ca parafin m du

Bch H v Rng Bng 3.1: Nhit nng chy ca mt s cc parafin rn trong LPA m

Bch H

TT Ankan Cng thc Nhit nng chy, oC

1 n-octadecane C18H38 28,0

2 n-nonadecane C19H40 32,0-34,0

3 n-licosane C20H42 36,7

4 n-heneicosane C21H44 39,0

5 n-docosane C22H46 42,0

6 n-tricosane C23H48 47,7

7 n-tetracosane C24H50 49,0-52,0

8 n-pentacosane C25H52 53,3

9 n-hexacosane C26H54 56,4

10 n-heptacosane C27H56 -

11 n-octacosane C28H58 64,5

12 n-nonacosane C29H60 -

13 n-triacontane C30H62 66,0

14 n-hentriacontane C31H64 67,9

15 n-dotriacontane C32H66 67,0-72,0

16 n-tritriacontane C33H68 -

17 n-tetratriacontane C34H70 -

18 n-pentatriacontane C35H72 -

19 n-hexatriacontane C36H74 -

20 n-heptatriacontane C37H76 -

21 n-octatriacontane C38H78 -

22 n-nonatriacontane C39H80 78,0-82,0

23 n-tetracontane C40H82 81,3

7

Nhn xt: - Nhit nng chy ca cc LPA l khong >60oC, ph

thuc vo thnh phn cc n-parafin trong mu lng ng;

- Thnh phn chnh trong LPA l n-parafin (chim khong >80%);

asphanten v nha chim 3-4%, cn li l phn on nh v cc

khong v c, nc...

3.1.2. Phn b LPA dc theo ng (cn) khai thc

Nhn xt: parafin c th bt

u kt tinh su

1.500m, cn su

1.000m lng ln parafin

c th bt u kt tinh.

Hnh 3.1: Quan h Nhit - su ging 64

Tuy nhin do c s chuyn dch ln gia v tr bt u kt tinh so vi

v tr lng ng, nn chiu su c xc sut cao trong LPA thng

khng vt qu 1.000 1.200m. Chiu su ny lin quan mt thit

vi lng ha phm cn trong cng tc x l loi b lng ng.

3.1.3. Phn tch hnh thi LPA (nh SEM)

Hnh 3.2: nh SEM ca cc LPA m Bch H

8

Hnh 3.2 cho thy hnh thi hc ca lng ng parafin khng

c hnh dng xc nh. Cc lng ng ny ging hnh vy vi kch

thc vy khong 1 m.

3.2. Kt qu ch to cc h nh tng ha phm sinh nhit da

trn phn ng oxi ha kh

3.2.1. Kh nng sinh nhit v ng hc ca phn ng NH4Cl v

NaNO2

3.2.1.1. nh hng ca nng xc tc H+

Gi khng i nng : [NH4Cl]o = [NaNO2]o = 4M; thay i

nng axit axetic [CH3COOH] tng ng l 0,1M, 0,24M, 0,6M,

0,8M, 1M, 1,2M, 1,4M v 1,6M. Bng 3.2: nh hng ca nng axit khc nhau ti tc phn ng

c biu th bng Tmax (nhit t im cc i ca hn hp phn ng)

TT Nng axit

axetic, M Tmax,

oC Thi gian t

Tmax, pht Ghi ch

1 0,1 54 16 Phn ng chm ko di

2 0,24 76 13 Phn ng chm

3 0,6 82 9 Phn ng trung bnh

4 0,8 87 7 Phn ng nhanh

5 1 94 6 phn ng nhanh

6 1,2 98 5 phn ng nhanh

7 1,4 97 5 Phn ng nhanh

8 1,6 96 5 phn ng nhanh

- Nhn xt: tc bin thin ca nhit tng nhanh khi tng hm

lng axit tng, chng t axit axetic l cn thit cho phn ng ny v

iu ny hon ton ph hp vi l thuyt ca phn ng.

- Vi nng [NH4OH]o = [NaNO2]o = 4M th nng axit axetic

1,2M l thch hp nht cho phn ng.

3.2.1.2. nh hng ca nng NH4Cl

Gi nng [NaNO2] khng i khong 4M, xc tc axit acetic

cng c gi nguyn khng i l 1,2M, cn nng ca [NH4Cl]

thay i t 1,2 n 4,4M.

9

- Nhn xt: khi nng NH4Cl

tng th nhit ti a tng ln, do

tc phn ng tng ln, trong khi

thi gian t nhit Tmax gim

xung. Hnh 3.3: Quan h gia nng NH4Cl,

thi gian t Tmax v nhit phn ng

V l do cng ngh, thc t chng ti chn [NH4Cl]=4M,

[NaNO2]=4M v [CH3COOH]=1,2M cho nhng nghin cu tip

theo.

3.2.2. Kh nng to nh ca dung dch cc cht phn ng NH4Cl

v NaNO2

3.2.2.1. La chn cc cht HBM

Trong lun n ny, chng ti chn cht HBM: Span 80,

Tween 20, ethoxylate alcohol, NP9 nghin cu kh nng nh ha

ca chng, v y l cc cht nh ha d kim v tng i r.

3.2.2.2. Chun b cc cht HBM

Nh vy c 4 cht HBM l nguyn cht v 9 mu l hn hp

ca hai cht HBM c cc t l khc nhau.

3.2.2.3. Cc iu kin la chn cht HBM

- Pha du: Kerosen, c tc dng nh dung mi ha tan parafin; - Pha

phn tn: Cc dung dch NH4Cl 4M, NaNO2 4M; - T l pha

nc/pha du = 1:3; - Xc tc axit axetic: 1,2M (pha trong dung dch

NH4Cl); - T l cc cht HBM: 3%KL; - Nhit pha lin tc:

35oC;- Tc khuy: 2.500 vng/pht; - Thi gian khuy: 7 pht.

* Vi hn hp cht HBM Tween20 + Span 80

* Vi hn hp cht HBM Ethoxylate alcohol + Span 80

10

Bng 3.3: Kh nng sinh nhit ca h nh tng s dng hn hp HBM

Ethoxylate alcohol + Span 80

TT T l Span 80

/Ethoxylate

Tmax, oC

Thi gian t

Tmax, pht

bn nh

NH4Cl, %

bn nh

NaNO2, %

1 0 83 8 12 9

2 20 65 29 27 25

3 40 76 14 22 19

4 60 81 9 14 11

5 80 86 8 8 6

6 100 89 7 3 2

Hnh 3.4: Quan h gia loi cht HBM v bn nh, nhit Tmax ca h

* Vi hn hp cht HBM NP9 + Span 80:

- Nhn xt: hn hp cht HBM Ethoxylate + Span 80 cho hiu qu

nh ha cao nht; h nh tng tng i bn, m bo thi gian

bo qun, vn chuyn v bm ha phm; vi thnh phn 60%

Ethoxylate + 40% Span 80 cho hiu qu sinh nhit tt nht.

3.2.3. La chn pha du dung mi

- Pha du: cc dung mi kerosen, heptane v hn hp ca chng; -

Pha nc: Dung dch NH4Cl 4M, NaNO2 4M; - T l pha nc/pha

du = 1:3; Thi gian khuy: 7 pht.- Xc tc axit axetic: 1,2M (pha

trong dung dch NH4Cl);- T l cc cht HBM: hn hp 60%

Ethoxylate + 40% Span 80; 3%KL; Nhit pha lin tc: 35oC; Tc

khuy: 2.500 vng/pht;

* Vi hn hp dung mi kerosen + xylen

11

Bng 3.4: Nhit Tmax v hiu qu x l parafin khi s dng h dung mi

kerosen + xylen

STT % xylene trong

kerosen Tmax,

oC Thi gian t

Tmax, pht

% parafin ha

tan Ghi ch

1 0 72 14 68 Y

2 20 74 14 77 N

3 40 75 14 79 Y

4 60 74 14 76 Y

5 80 74 14 76 Y

6 100 75 14 74 Y

* Vi hn hp dung mi heptan +

xylen

- Hn hp dung mi 20% Xylene +

80% kerosen cho hiu qu ha tan

parafin tng i tt v khng c s

lng ng tr li ca parafin theo

thi gian v hn hp ny cng m

bo kh nng sinh nhit, lm sch,

va m bo yu t gi thnh ca h

ha phm.

Hnh 3.5: Quan h gia % xylen

trong kerosen v kh nng t

nhit ti a Tmax, ha tan

parafin

3.2.4. Cc yu t nh hng n kh nng sinh nhit v kh nng

x l LPA

3.2.4.1. nh hng ca nng cht HBM

- Pha du: dung mi hn hp 20% xylen + 80% kerosen; - Pha nc:

Dung dch NH4Cl 4M, NaNO2 4M; - T l pha nc/du = 1:3; -

Xc tc axit axetic: 1,2M (pha trong dung dch NH4Cl); - T l cc

cht HBM: hn hp 60% ethoxylate + 40% span 80, vi cc nng

thay i t 1 - 6%; - Nhit pha lin tc: 35oC; - Tc khuy:

2.500 vng/pht; Thi gian khuy: 7 pht.

12

Bng 3.5: Th nghim kh nng sinh nhit v hiu qu x l parafin nng

cht HBM khc nhau

STT Nng

HBM, % Tmax,

oC

Thi gian

t Tmax,

pht

bn nh

NH4Claq, %

bn nh

NaNO2aq, %

% parafin

ha tan

1 1,0 90 7 2 1 84

2 2,0 81 10 14 11 82

3 3,0 74 14 22 19 77

4 4,0 68 18 27 24 68

5 5,0 62 22 30 27 51

6 6,0 58 27 31 28 30

Hnh 3.6: Quan h nng HBM ti

bn nh v nhit ti a Tmax

Hnh 3.7: Quan h nng HBM ti

kh nng ha tan parafin

- Khi tng nng cht HBM th bn nh tng tng ln nhng

kh nng sinh nhit v ha tan parafin gim xung; nng cht

HBM 3% l nng ti u i vi h cha 25% dung mi.

3.2.4.2. nh hng ca hm lng pha du

- Pha du: dung mi hn hp 20% xylen + 80% kerosen; - Pha nc:

Dung dch NH4Cl 4M, NaNO2 4M; - T l pha nc/pha du: thay

i; - Xc tc axit axetic: 1,2M (pha trong dung dch NH4Cl); - T l

cc cht HBM: hn hp 60% Ethoxylate + 40%span 80, thay i

ph hp vi nng dung mi; - Nhit pha lin tc: 35oC; - Tc

khuy: 2500 vng/pht; - Thi gian khuy: 7 pht. Bng 3.6: bn nh ha, kh nng ha tan parafin cc nng dung mi

khc nhau

TT

Nng dung

mi/ cht

HBM, %

Tmax, oC

bn

nh ca

NH4Claq %

bn nh

ca NaNO2aq

%

%

parafin

ha tan

Ghi ch

1 20 2,4 83 28 20 71

2 25 3 74 19 14 77

13

3 30 3,6 70 9 5 76 Kh to nh

4 35 4 65 4 1 72 Kh to nh

5 45 4,5 59 - - - Phn lp

6 50 5 54 - - - Phn lp

3.2.4.3. nh hng ca tc khuy

- Pha du: dung mi hn hp 20% xylen + 80% kerosen; - Pha nc:

Dung dch NH4Cl 4M, NaNO2 4M; - T l pha nc/du = 1:3; -

Xc tc axit axetic: 1,2M (pha trong dung dch NH4Cl); - T l cc

cht HBM: hn hp 60% Ethoxylate + 40%span 80; 3%; - Nhit

pha lin tc: 35oC; - Tc khuy: thay i t 1.500 4.000

vng/pht; - Thi gian khuy: 7 pht. Bng 3.7: bn nh ha, kh nng ha tan parafin cc tc khuy khc nhau

TT

Tc

khuy,

vng/pht

Tmax, oC

Thi gian

t Tmax,

pht

bn nh

ca

NH4Claq, %

bn nh

ca NaNO2aq,

%

%

parafin

ha tan

1 1500 83 7 14 9 84

2 2000 76 10 17 12 82

3 2500 74 22 19 14 77

4 3000 69 19 22 17 68

5 3500 63 23 23 18 51

6 4000 58 27 24 19 36

- Nhn xt: t 1.500 2.000 vng/pht b nh tng tng nhanh,

cn t 3.500 4.000 vng/pht bn nh tng khng ng k.

Hnh 3.8: nh hng ca tc

khuy n bn nh, Tmax v kh

nng ha tan LPA

Hnh 3.9: nh hng ca tc khuy

ti thi gian t nhit ti a

14

Hnh 3.10: nh hng ca tc

khuy ti kh nng lm sch parafin

3.2.5. Ch to ha phm nh tng sinh nhit t phn ng oxi

ha kh

3.2.5.1. Chun b cc dung dch mui

3.2.5.2. To h nh tng Hnh 3.11: S nguyn l ch to cc h

nh tng

Hnh nh SEM thu c t cc

nh tng ch to

Hnh 3.12: Hnh nh SEM ca nh tng (kerosen+ xylen)/Dd nc NaNO2 v nh tng (kerosen+ xylen)/Dd nc NH4Cl

3.2.5.3. nh hng ca s hnh thnh nit trong phn ng oxi ha

kh

Do phn ng gia cc mui c sinh ra kh N2 c th xy ra cc hin

tng: - Hnh thnh bt nc/du/Nit; - Tng th tch chon ch

ca cht lng v gim s mt mt nhit ra mi trng; - Tng p sut

trong ng ng: gy ra h hng ng ng, c bit l khp ni

gia cc ng ng.

15

khc phc mt s nhc im ca hai h vi nh tng trn phn

ng oxi ha kh, chng ti tip tc nghin cu ch to hai h nh

tng sinh nhit t phn ng trung ha.

3.3. Kt qu ch to cc h nh tng sinh nhit t phn ng

trung ha

3.3.1. Kt qu th nghim khi s dng baz l etanolamin

Nhn xt: - T l mol baz:axit = 1,2:1,0 to hn hp sn

phm c mi trng kim, pH ~ 9;

Thnh phn thit k cho hn hp phn ng nh sau: + T l mol

baz: axit = 1,2:1; + Hm lng axit axetic chim trn 30% khi

lng hn hp hai axit;

+ Hm lng dung mi chim 35 % khi lng khi phn ng.

3.3.2. Kt qu th nghim khi s dng baz l etylenamin

Nhn xt: Nhit Tmax ca khi phn ng rt cao, c th ln ti

>100oC (124

oC t l mol B/A=1,3 hoc 118

oC t l mol

B/A=1,2). l do etylen iamin c tnh baz mnh hn etanol

amin, tuy nhin sn phm phn ng c nht cao.

3.3.3. Kt qu th nghim khi s dng baz l n-butylamin

Nhn xt: n-butylamin (H2N-CH2-CH2-CH3) cho nhit Tmax t

c kh cao v ng u ~110oC, nht thp t 8,5-9,5. y l

cc kt qu rt thch hp chn n-butylamin l baz cho phng

php ny.

3.3.4. Kt qu th nghim khi s dng baz l N,N-ibutylamin

Nhn xt: Nhit Tmax thp, t 85-87oC, nht ca sn phm thp

d gy n mn thit b, h sn phm khng bn d tch lp.

3.3.5. Kt qu th nghim khi s dng baz l hn hp ca hai amin

etanolamin (EA) v etylendiamin (EDA). Nhn xt: Nhit Tmax

kh cao, Tmax~110oC, pH cao, nht cao.

16

Bng 3.8: Nhit Tmax ca phn ng ha nhit khi s dng baz l n-butylamin

Thnh phn thit k dung dch phn ng Thng s thu c

TT

T l

baz/axit

(mol/mol)

T l

A.axetic/A.L

AS (%)

Hm lng

DM trong hn

hp (%)

Khi lng n-

butylamin

(g)

Khi

lng

LAS (g)

Khi lng

axit axetic

(g)

Khi lng

DM kerosen

(g)

Tu

(oC)

Tmax

(oC) pH

Ghi ch (cm

quan bng mt

thng)

1 1,2 20 35 58,18 61,55 24,33 60,03 27,0 111 9 nht thp

2 1,2 30 35 43,15 53,07 25,34 73,58 27,0 114 9 nht thp

3 1,2 40 35 55,03 48,98 22,09 68,06 27,5 112 8,5 nht thp

4 1,2 50 35 33,67 46,23 22,57 65,98 27,0 115 8,5 nht thp

5 1,2 60 35 25,55 50,02 20,98 66,45 26,0 115 8,5 nht thp

6 1,2 70 35 32,44 53,67 19,03 64,33 26,0 115 8,5 nht thp

7 1,3 20 35 43,03 55,55 23,22 60,07 25,0 105 9 nht thp

8 1,3 30 35 45,98 52,03 26,58 61,33 27,0 108 9 nht thp

9 1,3 40 35 49,05 50,98 20,07 64,01 25,0 108 9 nht thp

10 1,3 50 35 42,78 51,33 23,98 63,58 25,0 109 8,5 nht thp

11 1,3 60 35 40,98 49,89 35,33 64,97 26,0 110 8,5 nht thp

12 1,3 70 35 41,23 50,56 26,44 62,85 26,0 111 8,5 nht thp

13 1,4 20 35 45,09 54,09 24,66 64,33 27,0 109 9,5 nht thp

14 1,4 30 35 43,45 52,32 25,09 60,99 27,0 109 9 nht thp

15 1,4 40 35 44,35 55,46 23,98 62,54 27,0 107 9 nht thp

16 1,4 50 35 46,09 51,07 22,68 64,39 26,0 110 8,5 nht thp

17 1,4 60 35 47,87 52,90 25,33 63,32 26,0 112 8,5 nht thp

18 1,4 70 35 42,86 52,33 22,88 64,46 27,0 113 8,5 nht thp

Nh vy khi dng hn hp hai amin EA v EDA, hn hp sau phn ng c nht cao v pH cao mc d

nhit Tmax kh cao. iu ny khng thch hp cho s dng cng ngh x l LPA. V vy, trong cc

nghin cu tip theo, chng ti dng baz l n-butylamin.

17

3.3.6. Kt qu th nghim vi hm lng axit axetic khc nhau

Nhn xt: vi t l axit:baz = 1:1,2 v

hm lng axit axetic chim 50% trong

hn hp axit th nhit ca khi phn

ng l cao nht.

3.3.7. Kt qu kho st nh hng ca

thnh phn dung mi (kerosen + xylen)

n nhit cao nht Tmax ca khi

phn ng v kh nng ha tan LPA

Hnh 3.13: S ph thuc ca

nhit ti a Tmax ca phn

ng vo hm lng axit axetic

ng vi cc t l baz:axit

khc nhau

- S dng baz l n-butylamin; - Axit l hn hp ca 50% axit axetic

v 50% LAS; - T l mol gia baz:axit = 1,2 : 1; - Duy tr tng th

tch ca ton b khi phn ng mc 400 ml; - Thnh phn dung

mi gm kerosen v xylen chim 35% tng khi lng phn ng.

Thay i t l gia kerosen v xylen tm c thnh phn dung

mi thch hp; - Nhit ban u ca hn hp phn ng l 26oC.

Bng 3.9: nh hng ca thnh phn dung mi n nhit cao nht ca khi

phn ng v ho tan LPA

TT

Thnh phn DM Thng s thu c Trng thi sn

phm phn ng

c ho tan LPA

sau 24h, 25oC

% KL

kerosen

trong DM

% KL

xylene

trong DM

Tmax, oC

Khi

lng

LPA

u, g

Khi

lng

LPA

cui, g

T l

LPA

ho tan,

%

1 100 0 107 60.03 12.01 80 ng nht

2 90 10 109 59.98 7.32 88 ng nht

3 80 20 110 60.01 5.40 91 To mng mng

trn b mt

4 70 30 111 60.05 3.00 95 To lp mng dy

5 60 40 111 59.95 4.88 92 To lp mng dy

6 50 50 110 59.99 5.49 91 To lp mng dy

18

Hnh 3.14: S ph thuc ca nhit

Tmax ca khi phn ng v kh nng

ho tan lng ng vo thnh phn hn

hp dung mi s dng

Nhn xt: Thnh phn dung mi gm 10% xylen v 90% kerosen c

th ho tan cn lng ng tt hn thnh phn dung mi khng c

xylen; vi thnh phn dung mi ny cng c kh nng dung np

parafin cao hn so vi dung mi c hm lng xylen t 20% tr ln

(khng c hin tng ti lng ng cn, to mng). Do , thnh

phn dung mi thch hp c la chn cho ho phm x l lng cn

lng ng bao gm: 10% xylen v 90% kerosen.

So snh u nhc im ca 2 h nh tng sinh nhit trong x

l LPA Bng 3.10: So snh u, nhc im ca cc h nh tng c ch to t cc

phn ng oxi ha kh v cc phn ng axit baz

TT Tiu ch nh gi

H nh tng c to

thnh t phn ng oxi

ha kh

H nh tng c to thnh

t phn ng trung ha

1 Nhit cao nht t c Tmax

, o

C 98 110

2 Kh nng ha tan LPA, % 77 80, ng nht

3 bn nh Kh bn Bn

4 nht Thp Thp

5 pH < 7 9

6 Cht HBM S dng h cht HBM Khng phi s dng cht HBM

7 Sn phm ph ca phn ng To ra Nit, mui NaCl Cc cht hu c d b ra tri sau

khi x l

3.4. Kt qu th nghim ngn nga LPA

c ch s lng ng ca cc parafin, chng ti tin hnh

th nghim i vi cc ha phm ngn nga s lng ng ny. Mt

trong cc ha phm s dng hin nay rt ph bin l dng ha

19

phm lm gim nhit ng c ca du th (PPD) kt hp vi mt

s cc ha phm khc (activator) ngn nga s lng ng ca

parafin trong khai thc du th.

3.4.1. La chn PPD v du th ph hp

i tng nghin cu trong khun kh lun n ny l du th

ca 2 ging 1002 v 1023 thuc gin 10 M Bch H. Trn c s 2

loi PPD ang c x nghip khai thc VSP s dng ( VX7484

ca Nalco, Sepaflux EC 3363) v 2 loi PPD c thu thp trn th

trng ( Basofux PD4119 ca BASF, PAO 83363 ca Baker

Hughes) tin hnh la chn ra mt loi PPD v mt mu du th ph

hp vi nhau nht. Mi loi du c tin hnh th ln lt vi tng

loi PPD trn vi nhng hm lng PPD khc nhau (200, 400, 600,

800, 1000, 1200, 1400, 1500, 1600 ppm). Qu trnh nh lng cho

mi loi PPD c tin hnh nh sau:

3.4.2. Kt qu la chn PPD

3.4.2.1. Kt qu xc nh nhit ng c ca mu du khi nh

lng bng Basoflux PD 4119

3.4.2.2. Kt qu xc nh nhit ng c ca mu du khi nh

lng bng Sepaflux ES-3363

Hnh 3.15: Quan h gia hm lng PPD Sepafux ES-3363 thm vo du vi

nhit ng c ca cc mu du th

20

3.4.2.3. Kt qu xc nh nhit ng c ca mu du khi nh

lng bng VX 7484

3.4.2.4. Kt qu xc nh nhit ng c ca mu du khi nh

lng bng PAO 83363

Nhn xt: Cng mt loi PPD vi cng mt hm lng nh nhau th

tc dng trn cc loi du th khc nhau cng khc nhau. Vi hm

lng PPD Sepaflux ES-3363 l 1000ppm, trn mu du th ging

1002 nhit ng c l 18oC cn trn mu du th ging 1023 l

9oC.

3.4.3. La chn, xc nh hm lng dung mi pha PPD

Vi nhng tiu ch la chn dung mi pha long ra nhm tc gi

la chn dung mi pha long PPD l du Diezen do du Diezen l

loi dung mi thng dng, ho tan tt PPD, rt d mua, t c hi i

vi con ngi, c thnh phn tng ng vi thnh phn ca du

th nn tan hon ton trong du th, khi tan vo du th khng lm

nh hng xu ti cht lng du th. Hn na, hin ti vic s dng

v cung cp du Diezen ti cc gin ca Vietsovpetro rt ph bin

v thng xuyn nn s dng du Diezen pha long PPD ti gin

rt thun tin. S dng t l pha long PPD bng Diezen l

PPD/Diezen = 1/1.

3.4.4. Ch to h ha phm activator

Nhng alcohol c dng kho st kh nng tng tc vi

Sepafux ES-3363 gm: Metanol, Etanol, Propanol, N-butanol, Iso-

butanol, Etylen glycol, Pentanol, Stearyl alcohol. T l gia Sepafux

ES-3363 : alcohol = 1 : 1

iu kin tin hnh: - Nhit 25oC; - T l activator/PPD = 1/1

(40ml activator v 40ml PPD pha long bng Diezen)

21

Nhn xt: Ch c nhng alcohol n chc l c kh nng tng tc

vi ha phm PPD ( y l Sepafux ES-3363); n-butanol v iso-

butanol l cho kt qu tt nht.

Kt qu kho st tng tc ca Sepaflux ES-3363 vi nhng loi

activator ch to c

Sau khi xc nh c nhng alcohol c kh nng tng tc

tt nht vi PPD Sepaflux ES-3363 gm n-butanol v iso-butanol,

tin hnh phi trn hai loi alochol ny vi nhau theo nhng t l (%

th tch) khc nhau t xc nh c ho phm activator vi t

l ca n-butanol vi iso-butanol ti u, c kh nng tng tc tt

nht vi PPD Sepaflux ES-3363. Qu trnh kho st ny c nh

gi thng qua: khi lng gel thu c sau ly tm siu tc sn phm

tng tc gia Sepaflux ES-3363 vi activator; Ch tiu bn gel

v nh gi qua vic th nghim trc tip trn m hnh th nghim.

iu kin tin hnh: - Nhit 25oC; - T l activator/PPD = 1/1

(40ml activator v 40ml PPD pha long bng Diezen)

nh gi qua ly tm siu tc sn phm tng tc gia

Sepaflux ES-3363 vi ho phm activator ch to c

Nhn xt: vi tt c nhng hn hp activator ca n-butanol v

iso-butanol sn phm gel thu c khi cho tng tc vi PPD

Sepaflux ES-3363 u l dng gel. Qua kt qu o bn gel trn

my fann rheometer model 286 nhn thy rng, bn gel ca

nhng ho phm activator vi nhng hm lng n-butanol v iso-

butanol khc nhau cng thay i khi hm lng ca n-butanol thay

i, bn gel t gi tr cao nht ng vi ho phm activator c

hm lng 60% n-butanol, 40% iso-butanol theo th tch.

nh gi qua th nghim trn m hnh th nghim

22

iu kin tin hnh th nghim: - Nhit ct cha vt liu xp:

60oC; - rng hiu dng ca vt liu xp: 37.5%; - Nhit

du thng cha: 60oC; - Tng lng du th qua m hnh:

2000ml; - T l ho phm activator/PPD = 1/1. Bng 3.11: nh hng ca hm lng n-butanol trong hn hp vi iso-butanol

(hn hp activator) ti kh nng nh hp ph PPD vo dng du (nh gi qua

nhit ng c ca du theo th tch du tch ly qua m hnh)

TT

Hm lng n-butanol

trong hh vi iso-

butanol, %V Nhit ng c ca du, oC

n-

butanol

iso-

butanol

Th tch du tch ly qua m hnh, ml

200 400 600 800 1000 1200 1400 1600 1800 2000

1 10 90 9 9 9 21 21 21 24 24 30 30

2 20 80 9 9 15 21 21 27 30 30 30 30

3 30 70 6 9 15 15 15 27 27 30 30 30

4 40 60 9 9 9 21 21 21 24 24 27 27

5 50 50 6 15 15 24 24 24 24 27 27 27

6 60 40 6 9 9 9 9 9 21 21 24 27

7 70 30 6 9 9 9 15 21 21 24 27 27

8 80 20 6 6 6 6 15 15 24 24 27 27

9 90 10 9 12 12 12 27 27 27 30 30 30

Nhn xt: Trong cc t l ca n-

butanol trong hn hp vi iso-

butanol (ho phm activator) th

nghim trn m hnh th t l

60% n-butanol l cho kt qu

gim nhit ng c du th

chy qua lp vt liu xp theo

th tch du tch ly l tt nht.

Hnh 3.16: Quan h gia nhit

ng c ca du vi th tch du tch

ly qua m hnh vi nhng hm

lng n-butanol khc nhau trong hn

hp vi iso-butanol ( rng hiu

dng vt liu xp 37,5%)

T y chng ti chn h ho phm activator ch to c gm 60%

n-butanol v 40% iso-butanol l ho phm activator VCA-12.

23

Bng 3.12: Th nghim i chng kh nng gim nhit ng c ca du khi

s dng ho phm activator EC 6443A ca Nalco v ho phm activator VCA12

ch to c trn m hnh va

TT

Th tch du

tch ly qua m

hnh, ml

Nhit ng c ca du, oC

Ho phm activator

EC6443A (Nalco)

Ho phm activator

VCA-12

1 200 9 9

2 400 9 9

3 600 9 9

4 800 9 12

5 1000 15 18

6 1200 21 21

7 1400 21 21

8 1600 27 27

9 1800 27 30

10 2000 30 30

Hnh 3.17: Quan h gia nhit ng c ca du theo th tch du tch ly

qua m hnh va khi s dng hai loi activator VCA-12 v EC 6443A

Nhn xt: Kt qu thu c khi th nghim trn m hnh va vi hai

loi ho phm activator cng mt iu kin tin hnh thy rng ho

phm activator ch to c (VCA-12) c hot tnh tng ng vi

hot tnh ca ho phm activator thng mi EC6443A. iu ny

chng t rng ho phm activator ch to c hon ton c th s

dng cho cng ngh ngn nga lng ng paraffin bng phng

php hp ph PPD ln b mt va.

24

KT LUN

1. nghin cu c h thng mt s h nh tng sinh nhit trn c

s ca cc phn ng ha hc nh phn ng oxi ha kh, trung ha

gia cc axit baz hu c nhm mc ch x l lng ng parafin

trong ng ng khai thc cc ging khai thc gaslift Vit Nam;

2. nghin cu tm c cc iu kin to thnh vi nh nc trong

du W/O ca cc h dung dch nc NH4Cl+CH3COOH/Du, dung

dch nc NaNO2/Du c bn vng tha mn yu cu cng ngh

x l LPA ng khai thc gaslift: - Nng NH4Cl:4M; - Nng

xc tc CH3COOH: 1,2M; - Nng NaNO2: 4M; - Cht HBM:

hn hp 60% ethoxylate v 40% span 80; 3%; - Dung mi: hn hp

20% xylen v 80% kerosen; - Tc khuy: 2 000 2 500

vng/pht; - Nhit pha lin tc: 35oC; - Thi gian khuy: 7 pht;

3. nghin cu ch to thnh cng v tm c cc iu kin ti u

cho s hnh thnh cc h nh tng: cht hu c phn cc ( l cc

axit hu c hay cc baz hu c) x l LPA trong ng khai thc

m khai thc gaslift: - Baz: n-butylamin; - Axit: l hn hp ca

50% axit acetic v 50% LAS; - T l axit:baz = 1:1,2; - Hn hp

dung mi: 10% xylen : 90% kerosen.

4. th nghim tc dng loi b LPA quy m phng th

nghim ca hai h ha phm oxi ha kh v axit baz, vi kh

nng loi b LPA tng ng l 77% v >88%;

5. nghin cu a ra phng php s dng cht h im ng c

PPD c ch s lng ng parafin, l PPD Sepaflux ES-3363.

ng thi a ra mt h activator c tc dng khng km activator

nhp ngoi trong vic ngn nga LPA. H activator ny l h ha

phm VCA-12 bao gm 60% n-butanol v 40% iso-butanol.

DANH MC CC CNG TRNH CNG B

CA LUN N

1. Nguyn Th Thu H, Nguyn Tn Hoa, Nguyn Khnh Ton,

Hoa Hu Thu (2013) Nghin cu x l lng ng parafin cho

mt s ging du c khai thc bng bm p kh (gaslift)

phn I. Tp ch Ha hc v ng dng, 6(22), Tr. 19-22.

2. Nguyn Th Thu H, Nguyn Khnh Ton, Nguyn Tn Hoa,

Hoa Hu Thu (2013) Nghin cu cng ngh loi b lng ng

parafin (LPA) bng vi nh tng sinh nhit ging khai thc

du th bng bm p kh Vit Nam. Tp ch Ha hc, T.

51(6ABC), Tr. 563-567.

3. Nguyn Th Thu H, Nguyn Tn Hoa, Nguyn Khnh Ton,

Hoa Hu Thu (2014) Nghin cu x l lng ng parafin cho

mt s ging du c khai thc bng bm p kh (gaslift)

phn II. Tp ch Ha hc v ng dng, 1(23), Tr. 30-34.

4. Nguyn Th Thu H, Nguyn Tn Hoa, Quang Thnh, Hoa

Hu Thu (2014) Vai tr ca cht hot ng trong h thng

Dung mi cht gim nhit ng c cht hot ng (DM-

PPD-Act) dng x l lng ng parafin cc ging khai

thc. Tp ch Khoa hc HQGHN, T. 30(5S), Tr. 162-169.

5. Nguyn Th Thu H, Nguyn Tn Hoa, Quang Thnh, Hoa

Hu Thu, Trn Th Nh Mai (2014) Nghin cu cng ngh loi

b lng ng paraffin (LPA) bng phng php s dng cht

h im ng c (PPDs) ging khai thc du th bng bm

p kh (gaslift) Vit Nam. Tp ch Khoa hc HQGHN, T.

30(6S), Tr. 61-68.