T6NG HOP PHU GIA GIAM NHIET DO OONG DAC CHO DAU THO NHlEU PARAFFIN M O BACH HO TRONG KHAI THAC V A VAN CHUYE'N
TREN N§N ESTER CUA POLY-TRIETHANOLAMINE
ThS. Dao Thj Hii Ha, CN. Hoang Linh, KS. LUtfng Min Tuydn V/e/iDdo/(h/Wef/Vam
Tdm t i t
sued mat cua paraffin trong ddu thd ddn den nhiiu hi luy trong khai thdc vd vdn chuyen. Ddu nhiiu parafUn de ddng ddc d nhiit dd eao, nhdt Id trong diiu kiin dudng dng khai thdc vd van chuyen trong mdi trUdng nUde itiin khdng dUde bpc cdeh nhiit vdi mdi trUdng bin ngodi. Mdt sdphu gia gidm nhiet dd ddng ddc (PPD - pour point de- I pressant) dUac nhdp khdu vd sd dung trong nUde cd chdt nen Id polymer bay copolymer cd gdc alkyl (met)aerylati bay maleic [1-3]. Gdn ddy, mdt sd nghiin cufu tdng hap phu gia PPD trin ca sd cdc hop chdt amine vd acid bio cho kit qud khd quan, cd chdc ndng ddng tbdi gidm nhiit dp ddng ddc vd edi thiin tinh lUu biin cbo ddu tbd. Ester cdo polyalkanolamine cd nhieu ddc tinh cua mdt chdt nin gidm nhiit dp ddng ddc hiiu qud cho ddu thd nhiiu parafRn dd mdra hUdng tiep cdn mdi trong viic tdng bap chdt gidm nhiit dp ddng ddc trong phdng thi nghiim. Nghiin cAt sau ddy tiep tbu nhdng tbdnb qud dd vd dixudt hudng nghiin edu dp dung ebo ddu thd nhieu paraffin md Bgch Hi
1. Gidi thieu
Viec sd dung cic biln phip tang eUdng thu hdi diu khiln luong nUde khai thic theo diu tang manh va l i mdt trong nhimg nguydn nhin ehinh lim giim nhidt dp midng gilng. Vile thay ddi cic dilu kien can bing hda ly, die biet l i vile giim nhidt 6g de giy ra hien tuong kit tinh v i Ilng dpng paraffin trong cic dng khai thie, trong h i thdng thu gom, xd ly v i van ehuyin dau, gay ra hien tuong tic nghdn dudng dng v i giim ning suit khai thic.
Hidn nay, phuong phip phd biln dupe cic edng ty khai thie d i u khi i p dung cho diu thd nhieu paraffin l i sd dung hda pham giim nhidt dp dong die (PPD).
Paraffin trong diu thd ehu yiu l i nhdng hydrocarbon no mach thing (n-paraffin, ehilm 80 - 90%), cdn lai l i mdt luong nhd hydrocarbon no mach nhinh, mach vdng (iso- paraffin, cycloparaffin).
Bdng I . Tinh chdt vd nhiit dd ddng ddc ci
Dau thd cua Viet Nam thude hp nhilu paraffin vdl ham lupng > 20%kl. Tinh chat ddng die eua d i u thd phg thude vio him lupng v i bin chit phin bd cua n-paraffin.
Do dd, diu thd eua Viet Nam cd nhidt dp ddng die dao ddng tu 20-36°C (Bingl).
Oie tinh paraffin va sU phin bd n-paraffin eua diu thd d cic md ed nhilu diem khic nhau. Bing 1 cho thiy him lupng n-paraffin eua dau thd mdOai Hung thip hon nhilu so vdi dau thd md Bach Hd va cic md khic. Diu thd
Hinh 1. Cdu true cua paraffin li mgt so md d Viet Nam [1,3,4)
D i e tinh Ty trpng d 20°C H i m luong n-paraffin (%kl) Nhidt d 6 ddng dac (°Q
M 6 R 6 n g ' RC-2 RP-1
0,851 19,6 32
0,892 14,4 30
M d O a i Hung Be Nam C6n Son
0,874 15 22
PM-3 Be Ma L a i - T h d C h u
0,834 28 36
M d B a c h H 5 Bd' Citu Long
0,823
36
PETROVIETNAM
Bdng 2. Nhiit dd ddng ddc cua ddu thd nhieu paraffin cua mdtsd nudc tren the gidi Quic gia .. , , . Trung Quck An Do _ ..
^x r u NewZealand ,_. ' , , „ .• Pakistan Die tinh (Zhongyua) (Nada) Ham luong n-paraffin (%) 35 25 27,83 15.6 Nhidt d6 d6ng die (°C) 30-32
Libya (Sarir) Mexico
3,83 Ngudn: IEA/2010, Hydrocarbon World Vol 5/2010(5,6,7]
cd him luong paraffin cing nhieu thi nhiet dp ddng die cing cao v l nguoc lai (Bing 2).
2. Thi/c nghidm tdng htfp ch^t n i n g i i m nhiet do tfdng tfie
Hiin nay, sin lupng khai thic eua Liln doanh Viet - Nga "Vietsovpetro" ehu y i u la tU md Bach Hd. Trong q u i trinh khai thic v l vin chuyin diu, Ilng dpng paraffin xuat hiin trin dudng dng thu gom diu, trong eae binh chUa, cic phin Ipc hay cic van nim trin dudng thu gom t h i m chf d trong cin khai thie khi nhiet dp rit cao (50 - 70°C).
Do d i u thd md Bach Hd ed nhilu paraffin nen xd ly v i van chuyin diu thd tUcIc gilng khai thie v l t i u ehUa ri't khd khin v l phUe tap.Trong dieu kiln dudng dng van chuyin
dau thd khdng cich nhidt vdi mdi trUdng nude biln, nhidt dp d vung can diy md Bach Hd dao ddng td 22 - 28''C.
thip hon nhidt dp ddng die eua dau tho khoing 10°C.
Do dd, rat de xiy ra sU cd Ilng dpng paraffin, tac nghdn dudng dng, giy thidt hai v l kinh t l .
Chit nen giim nhidt dp ddng die theo dang biln tinh tinh the paraffin ed khi nang Uc chl hoic xen cii trong qui trinh phit trien eua tinh t h i niy. Chit biln tinh tinh the thudng l i cic chat polymer eo khi nang ngan ngUa
Ch^taophugiaPPD
Hinh 2. Ca chi tdc dung cua phu gia gidm
nhiit dd ddng ddc (PPD) lin ddu thd Hinh 3. Tong hgp chdt gidm nhiit do dt Bdng 3. Mdtsd ddc tinh hda ly chung cua ddu thd md Bach Ho [19}
T i n g
D#ctinh ^ TJ trpng d20''C
Nhidt d d d d n g d ^ c C ' C ) Trpng lugng p h i n t i l (g/mol) Od nhdt d nhidt d6 50°C(cSt) Od nhdt d nhidt d d 70"^ (est) H i m lu<?ng luu huynh (% kl) H i m luong n-paraffin (% kl) Nhidt d d nOng c h i y n-paraffin l°Q) H i m luong nhi/a v i asphaltene (% kl) TJ Id (/Asphaltene + Resin)/Paraflin
i-
1 1
1 M i o c e n
dU«i 0,8646
33.8 272,9 12.78 7.18 0,093 20,6 59 9.86 0,48
Oligocen t r e n 0,8477
34.8
Oligocen dUdi 0,8354
35.5 265,9 248.8 19.88
9.31 0,0332 22,8 58 6,19 0.27
6.31 3,77 0.0371 25.8 58 1,80 0,07
OA m o n g
0,8326 34,8 244.4 6,14 3,54 0,0319 25,6 58 2,07 0,08
libini-SO 5/2013 27
I l n g d p n g p a r a f f i n t h o n g q u a vide p h i v d m a m k i t t i n h . d d n g k i t t i n h hoac t h a y d d i c a u t r u e t i n h t h e ; d d n g t h d i c u n g ed t h e h a p p h u Idn c i c t i n h t h e paraffin d l n g a n e i n sU k i t t u h o i c lang d p n g . O i y e u n g la h u d n g n g h i d n eUu d a n g d u p c n h i e u n h i k h o a hpc t r d n t h e g i d i q u a n t a m [ 8 - 1 0 ] .
T h e o n g h i d n c d u [ 1 1 . 12], p o l y m e r hda a l k a n o l a m i n e l i m t i n g k h d i l u p n g p h i n t d . P o l y - a l k a n o l a m i n e k h i p h i n d n g v d i c i c acid b d o k h d i l u p n g cao t a o t h a n h ester ed t i n h chat h o a t d d n g b l m a t , c d k h i n a n g d i l u e h i n h q u i t r i n h k i t t i n h , t r i n h vide k i t t u hay t a o m a n g b i n v U n g cua c i c t i n h t h i paraffin. Q u i t r i n h t d n g h p p v i c h l t a o chat g i i m n h i d t d p d d n g d i e s d d u n g a m i n e v i acid b d o l i n g u y d n lieu p h d b i e n , s i n c d t r o n g nUde, p h u c v u c h o n h i l u n g i n h c d n g n g h i e p . N h d c i c d i e t i n h n i y m i vide t d n g h o p t h i n h e d n g p h u gia g i i m n h i e t d p d d n g d i e sd d e m lai hidu q u i cao v i g i i t h i n h p h u h p p v d i d i l u k i l n c u a Viet N a m .
2 . 1 . Giai dogn 1 - tdng hap poly-triethanolamine
T r u n g n g u n g t r i e t h a n o l a m i n e d n h i e t d p cao (> 200°C) t a o lidn k i t e t h e r (-0-), t i e h n u d c (H^O) v i h i n h t h i n h p o l y - t r i e t h a n o l a m i n e . O p p o l y m e r h d a t d i da eua p h i n Ung t r u n g n g u n g t r i e t h a n o l a m i n e d a t d u o e d d i l u kien n h i d t d p nay l i 6 (m = 6), p o l y m e r c d n d u o e g p i l i h e x a - t r i e t h a n o l a m i n e .
I XuctdcCa(OH)^ \
Xue tdc ZnCI/CHfOOH \
2900 2000
I Xue tdc NaOH \
ZnCl2/CH3COOH
Bdng 4. Ddnh gid hiiu qud ciia cdc logi Nhiet do (°C) 180
Sinh ra nudc Tinh tan cua s i n pham
trong nudc Sinh ra nudc Tinh tan cua s i n p h i m
trong nudc Sinh ra nUdc Tinh tan cua s i n pham
trong nUdc
Lupng nudc sinh ra (ml) 0 Hidu suat p h i n Ung (%)
So song (cm') Hinh 4. Pho hong ngogi cua sdn phdm vdi cdc xue tc
thu polymer ue tdc ddc tinh vd hiiu si
2 0 0
+
•1-
20 Khong tan
Khong tan
r 2 2 - H M |
III^L_H
2 8 B i U i n l - s o 5/2013
PETROVIETNAM
Phuong trinh phin Ung:
CH2CH2OH CHaCHjOH I > 200''C I HOCH2CH2NCH2CH2OH <-» HO - (CHJCHJNCHJCHJO)^ - H -1- (n-1 )H20
Triethanolamine Poly-triethanolamine
Nguydn lieu: triethanolamine tinh khilt, xue tic.
acid acetic 5%. ether dau md (nhiet dp sdi 40 - 60°C).
Thilt bj, dung eu: binh eau 3 ed, sinh hin hdi lUu ngang, bip khuay tU nhiet dp cao.
Thlic nghiem: cho 149g triethanolamine vio binh elu 3 cd, sau dd eho tUtUxue tic kiem vao nguyin lilu dang dupe khuly diu. Duy tri phin Ung d nhiet dp trdn 200°C d i n khi thu dUOc I Upng nUde theo ly thuyet l i 54ml. San phim thu dupe rda qua dung dich acid acetic 5% de hda tan lupng kilm du. Sau khi trung hda, sin pham polymer dupe hda tan trong ether dau md (nhidt dp sdi 40 - ecC) de loai bd cic thinh phin ehUa tham gia phin Ung. Ldp hUu CO thu duoc sau khi chung cat duoe tieh ra khdi dung moi l i poly-triethanolamine Idng, quinh, mau ving nhat.
Kit qui: Oinh g i i eac yeu td nhu nhidt dp, xue t i e va luong nUde sinh ra anh hudng tdi hidu suit phin Ung polymer hoa. Hidu suit phin Ung dupe tinh dUa trdn khdi lUOng polymer thu 6dge sau khi chUng eat d l tich ra khdi dung mdi tinh khilt so vdi khdi lupng sin pham theo ly thuylt.
Ngoai tieu ehi v l lupng nude tich ra, dp tan eua polymer trong nUde cung giup nhan biit lidn kit ether cua polymer cd dUOc tao thinh hay khdng. Kit qui Bing 4 eho thay ehi cd Ca(OH)^ va hdn hpp ZnCI/CHjCOOH l i xue tie phu hpp. Phan tich phd hdng ngoai (IR) de xie dinh ehinh xac hon eau true cua sin pham tao thinh.
So sinh vdi pic hap thu v i dao ddng tU thU vien phd, kit qui phd hdng ngoai trong Hinh 4 v i Bing 5, vdi xue tic Ca(OH)j v i hdn hop ZnCI/CHjCOOH, sin pham polymer thu dupe ed ehUa lidn kit ether d bUde sdng 1.112,48cm' - nhdm ehde die trUng cua poly-triethanolamine. VOi die tinh han chl 6dgc qui trinh tao thinh sin pham mach vong ddi vdi cie alkanolamine, Ca(OH)2 l i xue tic vuot trdi so vdi cic xue tic vdi uu diem tich nUde v i hilu suit tao polymer eao hon.
Bdng 5. Cdc nhdm chdc cd trong sdn phdm thu duge vdi xdc tdc Ca(OH)^
T i n sd dao ddng (cmM 3.474,42 2.870,70-2.948,84
1.455,50
1.358,74 1.048,84
Pic hap thu
1 mui nhpn 3 mui nhon 1 mui nhpn
1 mui nhpn 1 mui nhpn
^ r T ^ Nhomchi^c cua nhom
C-H C-H
Alcol t h i n g CH2 C-H CH2 nitroethane
C-N amine bac 3 C-H i CH2-CH2lienketvdiOH
Sic ky Idng khdi pho LC/MS (Hinh 5) cho thiy polymer tdng hop 6uge vdi dilu kidn nhidt dp xue tic tdi Uu l i hdn hop cic polymer ed dp d i i mach tU 4 trd ldn va dat dp dai mach trung binh Idn nhat la 6 (tuong Ung vdi minh khdi lupng 763).
Polymer thu dupe dap Ung dieu kien ve eau true die trUng de ed t h i tien hinh giai doan 2 eua q u i trinh tdng hpp chat giim nhiet dp ddng die.
H
I n=4 I / 701 27475.51 / / 679A1 I I 610.54 U)tll))|ii>ht*.ili i\
I n=6 I
763.88
1783.57 980.35 112517 1245.60 1369.21 1536.82 1687.77 1905.84 ' " ' l ^ ' ^ I I' ' I l l l -^
800 1000 1200 1400
Hinh 5. Khdi pho LC/MS cua poly-triethanolamine
Kit luan: Oilu kidn tdi uu d l phin Ung trung ngung tao poly-triethanolamine ed lidn kit ether trong elu true: ty I I chit tham gia phin Ung TE/V xue tic l i 1/0.01 khdi lupng, phin Ung dUOc duy tri t r i n b i p khuly tU d nhidt dp 250°C vdi xue tie ehinh l i Ca(OH)j.
2.2. Giai dogn 2-ester hda poly-triethanolamine Sin phim cua phin Ung l i ester (R,-COO-R-,) khi eho acid hOu co phin Ung vdi nhdm chUe rUpu cua polymer. Polyalkanolamine tao ra d giai doan 1 phin Ung vdi acid earboxylic tao ester cd hidu q u i trong vide biln ddi kit tinh tinh t h i paraffin trong diu thd. Acid eho phin Ung ester hda l i nguyin lieu quan trpng inh hudng d i n die tinh cda sin phim. Cic acid cd khdi lupng phin tdcao (nhu acid laurie C^^H^fi^ acid myristic C,,HjjOj, acid palmitic C^^H^p^. acid stearic C^Jti^p^, acid oleic C,3H„0j,acid linoelic C^Jti^p^, acid rieinoleic C,gH„03,aeid mylissic Cj^H^Oj) dupe sddung de ting xu hudng hda tan trong pha dau eua ester sin pham, tinh chit hut diu (lipophile) eua sin
pham sd tang Idn. Sddung acid beo nhU acid oleic i t ^ khdng bio hda) hoic acid stearic (C,g bao hOa) thi tinh tham d i u cda estert?o thinh dupe tang Idn ding k l .
O
So sbng (cm')
Hinh 7. Phd hdng ngoai (IR) cCia ester poly-triethanolamine g 6. Cde nhdm chdc ed trong ester poly-triethanolamine tong hap dugc Tin %6 dao tf^ng 1 Pic
(cm') hip thu 3.444,64 j 1 mui nhpn 2.924,87 - 2.860,79 | 1 mui nhpn 1.652,37 j 1 mui nhpn 1.459,90 } 1 mui nhpn 1.370,85 I Imijinhpn 1.175,51 ] 1 mui nhpn 1.048,84 i 1 mui nhpn
Dao ddng cfla nhdm 0-H C-H C=C C-H cua CH3
C-N C-C C-C cda CH2
NhdmchilTc Ruou
CH2 CH=CH cua nhinh acid
CH3 cua nhinh acid amine bic 3 CC cda nhinh acid CHj-CHjIidnkltvdiOH
Acid stearic
Hinh 6. Cdu tnic hda hgc eua acid oleic vd acid stearic Acid oleic cd he sd cin bing nUde diu (HLB) t h i p nhit (~1) ndn cd the hda tan tdt trong dIu ma lai tan rit it trong nude. Vi viy, acid oleic dupe lua ehpn lim nguyen lieu d l thuc hien phin Ung ester hda vdi polymer tao thinh.
Phuong trinh phin dng:
C H J C H J O H O C H J C H J O H
I x o . . . II I
HO(CH;CH2NCH2CH,0)6H + C,7H„C00H *-y C„HjjCO(CH2CH2NCHjCH20),H -I- H2O poly-trlethanolamlne add oleic ester
Nguyin lieu: polyalkanolamine tdng hop dUOc d giai doan | I, acid oleic, p-toluene sulfonic, Na^CO^ndng 5%, ether diu m6
(nhidt dp sdi 40-60°C).
- Thilt bj. dung eg: binh elu 3 ciy' sinh hin hdi luu ngang, b i p khuay td
- Thuc nghiem: Rdt td tU 282g acid oleic vio binh cau 3 cd chita 45g poly-triethanolamine tdng hop duoc d giai doan 1. Xue tic khoi mio eho phin dng niy la acid p-toluene sulfonic. Phin dng duoc duy tri d nhidt do ISO-C d i n khi thu duoe lupng nudc theo ly thuylt. Sin phim thu duoc rda qua dung djch NajCO, 5%
ndng de trung hda h i t luong acid di/.
Ldp hdu CO thu duoc sau khi duoc hda tan rdi tieh ra khdi dung mdi ether d i u md l i ester poly-triethanolamine.
Kit qui: Oilu kidn tdi Uu d l duy tri phin dng ester hda: nhidt dp phin dng 150°C, t^ l | polymer/acid oleic li 0,15kl, tdc dd khuay 600 vdng/phiit, thdi gian phin Ung l i 12 gid.
Phin tich clu true sin phim thu dagc bing phd cd elu trdc qua ph6 hdngngo?inhuHlnh7.
30 i l i a l - S O s/2013
PETROVIETNAM
So sinh t i n sd dao ddng vdi cic cae nhdm chUe lidn quan trong thu vidn phd thay cic pie hap thu tuong Ung vdi clu true sin phim ester poly-triethanolamine (Bing 6). Lidn kit carbonyl C=0 d t i n sd dao ddng 1.735,68em-' - diln hinh cua nhdm ester, xuit hidn ro rang nhat trdn phd hdng ngoai IR eua sin pham thu duoc.
3. Dung mol cho phu gla
Phu gia giim nhiet do ddng die gdm chat giim nhidt
Bdng 7. Tinh chdt hda -1^ cda ddi tugng ddu thd md Bgch Hi
I
Tfnh chit2 Nhidt d6 ddng die (»C)
PhUomg phip phin tich ASTMD1298_
ASTM D97
Oau thd tang Miocen Dau tho I Dau tho II (BH-806) (BH-401)
0,875 0,863 36
; Od nhdft d6ng hpc (cSt) 6 50''C
• Od nhdt d6ng hpc (cSt) 6 70''C Him lupng n-paraffin (%kl) Him lupng asphaltene (%kl) Him lupng nhua (%kl) Trpng lupng phin tU (g/mol) Chlsd acid, mgKOH/g Him luong niidc (%ki)
GC IP 143 COST 11858 ASTM D2502 ASTIM D664-89
ASTM D95 59,1 19,20 23,67 1,51
63,75 19.95^
25.37 1.24 1,7
0.04 12
Hinh 8. Phdn bd n- qua paraffin pho sdc ky khi cua ddu thd md Bgch Ho (BH-806) Bdng 8. Hiiu qud eua dung mdi vd chdt gidm nhiit dd ddng dgc lin dd nhdt eua ddu thd
Od nhdt d70"C (est) Dung mdi Ndngdd
(% thi tich) ' Carbon
tetrachloride
^-
D i u tho 1 (BH-806) 19,20
18,0 19,20 17,19 19,20
Dau thd1 -I-1 .OOOppm
15,80 15,50 15,80 14,90 15,80
Dau tho II (BH-401) 19,95 17,66 19,95 17,11 19,95
D i u th6 II
•H.OOOppm 17,35 16,75 17,35 16,59 17,35 I 19,20 _ J
dp ddng die tdng hpp 6dgc v i dung mdi thich hpp. Chit nin eua phu gia l i ester poly-triethanolamine tdng hop d glal doan 2. Dung mdi duoc liia chpn dUa trdn tieu ehi hda tan tdt chat nin 6e thuan tidn khi i p dung va hd trp chat nin trong vide eii thien tinh luu biln eho diu thd khi van ehuyen.Tuy cd ham luong thap nhUng asphaltene tic ddng d i n nhiet dp xuat hien paraffin eua dau thd. Asphaltene tie ddng den paraffin d quy md phan td, ddng vai trd lam mam kit tinh cho paraffin. Vi cau true eua asphaltene cd nhieu nhin thorn aromatic vdi chudi alkyl ben ngoii d cau true Idp. Cae Idp nay dupe bao quanh bdi mdi trUdng phin t i n ed t h i kit hpp va tao thinh eie nhdm kit tu. Dau thd dat nhidt dp ddng die khi cic asphaltene tich hoin toan khdi paraffin [13 - 15]. Niu asphaltene van tdn tai d dang hda tan trong dau thi dau van giUdUOe trang thii Idng, nhd dd tinh lUu biln cua dau dupe eii thien. Dung mdi trong phu gia giim nhidt dp ddng die ed chUe ning hda tan tdt eie micelle eua asphaltene. Cic dung mdi hda tan tdt asphaltene l i carbon tetrachloride, benzene v i xylene. Hidu qui cua eie dung mdi nay dupe the hidn trdn dp nhdt eua dau thd khi chit giim nhidt dp ddng die dUOc pha loang bing eie dung mdi thich hop.
Nghidn eUu i p dung eho 2 ddi tuong diu thd cua md Bach Hd l i : BH-806 v i BH-401 vdi cic die tinh hda - ly quan trpng Inh hudng tdi nhidt dp ddng die cda dau thd (Bing 7).
Ngoii chit nin la hpp chit giim nhidt dd ddng die chinh, sU ed mit mdt lupng nhd dung mdi vda eii thidn tinh chiy eho d i u thd vda thuin tidn eho vide hda tan chat giim nhidt dd ddng die khi dng dung vio thue t l . Trong Bing 8, khi hda tan t h i m vio diu thd ed chit giim nhidt dd ddng die vdi 1,5% t h i tieh, xylene l i dung mdi cd khi nang giim dd oia uri - so s/2013 31
nhdt nhilu nhat tU 19,20cSt xudng 14,51 eSt.Trong nghien eUu niy, phu gia giim nhidt dp dong die dupe chl tao vdi chit nen giim nhidt dp ddng die tdng hpp v i dung mdi xylene d ty Id 1/1 t h i tieh - diy
l i ty Id tdi Uu hidn dang dupc sd dung tai Vietsovpetro [1,4].
4. Hieu q u i g i i m nhiet tfo tfdng tflc cua phu gia tong hop tfUOc [16]
sU dung tai Vietsovpetro va 1 phu gia thuong mai Adi (OUc) ldn dau tho Bach Hd d mot sd ndng dp de tim ra ndng dd tdi UU khi sddung.
Bdng 9. Hiiu qud gidm nhiit do ddng ddc cua phu gia tdng hgp duac len ddu thd Bach Ho chua tdch nude
Nghidn cUu inh hudng eua phu gia tdng hpp dupe tdi nhidt dp ddng die eua dau thd Bach Hd trdn miy xic dinh nhidt dp ddng die Lawler theo quy trinh dupe dua ra trong tidu chuan ASTM D97[17].
Mlu diu thd dinh gii dupe lay d d i u edn gilng khai thie (trudc khi dupc dUa Idn dudng dng d i n diu ve giin trung tim) v i chUa ed bit ky phu gia nio. Kit qui d Bing 9 cho thay, phu gia tdng hop dupe cd hidu q u i giim nhidt dp ddng die eua dau thd I (BH - 806) tU 36°C xudng 28°C, AT = 8°C; nhidt dp ddng die eua diu thd II (BH - 401) giim tU 38°C xudng 32''C, AT^^ = 6°C. Odi ehUng vdi cic chl tidu ve diu thd d i phin tieh d Bing 7, diu thd II cd him lupng nUde khi cao 20%, him luong paraffin trdn 25%.
NUdc trong d i u giy hidn tupng nhu hda, ting dp nhot giy khd khin khi van chuyin, nhidt dp ddng die cung ting cao. Nhu viy, phu gia ed hidu qui rd ret vdi dau thd I (ed him luong nUde 12%, him luong paraffin khoing 24%).
Vi viy, nghidn eUu tap trung sd dung diu thd I eua gilng niy cho eie dinh g i i v l sau trong nghidn cdu.
Nhdm tie gH so sinh hieu qui giim nhidt dp ddng die eua phu gia tdng hop dupe tnjng d l tai (ky hilu PPD) vdi phu gia ES 3363 hien dang
Ndng do PPD (ppm) Loai d i u thd Dau thoi (BH-806) Dau tho II (BH-401)
0 36 38
Nhiet do tfdng dac ("C) 600 800
31 29,5 36 33,5 1.000
28 33
1.200 28 32
1.500 28 32 Ghl chu: Lugng ddu thd theo dng dong tiiu chudn ASTM D97[17]
w 28
« - 2 6 35
\ < ^ ,
\ ^ 29,5
26 29.5
28,5
28 28,5
28
25,5 28
26
00 400 600 800 1.000 1.200 1.4 Ndng do phu gia (ppm)
—•—Adi —•—ES3363 —•—PPD h 9. Anh hudng cua nong do phu gia lin nhiit do ddng ddc
cua ddu thd Bgch Hd chua tdch nudc
34
^^'^'^^^^^r—-i.^
^^"^""^-^^
26 28
^ f t v - '
^
^ 2119 21
r " ^22 21
Ndng d& phu gia (ppm)
Hinh 10. Anh hudng cua nong do phu gia lin nhiit dd ddng ddc cua ddu thd Bach Ho dd tdch nUdc
32
P E T R O V I E T N A M
K i t q u i H i n h 9 v i 10 c h o t h i y , d n d n g d p 1.OOOppm, p h u gia t d n g h o p d u o e ed t i c d u n g g i i m n h i e t d p d d n g d i e c h o d i u t h d Bach H d da t i e h n u d e ( h i m l u o n g n u d c
< 1%) tU34"'C x u d n g 21''C, LJ^^=^3''C. N h U v i y , h i m l u o n g n u d e t r o n g d a u t h d I n h h u d n g rat Idn d e n q u a t r i n h g i i m n h i d t d p d d n g d i e cua c i c p h u gia PPD. Khi lan nUde, c i c c l u t U c d k h i n i n g h d a t a n t r o n g nuOc eua d i u t h d n h U c i c chat h o a t d d n g b l m a t ed s i n t r o n g d a u hda t a n , p h a n t i n m d t p h i n g i y m a t can b i n g hda hpc. D o d d , d a u lan n h i l u nUde c d x u h u d n g k i t t i n h d n h i d t d p cao, d a n d i n n h i d t d p d d n g d i e eao h o n so v d i khi da t i c h nUdc. D a y l i ly d o vi sao da sd c i c p h u gia k h d n g d a t h i d u q u a cao t r o n g vide g i i m n h i d t d p d d n g d i e e h o d d i t u o n g d a u t h d ehUa nUde hay eO h i m l u o n g nUde cao.
5. H i l u q u i c i i t h i e n t i n h li/u b i e n cua p h u gia t d n g h o p tfuoc [ 1 6 ]
5.1. Dd nhdt ddng hpc
O p n h d t d u o c d o t h e o t i e u c h u a n ASTM D445 [18]
t r d n m i y d o d p n h d t Buber d 2 n h i d t d p d i e t r U n g l i 50°C v i 70''C. D i u t h d I d u o e b d s u n g t h d m p h u gia d n d n g d p t d i Uu 1 .OOOppm.
Hidu q u i g i i m n h i e t d p d d n g d i e cua p h u gia PPD t d n g h p p d u o c t u o n g d u o n g v d i p h u gia h i d n d a n g s d d u n g tai Vietsovpetro n h U n g ve t i n h l u u b i e n , p h u gia t d n g h o p d u o e c d u u t h e vUOt t r o i h o n . Bang 10 eho t h l y , d l u t h d khi eho t h e m p h u gia PPD da g i a m d p n h d t d d n g hpc rd ret x u d n g 16,62eSt so v d i p h u gia ES 3363 c h i g i i m d p n h d t x u d n g 18,03eSt d n h i d t d p 70<'C. N h U v i y ,
Bdng 10. Anh hudng cua phu gia lin do nhdt ddng hge cua ddu thd Dau t h d / Dau thd/
ES3363 P P D _ 47.65 Chi tidu D i u thd
B d nhdt ddng hpc d50''C(cSt) 63.75 59,43
0 6 nhdt ddng hpc d 70»C (cSt) 18.03
Ghi chd: Lugng ddu thd theo dng dong tieu chudn ASTM D44S [18]
35.58mN/m [^ 23,02jTiN/m ^
^ ~ ^ ^ ^ ^ ^ ^ ^ ~ ^ r~^^^^^B^n , J 3 , 9 5 m N / m ,
Gipt d i u t h o chua t i c h nudc/PPD
Gipt dau th6 da tach nudc/PPD
!i n . StJt cdng bi mat d nhiit dd 70'C
khi s d d u n g p h u gia PPD t d n g h o p dupe, t i n h lUu bien eua d a u t h d t r o n g v a n e h u y e n d u o c e i i t h i e n h o n so v d i p h u gia hidn d a n g s d d u n g tai Vietsovpetro.
5.2. Sdc cdng be mdtd dp sudt, nhiit dp cao Phu gia bien t i n h t i n h t h e paraffin t r d n n e n ester cua p o l y - t r i e t h a n o l a m i n e c d d i e t i n h cua m d t chat hoat d d n g b l m a t . Cac p h a n t d chat hoat d d n g b e m a t khi t a o t h i n h e i e micelle, sU k i t c u m xay ra t h d n g qua lien k i t ky nude ( h y d r o p h o b i c ) eua c h u d i alkyl phai t h i n g d u p e lUe d a y giUa c i c d a u h o a t d d n g b e m a t ed ehUe n i n g n h U liie d a n t h u e day lien k i t .
SUc c a n g be m a t la m p t t i d u c h i q u a n t r p n g d d i v d i chat g i a m n h i d t d p d d n g d i e d a n g ester p o l y a l k a n o l a m i n e c d hoat t i n h be m a t nay. Phdp d o c h o p h e p x i c d i n h hieu q u a cua h o p chat khi t u o n g t i c v d i d a u d n h i d t d p gia n h i d t 70°C. H i n h 11 t h e hien k i t q u a d a n h gia sUc cang be m a t cua g i p t d a u t h d khi c h o t h d m p h u gia g i a m n h i d t d p d d n g d i e n d n g d p 1 .OOOppm t r o n g m d i t r u d n g m u d i ( m d p h d n g m d i t r U d n g nUdc bien).
d n h i e t d p eao, p h u gia g i i m n h i e t d p d d n g d i e ester p o l y t r i e t h a n o l a m i n e v a n g i U d U p c d i e t i n h g i i m sUc c i n g b e m a t khi hda t a n t r o n g d a u t h d . Phu gia PPD c d t i e d u n g g i a m sUc cang b e m a t t u o n g t i c d a u / n U d c . NhO chUc n a n g nay ma d d n g c h i y cua d a u t h o t r o n g van c h u y e n d u p e cai t h i d n h o n khi eo t h d m p h u gia. O i y la m p t u u d i e m cua p h u gia g i i m n h i d t d p d d n g d i e ed chat n e n l i chat hoat t i n h be m a t d a n g ester eua p o l y - t r i e t h a n o l a m i n e m i k h d n g p h i i p h u gia PPD n a o e u n g c d d u p e .
TU k i t q u a t d n g h p p v i d i n h g i i t h u d u p e , n h d m t i e gia n g h i d n eUu d e x u a t q u y t r i n h t d n g h o p p h u gia g i i m n h i e t d p d d n g d i e (PPD) t U n g u y d n lieu b a n d a u la t r i e t h a n o l a m i n e eho d a u t h d n h i e u paraffin t r d n H i n h 12.
6 . Ket l u a n
C i e k i t qua t h u e n g h i e m e h o t h i y chat n e n g i a m n h i d t d p d d n g d i e 6\ige t d n g h p p v d i d i l u kidn t d i Uu tai p h d n g t h i n g h i d m t r e n n g u y e n lieu cO b a n la t r i e t h a n o l a m i n e e h o ester p o l y - t r i e t h a n o l a m i n e q u a 2 giai d o a n p h a n Ung:
(1) p o l y m e r hda t r u n g n g U n g t r i e t h a n o l a m i n e d n h i d t d p 250°C v d i xue t i e C a ( O H ) j t y Id 1 /O.OI kl;
(2) ester p o l y - t r i e t h a n o l a m i n e t h u d u p e khi t i e n h a n h ester hda p o l y m e r v d i acid oleic t y Id 0.15kl, d t d e d p k h u a y t r d n t d i Uu 6 0 0 v d n g / p h u t d n h i d t d p 150°C;
16,62
i i n r i - s o s/2013 3 3
. Acid oleic fty H polymer/addO. IS WJ
• p-toluene sulfonic
Ifinh 12. Sa do khdi quy trinh tong Odi vdi diu thd nhilu paraffin md Bach Hd, phu gia tong hop trin nin ester polytriethanolamine v i dung mdi xylene cd khi ning giim nhidt dp ddng die 8°C (tU 36°C xudng 28°C) ddi vdi diu ehUa tieh nUde va giim nhidt dp ddng die U-C (tU 34°C xudng 2rC) ddi vdi dau da tich nude tuong duong vOi phu gia ddi ehUng ES 3363 hidn dang sU dung tai Vietsovpetro v i hda pham thuong mai Adi (Ode).
Vide tdng hpp thinh edng phu gia cd hidu qui giim nhidt dp dong die cho dau thd nhieu paraffin md Bach Hd tUOng duong phu gia thuang mai hien dang sd dung v i die tinh eii thien tinh lUu biln vucrt trdi cua phu gia - mdt trong nhUng tieu ehi quan trpng trong dinh gii Ilia chpn loai phu gia niy khi Ung dung trong khai thie v i vin chuyin diu tho eo gia tn thiic tien ldn. Phu gia tdng hop dupe dat yiu clu cua phu gia PPD Ung dung cho khau khai thic van chuyin dau thd nhieu paraffin khdng chi cua md Bach Hd ma edn md ra trien vpng Ung dung cho cic ddi tuong dau thd nhilu paraffin khic trong vide ngin ngUa Ilng dpng paraffin, ting nang suat khai thae, d i m bio chit lupng diu.
Tii lieu tham Ichio
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Synthesis of pour point depressant additives for production and transportation of high-paraffin Bach Ho crude oil based
on ester of poly-triethanolamine
Dao Thi Hai Ha, Hoang Linh, Luong Van Tuyen Vietnam Petroleum Institute
Summary
The presence of paraffin in crude oil has caused severe implications in production and transportation. The high- paraffin crude oil easily freezes at high temperatures, especially in the condition where the production and transportation pipeline is not heat-insulated from the external environment of seawater. Thus, a number of pour point depressant additives (PPD) that are based on polymer or copolymer with alkyl (met)acrylate or maleic are now being Imported and used domestically. Recently, studies on the synthesis of pour point depressant based on amine compounds and fatty acids have made good achievements in both reducing the pour point and improving the flow of crude oil. Particularly, ester of polyalkanolamine has many dominant properties of a base pour point compound that effectively reduce the pour point of high-paraffin crudes. It bas opened an alternative approach in synthesising the pour point additives in laboratory. This study acquires those results and proposes a new application for the waxy crude oils in Vietnam, specifically for the Bach Ho crude oiL
Bita o i - s o 5/2013 3 5