PETROVIETNAM

Nghincuphngphpxlthyngntrong khaithckh
KS. Hunh Vit Quang, TS. T Quc Dng i hc Bch khoa Tp. HCM TS. Nguyn Minh Hi Tng cng ty Thm d Khai thc Du kh

Tm tt S c mt ca thy ngn trong kh khai thc c th gy ra nhng thit hi khng nh cho nn cng nghip khai thc v s dng kh. Do vy, nghin cu phng php x l thy ngn trong qu trnh khai thc v x l kh l mt ti cp thit, ph hp vi hon cnh thc t nc ta hin nay. Trong qu trnh nghin cu, nhm tc gi tin hnh tnh ton thit k thit b hp ph thy ngn lm gim ng k hm lng thy ngn u ra ca dng sn phm.

1. Tng quan v v hin tng nhim thy ngn 1.1. Ngun gc hnh thnh Thy ngn (Hg) l kim loi t nhin, tn ti di nhiu dng khc nhau, tn ti dng lng nhit phng. Thy ngn d dng ha hi v c kh nng kt hp vi mt s nguyn t khc th to thnh thy ngn hu c hoc v c. Trong , thy ngn hu c cc k nguy him n sc khe con ngi cng nh mi trng xung quanh.

Thng k v hm lng thy ngn trong du th c x l ti cc nh my lc du ti M trong nm 2004 c trnh by trong Bng 1 [1]. 1.2.2. Trong kh t nhin Trong kh thy ngn thng c hm lng t 0 - 300g/ Nm3 v c hm lng kh cao ti mt s vng khu vc ng Nam , ng u, Bc M. Hm lng thy ngn cao xut hin Indonesia (Adun) v H Lan (Groningen) v c bit c vi ging vi hm lng thy ngn cc k cao nh North Germany mc 4.400g/m3 (Bng 2).

Thy ngn c tm thy t hot ng phun tro ca ni la, cc qu trnh bay hi hoc kh Bng 1. Hm lng thy ngn trung bnh trong du th x l ti M kh ca lp v tri t v trong cht thi trong nm 2004 [1] cng nghip. Trong cng nghip du kh, cc ngun thy ngn ch yu xut pht t phn gii cc ha thch trong lng t nhit cao, sau chng nhim vo va du, kh. 1.2. Tnh trng nhim thy ngn trong hydrocarbon 1.2.1. Trong du th Cc nghin cu v hm lng thy ngn trong du th M cho bit tng hm lng thy ngn trong du th (bao gm thy ngn dng nguyn cht v hp cht) dao ng trong khong t 0,1 - 20.000g/ kg du th [1].

(*): Trong cc ti liu thng mi, hm lng thy ngn trong du th thng phm thng c o bng n v ppb wt (parts per billion by weight = 1 phn t tnh theo khi lng) hoc ppm wt (parts per million by weight = 1 phn triu tnh theo khi lng).
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Bng 2. Nng thy ngn trong kh t nhin [21]

Hnh 1. S cng ngh ca h thng x l kh [10]

Thy ngn c mt trong kh trong mt s m ca b Cu Long vi hm lng vo khong 32,1ppb theo th tch (sau bnh lm khan nc ti CCP) [ngun PV Gas]. Tuy nhin ti u ra ca h thng x l (tng ng vi ng kh u ra trong Hnh 1) hm lng thy ngn ch c 5,1ppb theo th tch. Nh vy, lng thy ngn chnh lch c lu gi trong h thng thit b x l. Gi s mi ngy c 56
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5.000.000m3 kh th hi thy ngn lu li trong h thng vn hnh l 0,135m3 v mt nm l 48,6m3 (ch tnh gi s p sut 101.325kPa v nhit l 150C, cha tnh n p sut v nhit ca ngun kh c o). Lng hi thy ngn ny c th lu li trong h thng thit b x l kh dng ht hoc phn ng vi kim loi ca vt liu dn ti hin tng n mn [21].

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1.2.3. Trong condensate Theo nghin cu ca Sarrazin v cc cng s th hm lng thy ngn trong condensate dao ng trong khong 10 - 3.000ppb wt.
Bng 3. Hm lng thy ngn trong condensate [16], [19]

khc ca thy ngn nh hp cht thy ngn v c v hu c. Ngi ta tm thy nhiu thnh phn hp cht ca thy ngn trong lng kh thu c, v hn th na nguyn t thy ngn v cc dng hp cht ca n c th gy ra n mn rt ln. Thm vo , s c mt ca H2S loi kh thng c mt trong kh t nhin - chnh l cht xc tc trong phn ng ha hc ca thy ngn vi nhm, l cht c dng ch to mt s chi tit ca thit b trao i nhit v cc thit b khc ca h thng x l. Kt qu ca vic n mn ny l do hp kim ca thy ngn v nhm to nn c gi l hn hng [14]. bt u qu trnh n mn nhm, th lp nhm oxit trn b mt phi c loi b. Khi thy ngn kt hp vi nhm ti b mt, nhm s b ha tan ti mt tip xc vi thy ngn v d dng to ra Al(OH)3 bng phn ng vi nc. Al + Hg AlHg

Cng theo thng k ca Unocal (1998), hm lng thy ngn trong condensate ti vnh Thi Lan dao ng t 500 - 800g/m3 v c nh gi l c hm lng thy ngn cao c kh nng gy nh hng n qu trnh khai thc du kh trong khu vc. 1.3. nh hng ca thy ngn Thy ngn c mt trong du th, kh t nhin v condensate trong qu trnh khai thc du kh s gy ra nhng nh hng i vi: - Sc khe con ngi. - Trang thit b. - Gi bn du, kh, condensate. 1.3.1. nh hng n sc khe c t ca thy ngn ph thuc nhiu vo dng ha hc c bit. Nguyn t thy ngn Hg th tr v khng c hi, nhng khi ha hi p sut cao th rt c. Vic x l thy ngn ch nn c gii quyt trong khu vc thong kh ca ging v khi trn ra th phi gii quyt mt cch nhanh chng nht. Hi thy ngn khi ht vo c th s theo mu i vo no, gy nguy him cho h thn kinh trung ng. 1.3.2. nh hng n trang thit b Thy ngn trong kh t nhin khng ch tn ti di dng nguyn t m cn tn ti di nhiu dng hp cht

2AlHg + 6H2O 2Al(OH)3 + 3H2 + 2Hg Qu trnh phn ng ny s li to ra thy ngn t do, v sau quy trnh n mn s li tip tc cho n khi thit b b bo mn dn v dn n h hng khng th s dng c. Nguyn t thy ngn khi xm nhp vo mng tinh th ca thp - vt liu chnh ca ng ng - s lm gim bn ca thp. Nguyn t thy ngn cng lm gin cc cc hp kim ca ng, dn ti gim bn ca cc thit b lm t hp kim ng khi b nguyn t thy ngn xm nhp [2]. 1.3.3. nh hng n gi bn du kh V cc nh my lc du ch thit k x l du th, condensate vi hm lng thy ngn cao (mt s nh my c th chp nhn hm lng thy ngn n 500ppb wt). Do vy du th, condensate c hm lng thy ngn cao c mua vi gi thp hn so vi du th, condensate c hm lng thy ngn thp. Mc gim gi ph thuc vo hm lng thy ngn, ni bn, nhu cu th trng Du th, condensate c hm lng thy ngn cao hn 1.000ppb wt c th b gim gi hn 10USD/thng. Trong qu trnh khai thc m kh t nhin c hm lng thy ngn cao, nu khng x l thy ngn khi dng kh th mt phn thy ngn s i vo dng condensate. Cui cng s dn n vic gim gi bn condensate, lm nh hng n hiu qu kinh t ca d n.
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Nh vy thy ngn trong hydrocarbon d vi hm lng rt nh vn c th gy ra thit hi ln v sc khe con ngi, trang thit b v kinh t. Chnh v vy, nghin cu x l thy ngn trong khai thc l vn ht sc quan trng v cn thit. 2. Phng php x l thy ngn trong khai thc du kh 2.1. Phng php x l thy ngn Yu cu c bn dn n thnh cng trong vic kh thy ngn v p ng tnh kinh t ca vic kh thy ngn l h thng x l thy ngn phi p ng c cc yu cu sau: - C kh nng gim lng thy ngn trong dng lu cht n mc yu cu ca ngi mua. - C cng sut x l ln cho mc khai thc ca m.

- Lm vic hiu qu ti p sut v nhit ca dng lu cht i vo h thng. - C quy trnh c th v an ton v lu tr v x l thy ngn sau khi b kh v cc ha cht sau khi tng tc vi thy ngn. - C chi ph u t v vn hnh hp l. - Vn hnh d dng. Hin nay c kh nhiu phng php x l thy ngn. Tuy nhin, hai phng php ni bt hn c l hp ph bng than hot tnh v bng mui sulfur. Da trn nhng u im ca vic dng mui sulfur x l thy ngn, nghin cu xy dng hng thit k thit b x l thy ngn da trn phng php ny. 2.2. Thit b x l thy ngn Vic tnh ton bnh hp ph thy ngn cn ph thuc vo din tch sn cng nh chiu cao ti a cho php ph hp vi thng s k thut ca gin c sn ban u. Trong bnh hp ph, phn quan trng nht chnh l th tch tng hp ph. Mc ch chnh ca phn thit k bnh hp ph cng chnh l tnh ton th tch ca tng hp ph t a ra nhng thng s kch thc v ng knh trong ca thp cng nh chiu cao ca tng hp ph cho nh sn xut tham chiu v la chn thng s thch hp nht thit k mt bnh hp ph va ph hp vi yu cu v din tch ca gin va ph hp vi vt liu, chi tit sn c ca nh sn xut. C hai kiu bnh hp ph:

Hnh 2. Bnh hp ph theo nguyn tc hp ph dc trc

Hnh 3. Bnh hp ph theo nguyn tc hp ph theo bn knh

- Bnh hp ph theo nguyn tc hp ph dc trc: dng kh c dn vo trong bnh hp ph, i

Bng 4. u v nhc im ca 2 kiu bnh hp ph

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qua khong khng v lp bi cu ceramic n nh dng trc khi tham gia vo phn ng ha hc bn trong bnh theo phng thng ng dc trc ca bnh. Sau khi tham gia phn ng vi mui sulfur bn trong dng kh s i theo ng dn kh ra ngoi. Bnh hp ph theo nguyn tc hp ph theo bn knh (hp ph ngang): dng kh i vo bnh hp ph v ch yu c dn vo cc ng ng nh st thnh bnh v trn thn nhng ng nh st thnh bnh ny c nhng l nh dng kh thm ngc vo tm bnh xuyn qua lp ha cht hp ph v i vo ng ng thu hi kh nm dc trc bnh hp ph v i ra ngoi. C th phn tch u nhc im chnh ca 2 kiu thit k ny nh Bng 4. u v nhc im ca vic hp ph thy ngn bng mui sulfur: - u im: + C tui th lu. + Ph u t thp hn, bnh cha nh hn. + C th lm vic p sut cao. + C th thit k lm vic p sut thp. + C th dng cho kh kh v kh t. + Khng c ri ro tht thot lu hunh. + C th thit k tng t cho dng hydrocarbon lng (nh). + C th tn dng nguyn liu ti ch do nu chy kim loi. - Nhc im: + Chi ph sn xut mui sulfur cao hn than hot tnh. + S xut hin ca nc (H2O) s lm gim hiu qu x l thy ngn do nc khng phi l cht xc tc tt cho phn ng ha hc gia mui sulfur v thy ngn. Trong nghin cu ny, tc gi ch tp trung vo hng thit k cho bnh hp ph dc trc v n c thit k n gin nhng hot ng hiu qu p sut va (< 100 bar) - iu kin p sut lm vic phn ln cc gin x l ti Vit Nam. 3. Thit k thit b x l thy ngn tnh ton c th tch ca tng hp ph, cc nghin cu trc y cho thy nhng thng s ca

dng kh u vo v yu cu v iu kin lm vic ca gin, thng s v ha cht hp ph cng nh thng s v vt liu ch to bnh hp ph l iu kin cn thc hin tnh ton. Tnh ton bnh hp ph trong nghin cu ny c thc hin nh sau: 3.1. Tnh ton bnh hp ph Lng kh khai thc trong t nm: Vgas = q x t x 365 (Sm3) Trong : q: lu lng khai thc (trSm3/ngy) t: tui th cn thit ca cht hp ph (nm) Lng thy ngn trong kh cn c loi b trong t nm: mHg = (CHg1 - CHg2) x Vgas x 109 (kg) (2) (1)

Trong : CHg1, CHg2: hm lng thy ngn kh u vo, u ra (g/Sm3). Sau , da vo phng trnh phn ng gia thy ngn vi mui sulfur (Hg + MxSy = MxSy-1 + HgS) tnh khi lng ca cht hp ph cn thit m MxSy hp ph thy ngn trong thi gian t nm. Th tch cn thit ca lng cht hp ph hp ph thy ngn trong thi gian t nm: (3) Trong : : khi lng ring ca cht hp ph (kg/m3) : khi lng cht hp ph cn dng (kg) Nh vy, th tch ca tng hp ph (m3) cn thit x l thy ngn trong thi gian t nm c tnh theo cng thc sau: (m3) Trong : k: h s an ton ly bng 1,5 R: t l th tch ht cht hp ph hiu dng (c kh nng hp ph thy ngn). c lng R = 10% qua quan st thc t. Chiu cao (hbed - m) ca tng hp ph v ng knh trong ca thp hp ph (din - m) c tnh ton t cng thc:
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(4)

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(5) ng knh ca thit b hp ph c gii hn bi iu kin ca gin. Chiu cao ca tng hp ph cng b gii hn trn bi gim p ti a cho php. gim p ca kh khi qua tng hp ph c tnh ton nh sau: T thnh phn kh u vo ti tin hnh lp bng tnh ton khi lng ring ca hn hp kh (g) vi n v l kg/m3 [23]: (6) Trong : P l gim p (KPa)

(9) V ht ha cht m chng ta dng x l thy ngn c ng knh trung bnh l khong 4mm nn nghin cu mc nh gi tr A = 67. Da vo gim p ti a cho php nghin cu c th tnh ton c lng chiu cao ti a ca tng hp ph m bo yu cu v gim p ti a cho php theo cng thc nh sau [20]: (10)

(7) Trong : P: p sut lm vic (KPa) Ma: khi lng mole ca hn hp kh (kg/kmole) z: h s lch kh R: hng s 8,3145 T: nhit lm vic (0K) Mj: khi lng mole ca tng thnh phn (kg/kmole) yj: phn trm mole ca tng thnh phn H s lch kh z hon ton c th tnh c bng cch dng phng php tra th Standing-Katz hoc dng quan h Dranchuk & Abou - Kassem hoc Hall - Yaborough [3] tnh trc tip. Tip theo nghin cu tnh h s nht ca hn hp kh iu kin p sut kh quyn bng cch tra th h s nht ca cc kh sch p sut kh quyn ri dng cng thc sau [22]: (cp) Trong : Mj: khi lng mol ca thnh phn kh. j : nht ca thnh phn kh (cp) c xc nh bng cch tra th. Nhng thnh phn kh ca nghin cu ang xt iu kin nhit v p sut lm vic do nghin cu cn tm t s bng cch tra cc th xc nh t s (8)

V ht ha cht c ng knh trung bnh l khong 4mm v c hnh cu nn B = 5,36 v C = 0,00189. Da trn cc cng thc trn, nhm tc gi lp nhiu gi tr din v hbed tng ng nh sn xut c th la chn mt gi tr ph hp vi vt liu sn c v iu kin c th ca gin khai thc. Sau khi xc nh chiu cao ca tng hp ph cng nh ng knh trong ca thp hp ph, nhm tc gi c tnh chiu cao ca thp hp ph bao gm chiu cao tng hp ph, chiu dy ca lp phn phi v n nh dng kh v khong khng cn thit dng kh di chuyn v m bo gim p dc theo trc ca thp l ti thiu. Nh vy, theo thc nghim [5] v [20], chiu cao thm vo khong t 1 - 1,5m t c chiu cao n nh cho thp. B dy ca v bnh hp ph c th c tnh theo nhiu tiu chun khc nhau, tuy nhin trong bi bo ny tnh ton b dy v bnh hp ph thy ngn theo tiu chun ASME [22].

(11) Trong : : b dy ca v bnh hp ph (mm) din: ng knh trong ca bnh hp ph (mm) : ng sut ti a cho php (MPa) E : H s hiu dng ca mi hn ni : nh mc mi mn (mm) 4. Kim chng Nghin cu tnh ton mt thit b x l ti m X c thng s dng kh u vo bnh hp ph v ch lm vic nh Bng 5, 6.

nht theo t trng kh. c lng vn tc kh b mt vg (m/pht) [20], [22]:

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Bng 5. Ch lm vic ti m X

Bng 8. Kt qu tnh ton v so snh vi thc t

Bng 6. Thng s dng kh u vo bnh hp ph

Hnh 4. S x l thy ngn ti m X

Cc thng s v ha cht c dng (Bng 7).

Bng 7. Thng s ha cht c dng

b s dng ti m X. Theo , ti m X, vi cng thng s u vo v ch lm vic, th tch hp ph c dng l 19m3, ng knh thp l 3m v chiu cao ca tng hp ph l 2,7m, thp ny c dng trong 5 nm v thay ha cht sau 5 nm s dng. i vi phn tnh ton ca tc gi, sau khi p dng cc cng thc trong phn nghin cu dng b s liu ca m X tnh ton kch thc thp hp ph v t c kt qu tng ng nh thp ang s dng ngoi thc t. 5. Kt lun Vic thit k thit b v xy dng m hnh x l ph thuc vo nhiu yu t cng nh kh nng p dng cho tng trng hp c th. Vi mc tiu Nghin cu phng php x l thy ngn trong khai thc du kh, nghin cu gii quyt c nhng vn sau: + a ra thit k bnh x l thy ngn cho mt m c kh nng p dng ti Vit Nam. + Tnh ton thit k bnh hp ph thy ngn theo phng php hp ph dc trc bng mui sulfur, m
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S h thng x l thy ngn ti m X nh Hnh 4. Sau khi p dng cng thc tnh ton, nghin cu c c kt qu nh Bng 8. So snh kt qu tnh ton vi kt qu thc t ca mt bnh hp ph thy ngn c s dng ti m X trong thi gian 5 nm cho thy, vi cng mt thng s u vo, ha cht hp ph, thng s dng kh, nghin cu ch ra c kt qu tng ng vi kt qu thc t ca thit

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quan trng nht l tnh ton c th tch tng hp ph, t a ra cc thng s kch thc tng ng cho cc nh sn xut la chn thng s ph hp sn xut. + Kt qu bnh hp ph tnh ton sau khi so snh vi kt qu thit b x l m X v c th chp nhn c a vo sn xut th nghim. Ti liu tham kho 1. Wilhelm, S. M., Liang, L., Cussen, D. and D. Kirchgessner, 2007. Mercury in Crude Oil. Mercury in Crude Oil Processed in the United States (2004). Environmental Science and Technology, American Chemical Society, 41 (13), 4509. 2. Wilhelm, S. M., PhD. Johnson Matthey, April 2009. The interaction of mercury with metal surfaces - engineering implications. Mercury Technical Seminar - Ho Chi Minh City. 3. Butterworth - Heinemann, 2000. Reservoir Engineering Handbook. USA: Gulf Profesional publishing. 4. C.Visvanathan. Treatment and disposal of mercury contaminate waste from oil and gas exploration facilities. Thailand: Asian Institute of Technology. 5. Campbell, John M, 1996. Gas Conditioning and Processing. s.l.John M.Campbell and Company. 6. Canada, Environment. M e rcur y and the environment basic facts. Environment Canada website. [Online] http://www.ec.gc.ca/MERCURY/EN/bf.cfm. 7. Electric Power Research Institute, March 2008. Fixed Structure Mercury Removal. USA: EPRI. 8. Environmental Protection Agency, 2004. Mercury in Petroleum and Natural Gas: Estimate of emissions from production, processing and combustion. s.l.: United States Environmental Protection Agency. 9. Giacomo Corvini, Julie Stiltner and Keith Clark, 2002. Mercury removal from natural gas and liquid streams. Texas, USA: UOP LLC. 10. Johnson Matthey Catalysts, April 2009. Mercury removal technology. The UK. 11. Muhamad Rashid Sainal, T.Mohd Uzaini T.Mat, Azman Shafawi and Abdul Jabar Mohamed, November 2007. Mecury removal project: issues and challenges in managing and executing a technology project. SPE 110118.

12. S.Mussig, B.Rothmann, BEB Erdgas and Erdoel GmbH, April 1997. Mercury in natural gas - problem and technical solutions for its removal. SPE 38088. 13. Mercury Instruments - The experts in mercury analysis. Mercury Instruments website. [Online] http:// www.mercury-instruments.com/EN/index-en.html. 14. M. Abu El Ela, I.S Mahgoub, M.H.Nabawi and M.Abdel Azim, March 2008. Mercury monitoring and removal at gas - processing facilities: Case study of Salam Gas plant. SPE 106900. 15. L . Po r n s a k u l s a k a n d T.S o p o n k a n a b h o r n , September 2007. Metal recovery from spent mercury and H2S Absorbents. SPE 108875. 16. Oil Tracers L.L.C. 2009. Using gas Geochemistry to assess mercury risk. Gaschem website. [Online] http:// www.gaschem.com/mercury.html. 17. Peter J.H Carnell and Steve Willis, 2005. Mercury removal from liquid hydrocarbons. The UK: Johnson Matthey Catalysts. 18. Peter J.H Carnell, December 2005. Andra Foster and John Gregory. Mercury Matters. The UK: Johnson Matthey Catalysts. 19. Spiric, Zdravko, Februar y 2001. Innovative approach to the mercury control during natural gas processing. Texas, USA: Engineering Technology Conference on Energy. 20. Hong Trng Quang v H Quc Vit, 2008. Bi ging Cng ngh kh: Chng 7 - Lm kh kh bng cht hp ph. i hc Bch khoa Tp. HCM. 21. Nguyn Th Liu, Ng Quang Minh, 2008. Thy ngn: Mi him ha cho cc cng trnh kh v ha du. Tuyn tp bo co Hi ngh KHCN Vin Du kh Vit Nam: 30 nm pht trin v hi nhp, p. 588 - 593. 22. Thi V Trang, 2008. Thu gom - X l - Vn chuyn du kh. i hc Bch khoa Tp. HCM.

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