CA1131002A - Method for inhibiting corrosion in high temperature, high pressure gas wells - Google Patents
Method for inhibiting corrosion in high temperature, high pressure gas wellsInfo
- Publication number
- CA1131002A CA1131002A CA357,330A CA357330A CA1131002A CA 1131002 A CA1131002 A CA 1131002A CA 357330 A CA357330 A CA 357330A CA 1131002 A CA1131002 A CA 1131002A
- Authority
- CA
- Canada
- Prior art keywords
- phase
- inhibiting corrosion
- gas
- corrosion
- fatty amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method for inhibiting corrosion in a high tem-perature, high pressure gas well in which an aqueous or bring phase is present but no petroleum condensate phase exist at bottomhole conditions, involving the injection of a relatively high molecular weight predominantly aliphatic amine (e.g., a fatty amine, particularly, the N-alkyl-1,3-propane diamine) into the gas well on its own or in combination with conventional oil based corrosion inhibitor additives to inhibit corrosion. Such a method is particularly useful in sustaining a liquid film forming phase at hostile bottomhole conditions.
A method for inhibiting corrosion in a high tem-perature, high pressure gas well in which an aqueous or bring phase is present but no petroleum condensate phase exist at bottomhole conditions, involving the injection of a relatively high molecular weight predominantly aliphatic amine (e.g., a fatty amine, particularly, the N-alkyl-1,3-propane diamine) into the gas well on its own or in combination with conventional oil based corrosion inhibitor additives to inhibit corrosion. Such a method is particularly useful in sustaining a liquid film forming phase at hostile bottomhole conditions.
Description
~L3~ 2 M}~ OR_IN_IB1l_NG CORROS'I.ON_IN_~IL(~!_L~.s~ RAr~REL
I{IGII PR55URE GAS WEL.LS
BACKGROUND OF T~IE ~NVENTION
l. F:Le1_ o~ the 1n _nL n The present i.nvencion relates to ~In :improved corrosion inhi~itor system for use in high t-empe:rature :l5 hi.gh pressure gas wells. More specifical.l.y it is con-cerne<l wi~h c~ fatty arn:i.ne optionally containing an oil soluble corrosion :inhibitor whîch is capable of ' - .
maintaining a protective film at high temperature high pressure boL~ornho:l.e conditions in ~:he absence of a 20 petrolellm condensate p'hase.
I{IGII PR55URE GAS WEL.LS
BACKGROUND OF T~IE ~NVENTION
l. F:Le1_ o~ the 1n _nL n The present i.nvencion relates to ~In :improved corrosion inhi~itor system for use in high t-empe:rature :l5 hi.gh pressure gas wells. More specifical.l.y it is con-cerne<l wi~h c~ fatty arn:i.ne optionally containing an oil soluble corrosion :inhibitor whîch is capable of ' - .
maintaining a protective film at high temperature high pressure boL~ornho:l.e conditions in ~:he absence of a 20 petrolellm condensate p'hase.
2. Descri~i.on of Prior Art The utili.zation of chemi.ccll. cor-rosioll inhibitors to protect meral suraces in various stages of oil. ancl gas ~ .
production has long been recognized as a necessary feature 25 o.~ oil and gas production. During the past ha.L.f centwry mul~itudes of chemical corrosion systems ~nd methods of us:ing Lhe~ ave be~n cleveloped ancl have l~d to a vast nurnber of patents anci technical literature references.
Thus today corrosion engineering is considered an 30 integral par~ of ~he planning and operati.on of v:i.rtually every stage o~ oil and gas production.
With ever i.ncreasing worlcl ener~y demancls and the ~dvent of i.nternational uel shortages the oil and gas :i.nclustry has been forced LO drill. deeper cln<3 deeper 35 into rnore hosti.'le ellvironsneslts in searcs~ o~ che cri.tical:l.y needed fue:1.. As a resu:1t cert:ain shi.gsl ternperat~lre high press~lre delep hori~.on gas fields have l)een d:i~icovered throughollL the worl.d wll:ich present a severc chal.lenge to ~ , , " ~:
':' - ~ ; ' ~3~
contemporary corrosi.on technology when one attempts to produce l.arge volu!lles o~ natural gas :in these fiel.cls.
The ~as wells o.E partic~lar interesL in the present invention are characterized by a combi.nati.on of 5 properti.es that l.eac~ ~o cor-rosion rates manyfo:l.d hi.gher Lhan ex~eriencecl in other gas fields. F:irsL alld roremosL, the gas wel.ls ~re comp:Leted at great dept:hs wh:i.ch in mal)y cases e~ceed ~0>()00 ft. Conseguentl.y, the gas we:l.ls are categorically high temperature~ high pressure wel.l.s. As a 1.0 general r~lle, at bottomhole ternperatures in e~cess of ~50~E ancl bottomho:Le pressures of the order of abo~lt 4,000 psi, one can anticipate severe corrosion. ~s these bottomhol.e temperatures and pressures i.ncrease, the proh-lems become even more pronounced such that at 400F and 15 pressures in e~cess of 5000 psi, the use of many corrosion i.nhibiting systems and n~ethocls is virtual:Ly prohibited.
The gas wells of interest in the present invention are of this nature.
Furthermore, the particul.ar gas wells of 20 interest are dry wells in the sense that no liquid petro-leum phase exists at the bottomhole conditions. Thus~ no protecti.ve oil fi.llll will be presenL LO coat the casing and to act ~s a corrosi.on :inhi.bitor carrier. In fact, since no conclensate phase exists at these bottomhole conditions, 25 injection or~ oil.-sol.~lble inhibitors i.n a petroleum conclen sate carrier will. be ineffective because o premature vaporizat:ion of the carrier be~ore reaching the bottoln of the well. To furcher complicate the lack of petrol.eum condensate phase at: the bottomhole conditi.ons, the gas 30 well.s of :interest will have an aqueo~s or br:ine phase present, and t.his, in combination with acid gases such as h~d30gen sul.fide, carbon dioxide or t:he Like, creat:es an e~tremely corrosive environrnent. Wi~:h gas producti.on in terrns of tens of mi.l:Lions of standarcl cubic ~eet per day, 35 the poss:ibi.:Lity of mairltaini.ng an oil conden~ate phase at ~)ottorrlhole condit:i.ons is for al..L pra~matic purposes ruled ouL .
.. . .
production has long been recognized as a necessary feature 25 o.~ oil and gas production. During the past ha.L.f centwry mul~itudes of chemical corrosion systems ~nd methods of us:ing Lhe~ ave be~n cleveloped ancl have l~d to a vast nurnber of patents anci technical literature references.
Thus today corrosion engineering is considered an 30 integral par~ of ~he planning and operati.on of v:i.rtually every stage o~ oil and gas production.
With ever i.ncreasing worlcl ener~y demancls and the ~dvent of i.nternational uel shortages the oil and gas :i.nclustry has been forced LO drill. deeper cln<3 deeper 35 into rnore hosti.'le ellvironsneslts in searcs~ o~ che cri.tical:l.y needed fue:1.. As a resu:1t cert:ain shi.gsl ternperat~lre high press~lre delep hori~.on gas fields have l)een d:i~icovered throughollL the worl.d wll:ich present a severc chal.lenge to ~ , , " ~:
':' - ~ ; ' ~3~
contemporary corrosi.on technology when one attempts to produce l.arge volu!lles o~ natural gas :in these fiel.cls.
The ~as wells o.E partic~lar interesL in the present invention are characterized by a combi.nati.on of 5 properti.es that l.eac~ ~o cor-rosion rates manyfo:l.d hi.gher Lhan ex~eriencecl in other gas fields. F:irsL alld roremosL, the gas wel.ls ~re comp:Leted at great dept:hs wh:i.ch in mal)y cases e~ceed ~0>()00 ft. Conseguentl.y, the gas we:l.ls are categorically high temperature~ high pressure wel.l.s. As a 1.0 general r~lle, at bottomhole ternperatures in e~cess of ~50~E ancl bottomho:Le pressures of the order of abo~lt 4,000 psi, one can anticipate severe corrosion. ~s these bottomhol.e temperatures and pressures i.ncrease, the proh-lems become even more pronounced such that at 400F and 15 pressures in e~cess of 5000 psi, the use of many corrosion i.nhibiting systems and n~ethocls is virtual:Ly prohibited.
The gas wells of interest in the present invention are of this nature.
Furthermore, the particul.ar gas wells of 20 interest are dry wells in the sense that no liquid petro-leum phase exists at the bottomhole conditions. Thus~ no protecti.ve oil fi.llll will be presenL LO coat the casing and to act ~s a corrosi.on :inhi.bitor carrier. In fact, since no conclensate phase exists at these bottomhole conditions, 25 injection or~ oil.-sol.~lble inhibitors i.n a petroleum conclen sate carrier will. be ineffective because o premature vaporizat:ion of the carrier be~ore reaching the bottoln of the well. To furcher complicate the lack of petrol.eum condensate phase at: the bottomhole conditi.ons, the gas 30 well.s of :interest will have an aqueo~s or br:ine phase present, and t.his, in combination with acid gases such as h~d30gen sul.fide, carbon dioxide or t:he Like, creat:es an e~tremely corrosive environrnent. Wi~:h gas producti.on in terrns of tens of mi.l:Lions of standarcl cubic ~eet per day, 35 the poss:ibi.:Lity of mairltaini.ng an oil conden~ate phase at ~)ottorrlhole condit:i.ons is for al..L pra~matic purposes ruled ouL .
.. . .
3~ ~ 2 In an articl,e entitled "Deep ~el.].s - A Corrosi.on L~ g~:ineer~ g Challerlge", by R. N. Tuttle allcl T. W. Ilalrlby, presented ~t the Inr.er-r~cltiona:l. Corrosi.on lor~lltl, April L4-1~, 1975, held at Toronto, Ontario, it was ack- ~.
5 nowledged that recent emptlasis on de~p hi,gh cemperc~t~e, hi.~h press~lre horiæons as potential gas prod~lcer.s an~ t:he associ.ated hostil.e env:irorlmellts encounte~ecl pres~nts a se~e~e chal.l~llg~ t~ col~temporary technolog~y. rll th~
clrticl.e, it was poi,nted out thac the bottornhol.e tempera-10 t~res as higl-l as 5S0~ have been encountered :in south Texas, and boctomhoLe pressures exceedin~ 22~000 psi are : -present in llissi.ssippi. It was also.point,ecl out that tubing failure caused by corrosion in deep wells has heen e~Ypcri.enced in cns li.ttle as eigh~een rnonchs in the l,acq : :l.5 ~ ld :in France, Get-m.3lly, hl.lst,ria, an~:l al50 Mi;s:i.ss:ipp:i.
: The Thornasvi.lle-Pilley Woods Fiel.d near ~ackson, Missis-sippi, is exernplif:iecl as involving ~as wel:l.s that fic the above descript,ion and have severe corrosion problems. The ~alse ~i.ver Field in Lou:isiana i.s be].ieved to contain gas 20 wel:ls that woukl have bottomhol.e concli.tions characteristic of the present invention. The articl~e concludes with the aclrllissi.on that. a new corrosion inhi.biting syst.e~l to cover fl.owing conditions i.n the range o~ 18,000-20,000 psi and 3~0-~50~F is neecled for operation of alltici.pated future 25 ~ell,s in south Texas aTld Mississippi.
SUM~RY OE T}IE _NV NTI N
In v:i,e~ oE the severe corrosion probletns encoun-: tered in gas well~ proc!ucing from very deep high pressureand high ~emperacure horizons whereir, no petroleuln conden-30 sate phase exists at botton~hole but an a~ueous or brinephase can be present, we have developed a method for inhi-biti.ng cor~-osi,on in such wel.ls :involvi.ng the step of:
T.njec,t:ing an effeccive amount. of a h~ h rnolecular we-i.ght fatty amine having from a~out 12 to 30 ~5 carbon atorns i.nto said gas well thus producing a prote<tive filln Fortnirlg phase at botLomho1e conditi.ons.
In onc aspect of the inv(nc-io[l, t:r-c ~at:ty anline is injecte(l :int:o the boLtom of the ga.s weLI. I~y :i.t:se:Lf. I.n .
i:, :
~2 another aspect, a small but effective amount of an oil s(llul~le c)r o-il cornpa r:it,`1 e corros:ion -inh~ c,r is ~ (l to the f.ilnl forrni~ 'atty amine carrier pr-i.or to i.njectio i.nto the gas ~!e.l:l.. Thus~ the primary object:ive o:f~ the 5 present invellLion :is to ~rovicle a ~ n for~ g :I:iqlli.d ase which is c(~nlF)at:i.b.le with conventiona~l oi~1 base cor-rosi.oll inlli~;tol:s x~lch rllat :injection of slnal'l vol.umes Of the li.qu.i(l in~o the gas wellci wherein a pe~r-ol.e~rrl con(-lerl-sate phase does not ex-ist wi.ll. result in a protective cor-10 rosioll :inhib:it:ing 1:i.qui<l phase downhole. `rn o(her wordsthe pri.mary ohjecti.ve of the present inverlt:ion is to pr-o-vicle an alternate corrosi.orl inhibilor carrier that wil:l.
perforlll i.n high telllper-ature, h:i.gh press~lrt gas wcll.s wiLhout condellscl~.e in a lllclnller analogo~ls to he per.i'or1il-15 arlce o an o:i`l corlclellsate/illll:ib:iLoL syscelll in a gas we'L:I.corlLa:ining a :I.i.cl~li.cl petro.leum ph<lse.
BRIii' DESCRIP'rION O~ rl`l-ll'~` DRAWlNG
The l-~R~ NG ~ ustraces the volulne ~actor as a function of pressure for the N-al.kyl-l 3-propane dianlille 20 nlixture (sokl as Duomeen T) in presence of dry g~s at 350~F'.
Tl-iE i~ESCR~IPTION O~' THE PREFE~RD IMl~ODIMEN'rS
Uporl recogllition of che severe corrosion prob-l.ems associate(l ~:ith the aforementioned types of gas wells 25 an(~ the real.iz.acion that the lack of a protective film forming condensate phase at bottomhole conditions :is the callse of the prob:lems only a limited number of ~lt~rna tives are available aside from capping che wel:l al~d stop-ping procluct}oll. Ec~ch of these alterna~ives i.s i.n some 30 way ]ess than full.y accepcable. Since there is an aqueous phclse present at botton~hole cond-itions th~ use of a water so~ul~le corrosi.on i.nh:ibi~or .is one al.~ernaL:ive. Ilowever the protective l-'ilm ~orrning charac~eL-isLics oi' a ~clueous ptlclSe :iS aCkllOWledged clS i.nferior LO chat ol an o:il fi.lln ~5 ..llld in C:OIllbil~ai_:i.Orl W:i.tll lligll gclS flow l-clLeC;~ chclraCteris~
tic~ :in excesx o~' 10 ~ilSCir'D (n~ l s~:.lll(l.lr(l cubic fect per ~lay) inakes l-he use of cl wa~er corr-os.iorl inh-ib~.or systenl:ineffec~.ive. S-i.nce lhe o-i:l condenscltt ~ . . . .
: ' 3~ 2 phase is nonexi.stellt at bot,omhole conditions, convenci.onal, addi.t:ion of an oil. soluble corros-lon i,nhibit,or d:i.ssolvecl :;n an oi.'L. carrifr :is v:irtually -impossibl.e. ~owever, ove:rdisp:laci.ng the gas well. w:it:h S 'Iarge volurnes of oi.l. containing all o:il based i.nhib:itor is an alternative. S~lch an alternati.ve i.s e~pensive :in that vel~ l.arge vo~ rnes are requirecl wh:ich in turn recluce gas procluction rate and requi.re expensive oversiæec~ equiplnerlt~
~:o achieve ~he necessary injection rates. Less volatil.e .0 heavy oils have been employed in ttle overdi.spl.acement techn:ique ~:o part:ially o~fset the ex~remel.y :large volulnes.
'ft has also been suggestecl that rnore expensive, exotic, noncorLosive metals be ernployed. ~ncl more Erequent pulling and rep:Laci,ng of produc:ti.on Lub:ing has been imple-1.5 mented. ~s of now, none o che alternativcs or combina-Lions of the al.terllcltives have proven to be equivalent: of wh~t would be expecce(l if an oil con(lensate phase could he mclintained at bottomhole c~onditions. The prev:i.ously referenced R. N. Tllttle, et al., article sulrlmarizes arl 20 ideal sol-ltioll to t-he problem in the fo:L:I.o~ing way, "A
s-;mp?.ier approach ~ould be to use a heavy oil. whi.ch woul.d ~r,ov:icle a h:igh clew-point pressure at low concelltrations :in Lhe mixed gas/oil inhi.bitor phase (if one can be ~'ound)."
The present inventi,on i5 such a syste~i. We have ~5 discovered that high ~nolecu:Lar weight fatty alnines are capable of exi.~ting i.n a lig~:id phase aL bot tOl[lhOl.e COIldi.~
tions character:i.~.~ic of the dry ~as ~e:l.l.s of interest.
This liquid phase is ~ound to be an effective corros:ion inh:ibitor as well ~s an effective oil base corrosion inh~
30 bitor carr-i.er wi.th excellent filrn rorming properties.
'I'hus J such composi.tions are extremely use:L-Il. in sup-pressing corrosi.on i.n the very hostile envi.-ronrnents of interest. Accordingl.y, a l.iquid phase has been observed at high temper~tllres ancl h:igh pressures irl t.he preserlce of 35 what corresponcl.s to hi~h gas fl.ow r-a~es cven t:hougll rela- ,' ti.ve]y srrlal'l. c~ nti.ti,es of corrosi,oll -inhibil,:ing colnl)osi.-tions were e~ )Loyecl.
.
O~
By far the most important feat:ure of the present:
:i.nvelltioll rel.at:i.ve to what has previo-lsl.y beerl c~rnployc(l is that the cornpos:it-iorls i.n the prior art: are incal>ab:le of sustaini.ng a liqu:id phase at the conclitions chaL-acterist.i.c 5 o~ the gas wel.l.s of interest, whereas the c~olrlpositi.orls oS
the present inventi.on clo exist in a liquid phase under the same hoscile conditiorls. T11i.s phase behavi.or di.f~ererlce is a consequer~ce of the compositiona:l. di.stincti.ons i.nvolvecl in selecting ~:he fatty amine.
L0 The high molecular weight fat:ty amines used in the present invention are, :in pri.nci.p:le, long cha:i.n allcyl amillex usually syntllesizecl Erom naLural:Ly occurri.llg fatLy acids wherein tlle a:l.kyl groups invol.ved have an average length in eAYcess of twe:lve carbon at-oms. Commercia:Lly 15 available fatt.y alrlines will ~Isually contain m:i~tures of alkyl chain lengths s:ince they are deri.vecl from atty acids occurring in rlature. ~requently, this w:ill also result in an aburlclance of the even carbon nurnber species and the presenc~e of unsaturatiorl such as ouncl in the 20 oleic, palrnitic, and the like structures. However, any - -:Long chain predominately aliphatic amine, whether :ic be a s:ingle speci.es with either even or odd numbered carbon atoms or miA~tures of these species, is, viewed as an acceptable high molecular weight amine for the purposes of 25 this invention. These fatty amines are preferably wa~y solids or semi-solids which ~re easily me:l.ted at tempera-tures characteristic of ~h~ gas we1:ls of irlterest. 'L'he preferred arnines will involve carboll chaill lengths of 16-30 carbon atoms. This pre.Eerred range is consi.stent 30 wiL-h the present view Lhat increas.ing ~he molecu:l.ar weight :itl order to decrease the volatil:ity i.s of paramount -Lmpor-tance :i.n achieving the desi.red liquid phase at bottom1~ole hiKh temperat-lres and h.igh pressures. A preferred sub class o~ facty arnirles which have beell fo~lncl to be part:ic~
35 larl.y useful. ill the present irlvellti.oll is the ~-al.kyl-1,3-l)rc)pane diarlli.tles. I`or a Inore cornplete d:iscus.siorl of the h:igh molecul,3r wci.gh~. al:iphatic arnines, th(-i.r res;)ective cherrl-i.cal. identiti.es, cornmcrcia:l. sources, physical an(l chelnical.
~. ' ,, ~: '', 6~0;~
properties, kno~n uses, and methods of synthesis, the FATTY AMINES chapter starting on page 283 of the 3rd Edi-tion, Volume 2, KIRK-OT~ER, "Encyclopedia of Chemical Technology" is per~inent.
It is felt -that the presence of the liquid fatty amine phase in the presence of high flow rate gas at high temperatures and high pressures is critical to successul , corrosion inhibition. In order to confirm the presence of the desired liquid phase at bottomhole conditions, a 10 serie~ of phase distribution measurements in a variable volume window PVT cell were performed.
The particular fatty amine employed in the testing was a mixture of N-alkyl-1,3-propane diamines having an average carbon num'ber of 1~ supplied by Armak of 15 Chicago under the trade name Duomeen~ T. This fatty amine -is described as a N-tallow-1,3-propane diamine having the general formula, RNHCH2CH2NH2. The compositional distribution o~ a typical mixture of alkyl radicals (the R ~ ' in the above formula) and some typical properties of this ~ , -20 fatty amine are presented in TABLE I.
*A -trademar'k of Armour Industrial Chemical Company .. . . ..
.
-3:3L63~2 T~BLE I
Typical Properties o~ Duomeen T
Alkyl Apparent Specific Iodine Chain Length Molecular ~.P. M.P. Gravity Value 5 Distribution ~/O) ~ _ C F (25C) Min. Max.
Dodecyl C12 1.0 350 300 195 0.841 32 45 Tetradecyl C143.0 Pentadecyl C150.5 Hexadecyl C16 29.0 10 Septadecyl C171.0 Octadecyl Clg23.0 Tetradecenyl C16' 1.0 :.
~exadecenyl C14' 3.0 Octadecenyl Clg' 37.0 15 OctadecadienylC18 " 1.5 .
Initially, the PVT cell was charged with 3.80 cc of Duomeen T at 1700 psia and 110F (43.33C) and 7.011 gram mols of gas having a composition given in TABLE II.
~5 . . : . . : . , ;, : , : , ,. ~':. `. ~... ' : :: ' '.
... . . . .
39~ 02 TABL~ II
Com~onent Mol E'ercent Ni.trogen 4 3 Met:hane 86.S
Carbon Dioxide 9.2 'Ihis part;.cular composition corresponds to
5 nowledged that recent emptlasis on de~p hi,gh cemperc~t~e, hi.~h press~lre horiæons as potential gas prod~lcer.s an~ t:he associ.ated hostil.e env:irorlmellts encounte~ecl pres~nts a se~e~e chal.l~llg~ t~ col~temporary technolog~y. rll th~
clrticl.e, it was poi,nted out thac the bottornhol.e tempera-10 t~res as higl-l as 5S0~ have been encountered :in south Texas, and boctomhoLe pressures exceedin~ 22~000 psi are : -present in llissi.ssippi. It was also.point,ecl out that tubing failure caused by corrosion in deep wells has heen e~Ypcri.enced in cns li.ttle as eigh~een rnonchs in the l,acq : :l.5 ~ ld :in France, Get-m.3lly, hl.lst,ria, an~:l al50 Mi;s:i.ss:ipp:i.
: The Thornasvi.lle-Pilley Woods Fiel.d near ~ackson, Missis-sippi, is exernplif:iecl as involving ~as wel:l.s that fic the above descript,ion and have severe corrosion problems. The ~alse ~i.ver Field in Lou:isiana i.s be].ieved to contain gas 20 wel:ls that woukl have bottomhol.e concli.tions characteristic of the present invention. The articl~e concludes with the aclrllissi.on that. a new corrosion inhi.biting syst.e~l to cover fl.owing conditions i.n the range o~ 18,000-20,000 psi and 3~0-~50~F is neecled for operation of alltici.pated future 25 ~ell,s in south Texas aTld Mississippi.
SUM~RY OE T}IE _NV NTI N
In v:i,e~ oE the severe corrosion probletns encoun-: tered in gas well~ proc!ucing from very deep high pressureand high ~emperacure horizons whereir, no petroleuln conden-30 sate phase exists at botton~hole but an a~ueous or brinephase can be present, we have developed a method for inhi-biti.ng cor~-osi,on in such wel.ls :involvi.ng the step of:
T.njec,t:ing an effeccive amount. of a h~ h rnolecular we-i.ght fatty amine having from a~out 12 to 30 ~5 carbon atorns i.nto said gas well thus producing a prote<tive filln Fortnirlg phase at botLomho1e conditi.ons.
In onc aspect of the inv(nc-io[l, t:r-c ~at:ty anline is injecte(l :int:o the boLtom of the ga.s weLI. I~y :i.t:se:Lf. I.n .
i:, :
~2 another aspect, a small but effective amount of an oil s(llul~le c)r o-il cornpa r:it,`1 e corros:ion -inh~ c,r is ~ (l to the f.ilnl forrni~ 'atty amine carrier pr-i.or to i.njectio i.nto the gas ~!e.l:l.. Thus~ the primary object:ive o:f~ the 5 present invellLion :is to ~rovicle a ~ n for~ g :I:iqlli.d ase which is c(~nlF)at:i.b.le with conventiona~l oi~1 base cor-rosi.oll inlli~;tol:s x~lch rllat :injection of slnal'l vol.umes Of the li.qu.i(l in~o the gas wellci wherein a pe~r-ol.e~rrl con(-lerl-sate phase does not ex-ist wi.ll. result in a protective cor-10 rosioll :inhib:it:ing 1:i.qui<l phase downhole. `rn o(her wordsthe pri.mary ohjecti.ve of the present inverlt:ion is to pr-o-vicle an alternate corrosi.orl inhibilor carrier that wil:l.
perforlll i.n high telllper-ature, h:i.gh press~lrt gas wcll.s wiLhout condellscl~.e in a lllclnller analogo~ls to he per.i'or1il-15 arlce o an o:i`l corlclellsate/illll:ib:iLoL syscelll in a gas we'L:I.corlLa:ining a :I.i.cl~li.cl petro.leum ph<lse.
BRIii' DESCRIP'rION O~ rl`l-ll'~` DRAWlNG
The l-~R~ NG ~ ustraces the volulne ~actor as a function of pressure for the N-al.kyl-l 3-propane dianlille 20 nlixture (sokl as Duomeen T) in presence of dry g~s at 350~F'.
Tl-iE i~ESCR~IPTION O~' THE PREFE~RD IMl~ODIMEN'rS
Uporl recogllition of che severe corrosion prob-l.ems associate(l ~:ith the aforementioned types of gas wells 25 an(~ the real.iz.acion that the lack of a protective film forming condensate phase at bottomhole conditions :is the callse of the prob:lems only a limited number of ~lt~rna tives are available aside from capping che wel:l al~d stop-ping procluct}oll. Ec~ch of these alterna~ives i.s i.n some 30 way ]ess than full.y accepcable. Since there is an aqueous phclse present at botton~hole cond-itions th~ use of a water so~ul~le corrosi.on i.nh:ibi~or .is one al.~ernaL:ive. Ilowever the protective l-'ilm ~orrning charac~eL-isLics oi' a ~clueous ptlclSe :iS aCkllOWledged clS i.nferior LO chat ol an o:il fi.lln ~5 ..llld in C:OIllbil~ai_:i.Orl W:i.tll lligll gclS flow l-clLeC;~ chclraCteris~
tic~ :in excesx o~' 10 ~ilSCir'D (n~ l s~:.lll(l.lr(l cubic fect per ~lay) inakes l-he use of cl wa~er corr-os.iorl inh-ib~.or systenl:ineffec~.ive. S-i.nce lhe o-i:l condenscltt ~ . . . .
: ' 3~ 2 phase is nonexi.stellt at bot,omhole conditions, convenci.onal, addi.t:ion of an oil. soluble corros-lon i,nhibit,or d:i.ssolvecl :;n an oi.'L. carrifr :is v:irtually -impossibl.e. ~owever, ove:rdisp:laci.ng the gas well. w:it:h S 'Iarge volurnes of oi.l. containing all o:il based i.nhib:itor is an alternative. S~lch an alternati.ve i.s e~pensive :in that vel~ l.arge vo~ rnes are requirecl wh:ich in turn recluce gas procluction rate and requi.re expensive oversiæec~ equiplnerlt~
~:o achieve ~he necessary injection rates. Less volatil.e .0 heavy oils have been employed in ttle overdi.spl.acement techn:ique ~:o part:ially o~fset the ex~remel.y :large volulnes.
'ft has also been suggestecl that rnore expensive, exotic, noncorLosive metals be ernployed. ~ncl more Erequent pulling and rep:Laci,ng of produc:ti.on Lub:ing has been imple-1.5 mented. ~s of now, none o che alternativcs or combina-Lions of the al.terllcltives have proven to be equivalent: of wh~t would be expecce(l if an oil con(lensate phase could he mclintained at bottomhole c~onditions. The prev:i.ously referenced R. N. Tllttle, et al., article sulrlmarizes arl 20 ideal sol-ltioll to t-he problem in the fo:L:I.o~ing way, "A
s-;mp?.ier approach ~ould be to use a heavy oil. whi.ch woul.d ~r,ov:icle a h:igh clew-point pressure at low concelltrations :in Lhe mixed gas/oil inhi.bitor phase (if one can be ~'ound)."
The present inventi,on i5 such a syste~i. We have ~5 discovered that high ~nolecu:Lar weight fatty alnines are capable of exi.~ting i.n a lig~:id phase aL bot tOl[lhOl.e COIldi.~
tions character:i.~.~ic of the dry ~as ~e:l.l.s of interest.
This liquid phase is ~ound to be an effective corros:ion inh:ibitor as well ~s an effective oil base corrosion inh~
30 bitor carr-i.er wi.th excellent filrn rorming properties.
'I'hus J such composi.tions are extremely use:L-Il. in sup-pressing corrosi.on i.n the very hostile envi.-ronrnents of interest. Accordingl.y, a l.iquid phase has been observed at high temper~tllres ancl h:igh pressures irl t.he preserlce of 35 what corresponcl.s to hi~h gas fl.ow r-a~es cven t:hougll rela- ,' ti.ve]y srrlal'l. c~ nti.ti,es of corrosi,oll -inhibil,:ing colnl)osi.-tions were e~ )Loyecl.
.
O~
By far the most important feat:ure of the present:
:i.nvelltioll rel.at:i.ve to what has previo-lsl.y beerl c~rnployc(l is that the cornpos:it-iorls i.n the prior art: are incal>ab:le of sustaini.ng a liqu:id phase at the conclitions chaL-acterist.i.c 5 o~ the gas wel.l.s of interest, whereas the c~olrlpositi.orls oS
the present inventi.on clo exist in a liquid phase under the same hoscile conditiorls. T11i.s phase behavi.or di.f~ererlce is a consequer~ce of the compositiona:l. di.stincti.ons i.nvolvecl in selecting ~:he fatty amine.
L0 The high molecular weight fat:ty amines used in the present invention are, :in pri.nci.p:le, long cha:i.n allcyl amillex usually syntllesizecl Erom naLural:Ly occurri.llg fatLy acids wherein tlle a:l.kyl groups invol.ved have an average length in eAYcess of twe:lve carbon at-oms. Commercia:Lly 15 available fatt.y alrlines will ~Isually contain m:i~tures of alkyl chain lengths s:ince they are deri.vecl from atty acids occurring in rlature. ~requently, this w:ill also result in an aburlclance of the even carbon nurnber species and the presenc~e of unsaturatiorl such as ouncl in the 20 oleic, palrnitic, and the like structures. However, any - -:Long chain predominately aliphatic amine, whether :ic be a s:ingle speci.es with either even or odd numbered carbon atoms or miA~tures of these species, is, viewed as an acceptable high molecular weight amine for the purposes of 25 this invention. These fatty amines are preferably wa~y solids or semi-solids which ~re easily me:l.ted at tempera-tures characteristic of ~h~ gas we1:ls of irlterest. 'L'he preferred arnines will involve carboll chaill lengths of 16-30 carbon atoms. This pre.Eerred range is consi.stent 30 wiL-h the present view Lhat increas.ing ~he molecu:l.ar weight :itl order to decrease the volatil:ity i.s of paramount -Lmpor-tance :i.n achieving the desi.red liquid phase at bottom1~ole hiKh temperat-lres and h.igh pressures. A preferred sub class o~ facty arnirles which have beell fo~lncl to be part:ic~
35 larl.y useful. ill the present irlvellti.oll is the ~-al.kyl-1,3-l)rc)pane diarlli.tles. I`or a Inore cornplete d:iscus.siorl of the h:igh molecul,3r wci.gh~. al:iphatic arnines, th(-i.r res;)ective cherrl-i.cal. identiti.es, cornmcrcia:l. sources, physical an(l chelnical.
~. ' ,, ~: '', 6~0;~
properties, kno~n uses, and methods of synthesis, the FATTY AMINES chapter starting on page 283 of the 3rd Edi-tion, Volume 2, KIRK-OT~ER, "Encyclopedia of Chemical Technology" is per~inent.
It is felt -that the presence of the liquid fatty amine phase in the presence of high flow rate gas at high temperatures and high pressures is critical to successul , corrosion inhibition. In order to confirm the presence of the desired liquid phase at bottomhole conditions, a 10 serie~ of phase distribution measurements in a variable volume window PVT cell were performed.
The particular fatty amine employed in the testing was a mixture of N-alkyl-1,3-propane diamines having an average carbon num'ber of 1~ supplied by Armak of 15 Chicago under the trade name Duomeen~ T. This fatty amine -is described as a N-tallow-1,3-propane diamine having the general formula, RNHCH2CH2NH2. The compositional distribution o~ a typical mixture of alkyl radicals (the R ~ ' in the above formula) and some typical properties of this ~ , -20 fatty amine are presented in TABLE I.
*A -trademar'k of Armour Industrial Chemical Company .. . . ..
.
-3:3L63~2 T~BLE I
Typical Properties o~ Duomeen T
Alkyl Apparent Specific Iodine Chain Length Molecular ~.P. M.P. Gravity Value 5 Distribution ~/O) ~ _ C F (25C) Min. Max.
Dodecyl C12 1.0 350 300 195 0.841 32 45 Tetradecyl C143.0 Pentadecyl C150.5 Hexadecyl C16 29.0 10 Septadecyl C171.0 Octadecyl Clg23.0 Tetradecenyl C16' 1.0 :.
~exadecenyl C14' 3.0 Octadecenyl Clg' 37.0 15 OctadecadienylC18 " 1.5 .
Initially, the PVT cell was charged with 3.80 cc of Duomeen T at 1700 psia and 110F (43.33C) and 7.011 gram mols of gas having a composition given in TABLE II.
~5 . . : . . : . , ;, : , : , ,. ~':. `. ~... ' : :: ' '.
... . . . .
39~ 02 TABL~ II
Com~onent Mol E'ercent Ni.trogen 4 3 Met:hane 86.S
Carbon Dioxide 9.2 'Ihis part;.cular composition corresponds to
4.0G barrels oL ia~:t:y alll.irle bein~ :injectecl i.nto gas well per Irlillion stanclard cubic feet of gas be:iilg procluced froln the well (Bbl/MMSC~. The PVT cell was held at 351~ .
IO (1.77'~C) while Lhe vo:Lume was varied such that the press-lre in the cell ranged frotm approxirnately 3,~00 psia up to : 15,000 psia. The total volurne of the ce:Ll and the volume of the liclui.d phase present in the cell. were recor<le<l at ~.he vari.ous pressures and are presented in TABLE :LI~ and lS the DRAWING.
TABL~
Phase Distrih-ltion Test Results and Volume Factors for Duorneen T
in a Mixture of 4.06 Bbl Duomeen T/MMSCF Gas at 350E
Vol.ume I.iquid at ~0 Pressure, Total Licluid Volume % T~P per Volume psia Volume(2), cc Vol~lrne, cc L.iq~lid Duon~een r c 2976 1301.. 7~i 3.4 0.26 0.~'35 5103 811.99 3.0 0.37 0.7~9 7057 637.15 2.4 0.38 0.631 25:9061 5~i~.27 1.8 0.33 0.~17~
llO18 486.39 l.~ 0.2~ 0.3~j8 13080 ~1~15.50 1.0 0.22 0.~)3 15036 l~l7.38 0.9 0.22 0.237 As indi.cated in the:third and fourth columns o.
30 'rABLE III, a significant amount of liquid phase was pre-sent throughout the entire pressure range at che tested conditions. This establ.ishes that the cr:itically neeclecl liq~li.d phase wi.ll ex:ist at bottomhole condi.t:ions corre-spollcli.rlg to the test conditions. The fi~th co:l.unlll repre-serltC; the rati.o of volutne of li.q~l:id at: t:he specified terr;-peratur~ and pressure per volutne oF ~a~ty arnine i.njecte(l.
Such clata are of practiccll impor~ance for designillg a coln-meL^cia]. well. treatlnent in that ic clllant.ita~.:ively reflects ' ~. ' 1~3~Z
~-he relative volume of l:iquid phase rema:i.n:in.g at vari.ous pressures (del~th~;) in the wel.l. when ~l.06 Bl)l.s o~' ~'acty alni.nes are i.njectecl per MMSCI` oE g~lS bei.rlg prC~(IUC('(l. ~'`OI-exampl.e, at approxin~atel.y 15,000 psi 23.7% o~ the vol~lrne
IO (1.77'~C) while Lhe vo:Lume was varied such that the press-lre in the cell ranged frotm approxirnately 3,~00 psia up to : 15,000 psia. The total volurne of the ce:Ll and the volume of the liclui.d phase present in the cell. were recor<le<l at ~.he vari.ous pressures and are presented in TABLE :LI~ and lS the DRAWING.
TABL~
Phase Distrih-ltion Test Results and Volume Factors for Duorneen T
in a Mixture of 4.06 Bbl Duomeen T/MMSCF Gas at 350E
Vol.ume I.iquid at ~0 Pressure, Total Licluid Volume % T~P per Volume psia Volume(2), cc Vol~lrne, cc L.iq~lid Duon~een r c 2976 1301.. 7~i 3.4 0.26 0.~'35 5103 811.99 3.0 0.37 0.7~9 7057 637.15 2.4 0.38 0.631 25:9061 5~i~.27 1.8 0.33 0.~17~
llO18 486.39 l.~ 0.2~ 0.3~j8 13080 ~1~15.50 1.0 0.22 0.~)3 15036 l~l7.38 0.9 0.22 0.237 As indi.cated in the:third and fourth columns o.
30 'rABLE III, a significant amount of liquid phase was pre-sent throughout the entire pressure range at che tested conditions. This establ.ishes that the cr:itically neeclecl liq~li.d phase wi.ll ex:ist at bottomhole condi.t:ions corre-spollcli.rlg to the test conditions. The fi~th co:l.unlll repre-serltC; the rati.o of volutne of li.q~l:id at: t:he specified terr;-peratur~ and pressure per volutne oF ~a~ty arnine i.njecte(l.
Such clata are of practiccll impor~ance for designillg a coln-meL^cia]. well. treatlnent in that ic clllant.ita~.:ively reflects ' ~. ' 1~3~Z
~-he relative volume of l:iquid phase rema:i.n:in.g at vari.ous pressures (del~th~;) in the wel.l. when ~l.06 Bl)l.s o~' ~'acty alni.nes are i.njectecl per MMSCI` oE g~lS bei.rlg prC~(IUC('(l. ~'`OI-exampl.e, at approxin~atel.y 15,000 psi 23.7% o~ the vol~lrne
5 injected is the vol.ume of liqui.d phase at ~el:l cond-itions.
This feature i.s frlrther il.lustrate~l in the ~AW'LNC where a COllt:in~lOUS c~lrve dep:icting the vo'Lume fac~.or Or l~uomeen rl' fr<)rn approxim<l~.el.y 3,000 ps:ia up to l5,000 psi.a estab-I.ishes the presence of a critical. I.iquid phase throughouc 10 ~he entire range. It is significant to note that the li.qui.d phase is present even though the cluant:ity heing inject:ed corresponcls to approximately L~ Bbls/MMSCF of gas being produced. In contrast, it is not utlcommon i.n extre~ el.y hosti:l.e dow~ ol.e environmellts of :inLerest to 15 previously measure the amo-lnt of ii~jected flui.cl :in terrns o~ hundreds o~' barre:ls per ~MSCf~ s such, che present invention accompl.ishes what the prev-i.o-lsly ceferenced . N. Tutcle, et al., article describecl as an ideal solu-ti.on to the probleln. In doing so, the proposed methc~d 20 rnakes the volurrle o :injected fl~licl essencially eq~lival.ellt to what is conventionclLly employecl in shall.ower we].ls wherein the bottomhole conditi.ons are compatible witll che presence o a liquid petroleu'm condensate phase. This means that the present inven~ion can be imp'Lem~nt,ed i~ith 25 equipment and procedure~ essenti.ally i.denti.cal to the less hos~.ile oil an(~ gas wells.
F'rom the cornposite of the phase discril~lti.on clata presented ~here, certain basic concepts re.Lati.ve t:o tlle practice of the present invent:ion can be esLabl.:i.shecl.
30 First arld foremost the use of the fatty am-ine as a corro-sion i.nhibicor or corrosion inhibitor carrier res~llts in the presellce oL a liqu:icl phase even ullcler severe h:igh ~e~
peratures and l-ligh press-lres assoc:i.a~ed wi.~.h l:he deep clry gas well of incerest:. I;`urthermc>re, sign:i.L:icant volulnes of 35 I.;.(:l-lid pllclse can be mai.ntained at: bol.l,ollll-lo'le cond:it:i.ons :in tlle presence of very h:i.gh rates oC ~Iry gas pro(l~lcc:i.orl w-ich as little a<; ~l ~bls of injected o:i~/MM~CI;` c)f clry gas beillg procluce~ s previ.o-lsly stacecl, 5il1Ce ~he compos:i.t.i.ons oL
. ~
- , i ~13~Z
the present invention achieve the desired li.quid phase at very .fclvorab:Le low in,jection ra~es, ~,hc~y can ~e ernployed in a manner anal,ogous to prev:ious prac:cices associclte wit:h inhibiting corrosion in ~as wells ~.~herein a conclen-5 sate pllase can e~ist at bottomhole conditi,ons. Suchmethods inc'l.ude periodic or continuous injectioll of t~he corros;.on inhi,b:itol- Wit}l or without a cli.luent ancl the ].:ike.
I-n additi.on to the presence of a l:iq-licl phase at l.0 these hostile bottomhole conditi.ons, the fal~ty ami.nes oi-' the present inventi,on inherently possess ot:her acl~anta-geous properties. ~irst, the fatty amines exh:ibi.t. excel.-l,ent fi,lm forrning properti.es at high temperatures ancl pressures. Thi.s i,s vi.ewed as being beneficia'L in sur-15 press:ing corrosion :in that good fi,lm formlng propertiesresult in more uniforrn coating of the exposed steel sur-faces and optimizes corrosion i.nhibicion. Secondly, the ~'atty amines exhibit corrosion inhibition in and of itself in a manner anal,ogous to what is known with respect to 20 organic amines when used at less severe telnperatures and pressures. With re~ards to the corrosion i,nhibition pro-perty, th~e N-alky'L-1,3-propane di.amines are again viewed as being the preferred atty amine in that the presence of t:he second a~ine ni.trogen enhances the corrosion inhi'bi-25 tion.
In order to further enhance the corrosion inhi-bition properties of the fatty amine, an effective amo~lnt of an oil soluble or oil base corros:ion inhibitor can be ad~ded prior to injection into the well. In th:is manner, 30 the fa~ty amine is functioning as a corrosion inh:ibitor carri.er similar to what is commonly pract:i.ced i.n the oil and gas production industry at lower presswres and tem atures wherein various oi:L condensates, diesel oil., and the Like are usecl as carriers. Such a process invoLves 35 t:he acklitioll of an effecti.ve amourlt o~ the convent:ionc oil sol.ul>le or so-calle(l oil basecl coLrosk~rl inhibitol- to the f-'a~ty amine ancl then injecti.llg the mixt,ure l.nto the gas well to be trc.atecl. These oil soluble or oi.:l hased ~3~0Z
eorrosion inhibi.tors inelude, but are not ].irnited to, such additives as organie po:Lar ancl het:eropolar eompounds containing nitrogen, oxygen, su:lfur, ancl/o-r other el.ements in Groups V and VI which inclucle amines, alllids, S mercaptans, heteroeycl.:ie nitrogen eompounds, ~Ireas, th:ioureas, phosphates, po1yphosphate~" o.~ya:LkyLates, and the like. A~ain, the uniclue aspect of the use oL ~:he faLty ami.ne as a corrosion :inl-lib:icor carrier :invo~ves ~he abili.Ly of fatty amine to sustain a liq-~icl fil.rll ~orrning 10 phase at severe hosli.le eoriditions even whell us:ing v~ry sln.lll vo]-]mes of ir-jeetecl f:l.uicl.
The actual. injection of the corrosion irlh:il):iti.rl~, compositions of the present invent:ioll can be accorllpllslled by any of the methods cornmonLy practiced :in the oi.l and 15 gas industry for surpressing eorrosi.on or adding aclditives to downhole fluids. Sinee the desired liquid phase can be achievecl at relatively srrlall volumes of injected fatty arllines, the use of a spaghetti string injeetion system or the like is preferred.
Having thus deseribed the preerred ernbodiments, the invention :is not to be eonstruecl as limited to the partieular forms di.selosed and tests, since these are regarded as illustrative rather than r-estrictive. rhere-fore, the fol:Lowing elaims arè i.ntended to eov~r all pro-25 eesses whieh clo not depart from the spirit and seope o~
using irl high tempercl~ure, high pressure wel.1s, a rela-t:ively nollvol.a~ile high moleeul.ar weigh~ ratty arll:ine as a eorrosion inhibitor or eorrosion inhibitor car-r:ier.
This feature i.s frlrther il.lustrate~l in the ~AW'LNC where a COllt:in~lOUS c~lrve dep:icting the vo'Lume fac~.or Or l~uomeen rl' fr<)rn approxim<l~.el.y 3,000 ps:ia up to l5,000 psi.a estab-I.ishes the presence of a critical. I.iquid phase throughouc 10 ~he entire range. It is significant to note that the li.qui.d phase is present even though the cluant:ity heing inject:ed corresponcls to approximately L~ Bbls/MMSCF of gas being produced. In contrast, it is not utlcommon i.n extre~ el.y hosti:l.e dow~ ol.e environmellts of :inLerest to 15 previously measure the amo-lnt of ii~jected flui.cl :in terrns o~ hundreds o~' barre:ls per ~MSCf~ s such, che present invention accompl.ishes what the prev-i.o-lsly ceferenced . N. Tutcle, et al., article describecl as an ideal solu-ti.on to the probleln. In doing so, the proposed methc~d 20 rnakes the volurrle o :injected fl~licl essencially eq~lival.ellt to what is conventionclLly employecl in shall.ower we].ls wherein the bottomhole conditi.ons are compatible witll che presence o a liquid petroleu'm condensate phase. This means that the present inven~ion can be imp'Lem~nt,ed i~ith 25 equipment and procedure~ essenti.ally i.denti.cal to the less hos~.ile oil an(~ gas wells.
F'rom the cornposite of the phase discril~lti.on clata presented ~here, certain basic concepts re.Lati.ve t:o tlle practice of the present invent:ion can be esLabl.:i.shecl.
30 First arld foremost the use of the fatty am-ine as a corro-sion i.nhibicor or corrosion inhibitor carrier res~llts in the presellce oL a liqu:icl phase even ullcler severe h:igh ~e~
peratures and l-ligh press-lres assoc:i.a~ed wi.~.h l:he deep clry gas well of incerest:. I;`urthermc>re, sign:i.L:icant volulnes of 35 I.;.(:l-lid pllclse can be mai.ntained at: bol.l,ollll-lo'le cond:it:i.ons :in tlle presence of very h:i.gh rates oC ~Iry gas pro(l~lcc:i.orl w-ich as little a<; ~l ~bls of injected o:i~/MM~CI;` c)f clry gas beillg procluce~ s previ.o-lsly stacecl, 5il1Ce ~he compos:i.t.i.ons oL
. ~
- , i ~13~Z
the present invention achieve the desired li.quid phase at very .fclvorab:Le low in,jection ra~es, ~,hc~y can ~e ernployed in a manner anal,ogous to prev:ious prac:cices associclte wit:h inhibiting corrosion in ~as wells ~.~herein a conclen-5 sate pllase can e~ist at bottomhole conditi,ons. Suchmethods inc'l.ude periodic or continuous injectioll of t~he corros;.on inhi,b:itol- Wit}l or without a cli.luent ancl the ].:ike.
I-n additi.on to the presence of a l:iq-licl phase at l.0 these hostile bottomhole conditi.ons, the fal~ty ami.nes oi-' the present inventi,on inherently possess ot:her acl~anta-geous properties. ~irst, the fatty amines exh:ibi.t. excel.-l,ent fi,lm forrning properti.es at high temperatures ancl pressures. Thi.s i,s vi.ewed as being beneficia'L in sur-15 press:ing corrosion :in that good fi,lm formlng propertiesresult in more uniforrn coating of the exposed steel sur-faces and optimizes corrosion i.nhibicion. Secondly, the ~'atty amines exhibit corrosion inhibition in and of itself in a manner anal,ogous to what is known with respect to 20 organic amines when used at less severe telnperatures and pressures. With re~ards to the corrosion i,nhibition pro-perty, th~e N-alky'L-1,3-propane di.amines are again viewed as being the preferred atty amine in that the presence of t:he second a~ine ni.trogen enhances the corrosion inhi'bi-25 tion.
In order to further enhance the corrosion inhi-bition properties of the fatty amine, an effective amo~lnt of an oil soluble or oil base corros:ion inhibitor can be ad~ded prior to injection into the well. In th:is manner, 30 the fa~ty amine is functioning as a corrosion inh:ibitor carri.er similar to what is commonly pract:i.ced i.n the oil and gas production industry at lower presswres and tem atures wherein various oi:L condensates, diesel oil., and the Like are usecl as carriers. Such a process invoLves 35 t:he acklitioll of an effecti.ve amourlt o~ the convent:ionc oil sol.ul>le or so-calle(l oil basecl coLrosk~rl inhibitol- to the f-'a~ty amine ancl then injecti.llg the mixt,ure l.nto the gas well to be trc.atecl. These oil soluble or oi.:l hased ~3~0Z
eorrosion inhibi.tors inelude, but are not ].irnited to, such additives as organie po:Lar ancl het:eropolar eompounds containing nitrogen, oxygen, su:lfur, ancl/o-r other el.ements in Groups V and VI which inclucle amines, alllids, S mercaptans, heteroeycl.:ie nitrogen eompounds, ~Ireas, th:ioureas, phosphates, po1yphosphate~" o.~ya:LkyLates, and the like. A~ain, the uniclue aspect of the use oL ~:he faLty ami.ne as a corrosion :inl-lib:icor carrier :invo~ves ~he abili.Ly of fatty amine to sustain a liq-~icl fil.rll ~orrning 10 phase at severe hosli.le eoriditions even whell us:ing v~ry sln.lll vo]-]mes of ir-jeetecl f:l.uicl.
The actual. injection of the corrosion irlh:il):iti.rl~, compositions of the present invent:ioll can be accorllpllslled by any of the methods cornmonLy practiced :in the oi.l and 15 gas industry for surpressing eorrosi.on or adding aclditives to downhole fluids. Sinee the desired liquid phase can be achievecl at relatively srrlall volumes of injected fatty arllines, the use of a spaghetti string injeetion system or the like is preferred.
Having thus deseribed the preerred ernbodiments, the invention :is not to be eonstruecl as limited to the partieular forms di.selosed and tests, since these are regarded as illustrative rather than r-estrictive. rhere-fore, the fol:Lowing elaims arè i.ntended to eov~r all pro-25 eesses whieh clo not depart from the spirit and seope o~
using irl high tempercl~ure, high pressure wel.1s, a rela-t:ively nollvol.a~ile high moleeul.ar weigh~ ratty arll:ine as a eorrosion inhibitor or eorrosion inhibitor car-r:ier.
Claims (7)
1. A method for inhibiting corrosion in a high temperature, high pressure gas well, characterized in that no petroleum condensate phase exists at bottomhole condi-tions, involving the step of: injecting an effective amount of a high molecular weight fatty amine, having from about 12 to 30 carbon atoms, into said gas well thus producing a protective film forming phase at bottomhole conditions.
2. A method for inhibiting corrosion according to Claim 1 wherein said fatty amine contains an oil soluble corrosion inhibitor.
3. A method for inhibiting corrosion according to Claim 1 wherein said fatty amine is a N-alkyl-1,3-propane diamine.
4. A method for inhibiting corrosion according to Claim 3 wherein the alkyl group contains from about 16 to 30 carbon atoms.
5. Method as in Claim 1 wherein the high tempera-ture, high pressure gas is further characterized in that an aqueous or brine phase is present.
6. A method for inhibiting corrosion according to Claim 2 wherein said fatty amine is an N-alkyl-1,3-propane diamine.
7. A method for inhibiting corrosion according to Claim 6 wherein the alkyl group contains from about 16 to 30 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6445979A | 1979-08-06 | 1979-08-06 | |
| US064,459 | 1987-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131002A true CA1131002A (en) | 1982-09-07 |
Family
ID=22056139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA357,330A Expired CA1131002A (en) | 1979-08-06 | 1980-07-30 | Method for inhibiting corrosion in high temperature, high pressure gas wells |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA1131002A (en) |
| DE (1) | DE3029790A1 (en) |
| FR (1) | FR2463197A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6939483B2 (en) | 2000-02-28 | 2005-09-06 | Pabu Services, Inc. | Brine fluids with improved corrosion properties |
| US11474045B2 (en) | 2018-04-03 | 2022-10-18 | Framatome Gmbh | Method and device for the determination of film forming amines in a liquid |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2658558B1 (en) * | 1990-02-22 | 1992-06-12 | Ungemach Pierre | WELL PROTECTION DEVICE AGAINST THE RISK OF CORROSION OR DEPOSITS DUE TO THE NATURE OF THE FLUID PRODUCED OR IN PLACE IN THE WELL. |
| WO1997002085A1 (en) * | 1995-07-06 | 1997-01-23 | Reicon Wärmetechnik Und Wasserchemie Leipzig Gmbh | Method of washing acid gases out of gaseous mixtures in order to reduce corrosion and corrosion owing to erosion |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2840525A (en) * | 1953-10-01 | 1958-06-24 | Pan American Petroleum Corp | Method of inhibiting corrosion of metal surfaces |
| US2846440A (en) * | 1955-12-12 | 1958-08-05 | Citics Service Res And Dev Com | Composition for and method of inhibiting corrosion of metals |
| US3749554A (en) * | 1970-06-08 | 1973-07-31 | Union Oil Co | Method for reducing erosion and corrosion of metal surfaces |
| DE2604203A1 (en) * | 1976-02-04 | 1977-08-11 | Peter Siegfried | Corrosion protection of delivery pipes for acidic natural gas - by addn. of amine salts of benzolc acid |
-
1980
- 1980-07-30 CA CA357,330A patent/CA1131002A/en not_active Expired
- 1980-08-06 FR FR8017406A patent/FR2463197A1/en active Granted
- 1980-08-06 DE DE19803029790 patent/DE3029790A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6939483B2 (en) | 2000-02-28 | 2005-09-06 | Pabu Services, Inc. | Brine fluids with improved corrosion properties |
| US11474045B2 (en) | 2018-04-03 | 2022-10-18 | Framatome Gmbh | Method and device for the determination of film forming amines in a liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2463197A1 (en) | 1981-02-20 |
| DE3029790A1 (en) | 1981-02-26 |
| FR2463197B1 (en) | 1984-04-06 |
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