Маркин А.Н., Низамов Р.Э. СО2-коррозия нефтепромыслового оборудования
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KoHIIeHTpa\Hfl, rl3a B xfl,rAKocru, naorufuurp,
G
-
noc'ro-
flHr,afl
(roHcraura)
f
enpa.
VpanHeuue
(1.3)
cnpaoegruBo
Nts
BeulecrB, He MeHrroulrx
cnoeft
MoJreKynrpHofi
uaccu
npu
pacrBope$t4lfl'.
flocrcomny co2,
pacrBope-
rcb
B BoAe, o6pasyvr
cna6Fo
yrorrbnyro
KHcJrory HzCOI
(nuor4a
ee
o6ognaqaror rax CO2'O),
Auccorluupyroqyo
c o6pa3oBaHueu 6urcap-
6osar-
u rap6ouar-HoHoB
(roucraHru
Ar.rccorluar{fiH
npu 25
"C
co-
craBJrrror:
R1
:
4,47. l0-7, K2:
4,68.
I 0-l
l)
co2
+
H2o
<>
H2co3
H2Co3
(
K'
>Ff
+HCo3
HCO3 <
Kz
>Ff
+
cor'-,
(1.4)
(l.s)
(1.6)
7
C O
2
- rcopp osun H ebm enp orn br cl
06
oz
o o 6 opyd oa auua
To 3aKoH
feupu 3Aecb BbrnoJrHqercr roJrbKo
AJr{
HeAHccorIHHpoBaHHofr
lIzCOl
(COraq).
KoHcrauta
feupn orucrlBaer
paBHoBecLIe
cl{creMbl
"ra3
-
pacrnop"
H
3aBncr,rr
or reMneparypbr B coorBercrBau
c reM )Ke
3aKOHOM,
.rrO
r.r
rro6afl
KoHcraHTa
paBHoBecHt
dlnG
LH
dr
=
RTz'
(1.7)
rle LH
-
r€MeHeHr.re 3HTaJrbrrnlr rrpu
pacrBopennvr,
Z
-
reunepa-
Typa, K.
CoorHouresue
(1,7),
onpeAeJrrroulee 3aBncuMocrb KoHcraHTbr
paBHoBecr,rf,
or
reMneparypu, 6rtro BbIBeAeHo Barn-foQ$oM n H€t3bI-
Baercfl
ypaBHeHHeM
nso6apu BaHr-fo$Qa. CoornorueHr{e rroKzr3brBaer,
qro
3HaK npou3BoAHofi
roncranrbr
paBHoBecr4s.
rro
reMneparype onpe-
AeJrrercfl
3HaKoM
TerrJroBoro sQ$ercra
peaKrlun.
Pacrnopenae ra3oB B
)Kr,rAKocrrx o6uqso co[poBoxAaerc.fl
BbIAeJreHHeM
Terura
(AH<O)
u,
cJreAoBareJnuo, G
yMeHbrrraercr
c
yBeilllrreHr.reM
TeMfieparypu. To
ecrb,
npn
AaHHoM
naprluaJrbHoM
AaBneHr,rH
COz
(Pco2)
pacrBopr,rMocrb
coz
n BoAe
naAaEr
c Bo3pacraHHeM reMrreparypbr. B ra6n. l.l npnne-
AeHbr
3HaqeHr4rr
KoHcraurlr feHpu
gttx
co2 flpu
pa3rHquofi
reunepa-
Type,
paccqnTaHHbre
no
AaHHbrM
[2]
(cu.
Tarcr(e
flpruoxeHue 3).
Ta6nuqa I.l
3aslcnMocru
KoncranTbr lenpn m
reuneparypbr
rrpn
pacrBopeHln
cor B
AncTlnnnponanuofi
ao4e
(paccxxrauo
uo
aauurrnr
[2])
TeMneparyDa,
"C
l5 20 25 30
35
40 45
50 55
G,
uoru/(aw-r) 0,04539 0,03912 0,03383
0,02964 0,02638 0,02363
0,02134
0,0
I 944
0,ol77l
B nrreparype
(cu.,
HarrpuMep,
[2,3])
uoNHo Hairru
pr
6oree roqHrre
3aBlrcuMocrm
K1u 1{2
or
reuneparypbr
nuga K1, Kz
:
F
(a
+
bT
*
c/T
+
+
d/r2+elgT).
oAHarco
cpaBHeHre
sHaqeHufi K1 u R2,
paccqrraHHbrx
rlo
(1.8)
u
(1.9),
c nrreparypHbrMlr
AaHHbrMn,
noKa3aJro,
rrro
B
HrilepBare
TeMfleparyp
0...50
oC
cpe4uee orHoclrreJrbHoe
orKJroHeHr{e KoHcraHT or
Tor{Hbrx eHaqeHr,rfi
cocraBJrrer 0... I I Yo. B ro xe BpeMJ{ TeMneparypHbre
3aBucrrMocrr.r
(1.8)
ta
(1.9)
HarmaHbr H MeHee rpoMo3AKH.
Ilorouy,ta-
JIee, rAe 3To Bo3MoxHo, Mbr
6yaeivr
[pr.rBoAr,rrb
reM[eparypHbre 3aBrlcH-
Mocrr,r
KoHcraHr paBHoBecnfl nuga
(1.8), (1.9).
Kar ugnecrHo,
rrpucyrcrBr,re
B
pacrBope
Apyrnx
HoHoB,
AzDKe
He
f{acrByloqr{x
B
AaHHofi
xptuuqecrofi
peanqnu,
cyqecrBeHHo BJrHrer
Ha
xuMl4qecKoe
paBHoBecI,Ie.
9To Brr,rsHue 3aBHcHT or [apaMerpa, Ko-
ropuft HzubrBaercs
"HoHHar
crdJra
pacrBopa"
I tt
onpeAeJrrercr
KaK
IgKl
:
-
10,33
+
2,70
Q
-
_
29!2-
).
t
+ 273,2
'
r:
)zc,.z?
,
(l.e)
(1.10)
Ecru
noAa
[pon3BoJrbHoro
xHMuqecKoro cocraBa HaxoA]rrcs
noA
AaBJTeHHeM
CO2,
To
KoHrleHrpaqwxHzCOt-
6'Pcoz=
const
npn nocTo-
.sHuofi
TeMlepa1)rye t,
oC
tr Pcoz, a
KoJrI,IqecrBo
pacrBopeHlrofi
neAuc-
coqvtpoBaHnofi H2CO3 Mo)I(Ho orpeAeilHTb
no ra6l. 1.1. Konqerrpa-
qura
HCO:-, COt'- u
pH
6yayr
orpeAeJltrbcr Lr3
ycJroBufi panHonecu.n
no
peaKqr{f,u
(1.5)
n
(1.6)
c
)AreroM
BIrvIflHHt reMreparypbr H nplrc)rr-
cTBr{Jr
B
pacTBope
Apyrrx
BerrlecrB.
TeuneparypHble 3aBHcItMocrH
tcoHcrarrr
.I(1 u I(2
l#t
:
-
6,352
+
2,08
g
-
-2!!-1,
t
+
273,2"
rge
C;- KoHrleHTpaqus
i-ro rroHa B
pacTBope,
uonrh; 21-sapxg
,'-fo HoHa
B sJreMeHTapHbrx 3aprAax.
Ecru norHrtfi rouuoueursrrfi cocraB
BoAbI
HeH3BecreH, Ho
rr3-
BecrHa
o6ulax Mr.rHepanrnarlar
M, ro 1
(uonr/t)
:
IW40000, r,qe
M errpaxeno s Mr/r
[al.
Nts
KoJrr,rqecrBeHHoro oilHcaHut Brrufllenr.
noHnofi
cnJrrr Ha xnMnqecKoe
paBHoBecr.re
noJrb3yrorcr serfi.r4Hofi ax-
THBHOCTH
oi:
Ci.fi,
(1.
l 1)
t,la ai- aKTr{BHocrs
i-ro uoua,f- xos$SraqueHT aKTHBHocrI,r ,'-ro
HOHA.
flog
arcrnnHocrbrcl
noHuMaercr BeJrnrruHa, [oAcraHoBKa roropofi
BMeCTO KOHrIeHTparIHrr B
)paBHeHHg,
OttUCb.tBarOIrIHe XlIMlIqeCKOe
paB-
HOBeCHe,
AeJIaET
nOCJIeAHLTe
rrpHMeHlrMbru*t
NIt
pealrbHblx paCTBOpOB.
HcnonrgosaHne
BeJrr.rquH aKTHBHocreft srvrecro
KoHrlerrrpaqnft
npano-
Alrr
K He3aBHcHMocr[
rrncreHHblx
3HaqeHprfi
xoHcrant
paBHoBecE
or
rrpucyrcrBrrr
B
pacrBope
Apyrrx
HoHoB. Kosr[QnqueHT
aKTuBHocrr/r, a
cneAoBarenbHo,
H aKTr{BHocrb, 3aBr,rcrr or
uosnoft
crdlbr
pacrBopa.
lpn
pas6aarenubrx
pacrBopon
/
crperrrxrcr K l, c
ynernueHneM
noHsoft
(1.8)
(1.12)
tAe AD
v Bo
-
KoHcraurbl,
3aBI{csuIHe
or reMneparypbr,
ri
-
a{$en-
TrrBHbrfi
HoHHbrfi
paAl{yc
i-ro
uoua, A.
3Ha.{eHI,rt Ae
v Bp
AJI'
pa3nHqHblx reMrlepar)/p
npHBeAeHbI r IIpn-
Jrox(eHHH
l;
4
uoHon,
npncyrcrByrculnx
B BoAHrIX
Qasax
He$TtHbIx
H
rruoBbrx
MecropoxAeuuit,-
n flpuloxesuu2. VpaoueHue
(1.12)
cnpa-
BeAJTHBo
Ao
1< 0,1.
flpra 0,1
<
1< 1,0
uoxuo Boc[oJlb3oBarrcr
uo4n$N-
rIapoBaHHbIM
ypaBHeHltenr
.{e6aa-Xorrem
[2]
A,H. Mapxutt,
P.3. HusaMoe
cwuf craruoBuTcr
(1,
a
npn sstcorofi uonHoft cune rcos{SHqHeHT aK-
TTTBHOCTH
An-fl
HeKOTOp6TX
BerrlecrB Bo3pacTaer H Mox(eT nperucurr
l.
IL
,{e6afi
u
E.
Xroxrem
(1923
r.), ocuonuBascb Ha
MoAeJIbHbIX rpeA-
cTaBJreHnrx o
THApaTHpOBaHHH
HOHOB
B
pacTBopax
SJreK'rpOJIl,ITOB,
rpeAJroxuJrra
Soprrryrry,
cBt3btBaloulyro xosS$uqueHrrt
aKTHBHocTH
HoHoB c r.roHHofi curofi
Ilpunep
I . flycrr
P6q
:
0,03
5 rII4 t
:
25
oC,
H B pacrBope
coAepxr.rrct
50 nr/"rr
HCO|
(nocle
pacrBopeHrxr
NaI{CO3),
a raroKe
oKono
1,0 r/n NaCl,
raK
qro
HoHHiur
cllra paBHa
0,025
uons/t
TorAa Korqerrrparyrfl
H2CO3
(cnr.
ra6ir.
l.l)
6yaer panHa
(0,00035).(0,03383).(62)(1000)
=
0,73 ur/n.
flo-
cKoJrbKy
KoHrlerrrpaqnr
HCO3-
6onee
'{eNa
s 60
pa3
npeBburraer
KoHqeH-
Tpaqruo
H2CO3, TO,
KaK
cneAyeT
rc
pHc.
Ll,
SrO BO3MO)KHO
JrHrrrb
npH
pH
6olee
8.
flpu
ornx 3Har{eHgf,x pH
B
pacrBope
6yaer
npncyrcrBoBarb
LI Hexoropoe
KorrrcrecrBo
CO:2-. Toqsue
srnar"""": pH
:
8,07;
CO32-:
0,49
mr/t.
Vs
puc.
Ll auguo,
rrro
AJIq
pH
:
8,07 r.r HCO:-
= 50 ur/n
3HaareHns
KoHrleHTparlufi
COt2-
n H2CO3 (6es
ucnolr3oBaHnr
rcoss-
$uqueHron
aKTHBHocTH) panuu
0,30
u
0,95 urh coorBercrBenHo.
flo4craHonra
aKTHBHocrefi
srvrecro
KoHrIeHTparIuit
gaer:
COs2---
0,46
u
H2CO3
:
0,82 ur/rt,
uro
6lusrco
K ToqHbrM
3HaqeHHrM
-
ue6olsruae
oTKrroHeHHr
cBr3aHbr
c [orperxHocTbro
onpeAeJreHHr
rlo pHcyHKy.
,{auHrrfi
npHMep rroxa3brBaer,
qro
Aa)Ke
npu ne6olrurux
KoHqeHTpa-
Ilrlrx pacrBopeHHbrx
BerrlecrB
orrpeAeneHue
coorHoueHufi
naexAy
He-
Anccoqr,ruposaHHo
fi
yrureKacirorofi
u rap6oHar-
H 6n rap6oHar-
vo*avrvt
[o
puc.
1.1
6eg
]
{era soHHofi
cnJrbr
pacrBopa
rrpuBoAnr
K
3Har{HTeJrb-
urru
orun6rau.
Ilpwwep
2. Pcoz:0,035
rfl4 t
:25
oC,
xornlerrrpaq.rs
HCO3-
B
pac-
rBope
cocraBflqgr
300 nar/n,
NaCl
-10,0
rh, Kor{rrelrrparrar
HzCOI
(crra.
ra6n.
l.l) no-npe)rueMy
0,'73 v.r/q :aonHafl,
crua
pacrBopa
-
0,2575
rraolth.
Kar u B npeAbrAyrqeM
cJDAae,
pH
6yaer
)
8, n B
pac-
TBope
coAep)KnTcr
COr'-; Tor{Hbre
3HaqeHr,r{
pH
= 8,79; CO32-
:
20,16
ur/n.
flo
pr.rc.
LI
ws
pH
:
8,79 u
HCO3-
:
300 Narh
sHaqennt
H2CO3:
0,81 rvrrh;
COtz-: 10,70 ur/ry
ecnu He
yqnrbrBarb
r,roHHyro
cwlrtz Lt
HzCOr: 0,66
ur/ry COs2-:20,66
urh npn noAcraHoBKe
aK-
rusHocreft
BMecro
KoHqeHTparluit.
Ecnv
renepb HaA
gruM
pacrBopoM
co3Aarb
AaBneHr,re
CO2
n
l0 rfla, To KoHrIeHTpaUra.s
HzCO3
cr&Hor
paB-
uoft 0,0986'0,03383'62.1000
:
207
ur/n.
Orsoruesue rourleHrpa4afi
HCO3-/H2CO3
:
1,47
(rcoHqerrrparlnn
AoJrlr(Hrr
6srrs BbrpuKeHbr B
naorn/n)
no
pnc.
1.1 soslrorrffio
npH
pH
crr
6
Ao
'7,vt,TaK
KaK
Koru-1erilpar-u.rt
rap6onar-uoHa
s
yrofi
c6.rmLcrr
pH panHa
0, ro
3Haveruae
pH
pacrBopa
Mo)KlIo onpeAerrnrb ro
pHc.
l.l
(0,81'HCO37(0,81'HCO3-+
H2CO3)
:
0,54
(0,81
-
rcos$$marern aKrI{BHocrH HCO3). CoorrersrBeHHo rro
pl.rc.
1.1
a"rrs
HCO:-
:
0,54 onpeAeJl.f,eM
pH:
6,42. flpnuep 2 noxagunaer xoA
paccy)rqeH
uit,
y*If,wnarcIIlrx npHcyrcrBHe
COz
n
rasonoft
Sase.
t1
-lef,=
A'Z?
Ji=,
1+
Bor,JI
lg
f,
-
A,JT
__--;_
_
__________-_
_
_
0,21,
Z;
l+4,68oJI
(1.12,
a)
rAe 3a sr[Semunuufi
uoHsufi
paAl{yc
flpuHtro
cpeAHee ero
3Ha-
seHr,re
AJII
Bcex HoHoB,
cocraBr.f,Iotqee
4,6
A.
flpr,r 6onrurlrx
3HaqeHusx
llossofi cIuIbI
pacrBopa
rcosSQuIIHeHTbl
aKTr,rBHocrH
cJle,ryer
6parr
H3 crpaBoqHofi
nuTeparypbl.
I4Naeg s
BHAy BbIueH3JIolI(eHHoe,
BepHeMcs
K
paccMorpeHl{p
paB-
nosecHft
ro
peaKlrHtrra
(1.5)
u
(1.6)
B npHcyrcrsl'Ia
ra3osofi
Sasu,
co-
4epxau1efi
COz.
B
6olrruuscrse
nsAaHuft, tAe
paccMarpuBalor npo-
qecc
pacTBopeHr4t coz
s
BoAe Ll
AHCcOq[aI{Hro
yroJlbHofi nr'IcJlorrt,
HaFJrrAHo
oro6paxaror
coorHolrle
HHe Me)I(Ay
KoHlleHTpaqurn'ru
H2CO3,
HCO:-,
COr2-
u
pH
pac'rnopa
(puc.
l.l,
qn.
oru.).
flpu
3roM,
KaK npa-
Br4Jro,
He
yKa3blBalor,
qro
pnc.
Ll
nonyqsH
Nts Ar4crnnnupoeaHHofi
BoAbr
npu
25
oC
6es
yrvra nousofi cItJIbI
pacrBopa. Ho H c raKHM
yroqHeHaeM
cneAyer
qgrKo
npeAcraBntlt
ce6e,
qro
H
npn Hanuquu
3HaErrdreJrbHbrx
KoJIHqecrB
COz
s rasosofi
Qase,
n npw Pg6r,
orBeqato-
rrleM
coAepx(anuro
CO2
n aruoc$epe
(npnrvrepHo
0,035
rfla),
puc.
l.l
Aaer
HMeHHo coorHolflen""
t"NAf
pH
ll H2CO3,
HCO3
,
CO32-,
a ue
3HaqeHHt
KoHlreHTpaqprfi
HzCOl,
HCO3- u COsz-
npn 3aAaHHor'r
pH.
ffoscnalt
cKa3aHHoe
Ha npuMepax.
l0
A.H.
Maprcun,
P.3.
Husanoe
B o6qena
cJryqae
coorHoureHl're
MexAy
pH u H2CO3,
HCO3-,
COrz-
Mo)rcHO
IIoJryqHTb
no
oopMynaM
[Hrco,]
_
[t.h.
.
F*;k""q_
-
\
,
lcoi-jf,.;
Kz
Frco'-,f
/";
(1.
l3)
(1.14)
BbrreKaIoIrIHM
H3
orrpeAerenvs
KoHcraHT
Auccoqnaqun
R1 u
K2
(za-
K,rroqeHHat
B KBaAparHse
cro6xu
xHMHqecKzuI
$optuyla
BeurecrBa
o3Haqaer
ero
KoHIreHTpaIrHIo
B
pacrBope,
uonr/n).
flpn
srou
paBHo-
BecHalt
KoHIIeHTpaqrar
(nog'repKllBaeM
-
paBHoBecnar)
H2CO3
BcerAa
onpeAenreTcr
3aKoHoM
feupn.
Hs
ypauHeuufi
(1.13) u
(l.la)
crleAyeT,
qro
npH
HH3KI{X
Pse.,,
orB€tlarcllll{x
Ko-HIIeHTpaIIHU
coz
n
aruocsepe,
yMeHbulat
pH
pacrn5pa
c
uoHaMH
CO32-
u
HCOI-,
xap6ouar-
n 6urap-
6oHar-uoust
MolI(HO
nepeBecTl'I
n H2CO3,
KOTOpas
c
TeqeHHeM
BpeMeHH
(unr,l npn
uarpene)
BbrAeJrHrcs
r.r3
pacrBopa.
AsaloruqHo,
ecJIH
B
pac-
TBopecoAep}Kl,rTc'HeAHccoIIHHpoBaHHircyronEHa'KHcJIoTa'Toeerry-
reM
Ao6asreHut
Iqertoqu
MoxHo
nepeBecrn
n HCO3-
H
Aanee
s COr2-
'
Ha
grou
ocHoBaHo
orrpeAeneHHe
pacTBOpeHHOfi
yuerracJloTbl
w 6u-
rap6ouar-
u
rcap6ouat-HoHoB
B
pa3JII'IqHbIX
BoAax'
HzCOI
pearHpyer
c
rap6ouarou
(rr'rgporcuAor*r)
Hxrpvte''
o6pasyr
NaHCO:.
TurpouaHue
npoBoAtr
0,01-
unr'r
0,lN-pac'reopou
NaCO3
(NaOH)
B rpncyrcmnlr
SeHon$TaJIeHHa'
s KoHeqHofi
TorrKe
pH
=
8,3'
COrL
u
HCOI-
onpeAenf,KlT
THTpoBaHHeM
BoAbI
pacTBopoM
cllllnofi
KHCJTOTbT.
flpu
rarou
TrTIpOBaHHr,r
KOJrHqecTBo
KHCJIOTbI,
neo6xoAxuoe
.{rr AocrrDmennr
pH:
8,3
(rurpoBaHl'Ie
no
Senonstarentry,
CO32-
ne-
pexoAHT
n
HCO3],
eKBr{BuureHrHo
KoHrleHrpaqnn
6nrap6onat-nona'
a
KoJruqecrBo
KHcJIorbI'
Heo6xoAuuoe
Ar.f;
AocrruKeHHfl
pH:
4,5
(rtn-
poBaHue
no
MerHJIoBoMy
oparDreBoMy'
HCO|
repexoAnT
s
HzCO:)
-
sKBr{BaJTSHTHO
KOHrIeHTparyl,r
HCO:-.
Boo6qe
roBopt,
3KBLIBaJISHTHOe
KOJIHqeCTBO
KHCJIOT6I,
geO6XOAl,tt"tOe
AJII
AOCTHIK9HHS
pH
:
8,3,
UaSU-
Baerct
ceo6oAHofi
lrleJloqHocrblo'
a
AJII
AocrruKeHHJI
pH:
4,5
-
o6-
g1efi
UenOqHOCTbK).
f[OA
IrIenOqHOCTbrO'
CJI9AOBaTSJI6HO'
IOHHMaK)T
t2
C O
2
-
x o
p p
osun u e$m enp ou u cn oe o z o o 6 o
pyd
oe
a
u u,a
cnoco6Hoctb pacrBopeHHbrx
B
BoAe BerqecrB
cBt3blBarb
3KBHBzureHT-
Hoe KoJrlrqecrBo
cr,rJrbHofi rcuclorrr,
Koropiul 3aMeulaer ruApoKcr4nbHbre
HoHbr r{
aHuoHbr
cla6rx
KncJror.
Tarcuu o6pasona, cno6o4uar
z o6ulas
ureJloqHocrb paBHbr
coorBercrBeHHo KoHrIeHTparrHrM COrt- u HCO3-,
KorAa
Aoleft
Apyrr{x
aHnoHoB Mo)r(Ho npeue6pe't.
Ilocle4Hee c[pa-
BeAJIHBo
glr
6omuruHcrBa BoAHbrx
{as
ueQrenpoMbrcJroB,
rAe ocHoB-
HsIM Koppo3HBHbrM
KoMnoHeHToM
rBJr.f,ercr
yrneKucJrora. pH
3Aecb,
qalrle
Bcero,
MeHbure
8,
nosrouy
B
BoAe
oAHoBpeMeHHo
rrpucyrcrByror
roJIbKo H2CO3
u HCOr-. Me'roAnru onpeAeJreHnt H2CO3, HCO3- r.r
COzz- nogpo6Ho
onncaHbr B Jrr,rreparype no aHaJlnTti.{ecxofi n:a.vrra.
Karc norasaHo Bbrrrre, IIpH
pacrBopeuuu
CO2
B BoAe
pH
cueqaercr
B KHcJrorrq/ro
o6lacrr.
fut
pucruttlupoaauHofi
BoAbr
gro
vrntc,crpu-
pyer plrc.
1.2
(no
AaHHbrM
[5]).
MunnuzurbHoe 3Har{eHue
pH pacraopor
yrorruoft
KHcJrorbr n npecHofi BoAe
-
3,3
npu Pcoz
-l
Mna
[6].
Aam-
Hefiruee noBbrrrreHne
AaBJTeHHJT
[paKTHqecKH He
H3MeHrer pH.
OAsarco
c noBbIIrreHHeM
MuHepanlagarlrrt
pH
rrloxer
cHn)Karbc{
H
cl,urbHee,
BrrJrorb
Io
2 s
3Yo-u
pacruope
NaCl. B o6rUeu cJryqae
npHcyrcrBne B
soAuofi
Saee
gpyrrx
HoHoB H xr{MxqecKux
BerrlecrB
oKa3brBaer
3Har{H-
TeJIbHoe Blrvtxr.lae
HaBLTA 3aBI,rcHMocrH
pH:
F(Ps6).Ha
prac.
1.3 npn-
BeAeHbr KpHBbre
r.r3MeHeHr{rr
pH
cnurernqecrcofi ruacrosofi nogu
Ca-
MorJropcKoro HeSr.ruoro MecropolrAeHr,rt
pa3nnr{Horo
x}rMrdr{ecKoro
cocraBa B 3aBr,rclrMocrn or Ps6r.
fIpH
cpaBHeHHH
pnc
1.2 u
puc
1.3
BHAHo,
qro
pa3Jrr,rqHs
B 3Har{eHHrx
pH
npn
oAHI{x H Tex xe Pse, BecbMa
3HaqHTeJrbHu. O6rrqnuft
cocras
nogHofi
Sarrr
npo,qyKIIHH cKBzDKHH
ue$rrusrx
Mecropox(Aennfi,
r4e Koppo3l,Iq nporeKaer
no yrneKncnor-
HoMy MexaHrBMy npn orcyrcrnr.ru
H2S, BKJrloqaer uoHu Cl-, HCOr-,
Na*, Ca2*,
Mg2*,
Fe2*,
a
qacro
Soa-, Ba2*, Sr2*. 3anucaB
yparlHeHva
Bcex
Bo3Mo)r(Hbrx xnMurrecKr{x
pearqufi
MexAy vloHaMH, 3HarI KoHcraH-
Tbr
paBHoBecvt
:lrvrx
peaxquft
(a
raxxe
Lrx
reMneparypHbre 3aBHcHMo-
cru)
u KoucraHry lenpv,
Mo)r(Ho
AocraroqHo
roqHo
paccqnTarb
3Ha-
qeHHJI
pH
no4noft
Qasu
npo4yKrIHH cKBzDKHH KaK
$ynxqr,rro
Pcor.
Cy-
IqecrBylorrlne
MeroAr,rKH, Hanpr,rMep
[7,
8], noxasbrBarcT xopomyto
cxo-
AHMOCTb
paCr{eTOB
C SKCrrepHMeHTZurbHbrMH
AaHHbrMr,r.
l3
A.H.
Mapxuu,
P.3.
HusaMoe
4,2
4,7
4,0
3,9
o
3,8
3,7
3,6
3,5
0
50
100
150
200
flapuualrHoe
AaBJIeHI{e
CO2,
xfla
Pnc.1
.2. 3aeucuuocmt
pH
ducmunnupoaauuoii
u cna6ouuuepanusoeauuoil
eodat
om
napquanbHoeo
daeneuun
yeneKucnombt
(no
dannuu
[5])
8,0
7,5
7,0
6,5
A
o.
6,0
5,5
5,0
4,5
0
10
20
30
40 50
60
70
80
90
100
flapuualruoe AaBneHHe
CO2,
xfla
Prac.1'3.3aeucumocmtpHcuumemu.aecxoinnacmoeoilaodat
Canomnopcrozo
uefumnuoeo
uecmopoxdeHun
om nap4uanbHoeo
daeneuun
COz.
kuuu'aecruil
cocmae
eoda4
e/n:
NaCl
-
17,00;
CaClz
-
O'14;
ftngCfr
-
0,20;
NaHCO
g
-
0'127
(1)
ra 0,633
(2)'
Teruneparypa
-
50
"C'
Pacser'
l4
CO2 - rcopposun ueSmenpoubtcttoqozo
o6opydoeauua
Taxnu
o6pasou, KorAa BoAa HaxoAprrcr
rroA
AaBJTeHHeM
ragosoft
saru,
coAepx(arqefi
coz,
KoJrsqecTBo pacTBopeHHofi yrueracJrorbr
on-
peAeJltercr
sern.{uuofi Pcoz v TeMnepaTypofi,
a
pH
3aBHcr,rT errle H oT
xHMI,IqecKoro
cocraBa
no4u.
Ecln o6uee
AaBJreHHe
s raxofi
cucreMe
yBenHqHTCff
HJIH
yMeHbIUHTCt,
TO
coOTBeTcTBeHHO
II3MeHLITCr u Pg6r.
B
pesylrrare
lrcMenrrcc
KoHr{eHTpaqHr pacrBopeHHofi yrnexncJrorbr
H
pH
no4u
-
oHH 6ynyr orBer{arb HoBoMy
3HaqeHnro
Pgsr.
Ha npaKTrrKe
3HaqeHHJr
Pcoz
B
pa3Hbrx
Tor{Kax rrpoMbrcnoBbrx
cr4cTeM
(crnaxuurr,
rpy6onponoAbr
cr.rcreM
c6opa He$ru v ra3a
n
Ap.)
qacro
6rrsaror HeH3-
BecrHbr
-
Mfl
pacrrera
Pgsr'tpe6yercr [poBoAHTb
aHiurr,r3 ra3oBoft
0a-
3bI,
AJrr
Koroporo He BcerAa HMeerc.f, Heo6xo4urr,roe
o6opylosaHr,re. B
To xe BpeMs
xNrar+recxnfi aHaJIH3 BoAbr Ha co.qepx€Hue
pacmopeHnofi
yrureKucJlorbr
He
orJrnr{aerct
cJlox(Hocrbro.
Sruu
qacro
noJlb3yrcTct
MnqecKoro
arratnsa
BoA6I
-
H3 3aKoHa leHpu
Pcoz:
[H2CQ]/G.
Cle4yer: orMerr,rrb, wro
AJrr
norryr{eHnr KoppeKTHbx
gnaqesufi
rcou-
qerrpaqufi
COz s
soAHoft
Sa:e
cxnaxr.rn
n rpy6onpoBoAoB,
rro KoropbrM
Aeftcrel1frerbHo
Mo)KHo
orleHr{rb
Pcoz B
gTrrx
cHcTeMax, aHaJIH3 ueo6xo-
AI,IMO
[pOBOArfTb
B
yCJTOBHJX,
HCKrrOqruOUIrrX
rrOTepH co2 npn
AerA3A-
quu
npo6u.
BrrAeneuae COz
us npo6rl
BoAbr Mox(er npoHcxoAr.rrb npe-
xAe Bcero
nOToMy,
.rro
Ps6, n aruocSepe cocTaBnreT npHMepHo
0,035 rcfla,
TorAa KaK B cKBDKHHax
H
repMeru3r,rpoBaHHbrx cncreMax
c6opa
neSrn H ra3a
-na2...5
nop.r4xon
6orlrrue.
flo
erofi
npHqHHe aHa-
JrH3
Ha coAepxaHue
pasmopeHHoft
ymerucrorbr
AoJDKeH
rrpoBoAuTbcr
B
noJreBbrx
ycJroBr{f,x
HeMeAJreHHo nocJre or6opa npo6rr, x(eJrarenbHo npu
TeMneparype
oKpyxapqero
Bo3;qn€ sa
10...15
oC
saxe
rofi, roropar
6rua s rpy6oupono4e.
.{anHrre
re;6l. 1.2
r4rurrocrpupyror KrdHerHXy BbI-
AereHr,It
CO2uz npo6 no4u
(crnaNuHrr
Cauouopcxoro
ueQrxHoro Me-
cropox4ennr).
O4uorpeueHHoe rrpncyrcrBne B no4uofi
Qase
npoayKrlr,rr{
cKBa-
)KHH
[epeqplcJreHHbrx
BbIIIIe
aHHoHoB H KaTHOHOB
O6yClOr.nnnaeT BO3-
Mox(Hocrb
o6pasonaHn-r cJreAyroqnx
TpyAHopacrBopnMbrx
coeAHHe-
Huft
(oca4rcon
conefi)
-
CaCO3,
FeCO3,
CaSOa, BaSOa,
SrSOa,
Koro-
pbre,
HapsAy
c
FeS
ssr.flIorc{ Tr{nur{HbrMu cocraBJrrloqltMa
MuHepilIb-
Hbrx
orJro)K
eHuit s
6olruruncrne
neQrenpoMblcJloBblx
cncreM.
l5
Xapalcre-
pllcTrlKH
Ifaparuetp
Bpeun noc.ne
ordopa npo6u,
u
0'
I
)
3
M:28,2
rltl.
t:25'C
COz, ur/n
90 65
55
45
pH
6,88
6,93
7,04
7,06
M:26,5 rlt
t=29'C
COl ur/l 85
55
50
48
pH
6,61
6,73
6,78 6,83
M:24,3
rlt
,:
35
"C
COl ur/l
40
32
27 24
pH
6,44 6,54
6,58 6,62
A.H. Mapxuu, P.3.
Husauoe
Ta6ruqa L2
Kunerurca BbllereHtlq
COz xs sOAHOfi
Qa$l
npo4yxqflrl
cKBarcl|H
Cauornopcroro neQrrnoro
MecropoxAeurlq
*Asann
n
uouenr
or6opa
npo6sr
B
ycJroBr{lx,
rlcrurrcqauqIrx norepu
CO2
Kap6onar Kurnbrlnr
CaCO3
o6pa-:yerca B
p$yJrbrare peaKr{Hfi
ca2*
+
2(HCo3l
---
CaCogJ
+
coz
+
H2o
Ci*
+
COr2-
--
CaCO:l
HssecrHrr
Tpr.r
OopMbr
CaCO3
-
KaJrbrIHT, aparoHr'rT
r'r BaTepr'rT.
Kamqnr Hau6onee
pacnpocrpaHeH
B
paccMarpuBaeMbrx
cacreMax,
H
Aiulee
noA
CaCOI Mbr 6yAeM r,rMerb B BHAy nMeHHo
Kanbrlr{T.
.{nx
ro4Hslx
Qas
HeQre[poMbrcJroB,
rle KoHrleHTparlilr
Kap6oHar-
r.roHa
6ru3Ka K 0, o6pasonauae caco3 nAeT B
ocHoBHoM
no
peaKrlHr'r
(1.15).
OAuun
rc npoAyKToB orofi
peaKqHH
flBJrrercfl
yrureKucJrora,
[oSToMy ocaxAeHHe
CaCOs
3aBHcI{T oT Pgsr- c
yBenHqeHHeM
napqu-
€ulbHoro
AaBJreHr,IJI
COz
PeaKrIH-f
(1.15)
cMerllaercr
BJreBo.
Sror
atp-
Qem
n HecKoJrbKo
pa3
noBbrxaer
pacrBopuMocrb
CaCOI B
rrpecHofi
H
cJra6oMnHepann3oBaHHofi soAe
rrpn rlrMeHenvrz' Pgs,
or 0
Ao
I MfIa.
floerrxeHr,re reMneparypbr H
pH
cABr,rrarcT
peaKqr4ro
(1.15)
BrrpaBo, B
cropoHy
o6pasonauux CaCO3.
flpn
4o6srve
HeQTr,r
H t&3a reMneparypa
H o6rqee
AaBJreHHe,
a cre-
AOBaTeJIbHO,
tI Pcoz,
nOHTDIKaTOTCC Or
ga6O.fl
K
yCTbIO
CKBa)KHHbr rr nO
ArrHHe
Tpy6onpoBo,qoB oT cKBa)KHH K HacocHbrM
cTaHqlrrna.
OgHonpe-
MeHHOe
yMeHbIueHI,Ie
t H
PssT
IIpOTpIBO[OJIo)I(Ho
BJIIUIeT Ha
O6pa3OBa-
Hue
CaCOt. B cs.f,gl.r
c
9THM ocaAKoo6pffioBaHHe
CaCO3
Mo)r(er npoHc-
xoAr,rTb B Jrrc6oM MecTe rrpoMbrcnoBbrx cHcTeM, rAe H3MeHeHr,re
TeM[e-
paTypbr
Pcoz
H xHMr{qecKofo
cocTaBa
BoAbr
HapyrlaeT Kap6oHaTHoe
16
(1.
l
s)
(1.r6)
COr
-
."pp"t* r"Q."ry
paBHoBecHe,
nosToMy ocaAKH caco3 o6Hapyxunaror Ha pa3fiHrrHofi
rury6uHe rro
crBoJry cKBa)KrrH, B Tpy6onpoBoAax cucreM
c6opa He{TE
(CCH),
H
AalKe
B Tpy6onpoBoAax, TpaHcroprHpyroulx
o6no4ueuuyro
HeQTb
or
AoxHMHrrx
HacocHbrx craHrlufi
Ao
roBapHbrx
napKoB.
Ocax-
AeHI4e
CaCO3, KaK r,r nro6brx
ApyrI{X
coJrefi, Bbr3brBaeT
cepbe3Hbre oc-
Jrox(HeHr,rr rtpu
Ao6brqe
He+TH:
"3acoreHne"
HKT
-
yMeHbureHue
BlryrpeHHeto
Ar4aMerpa
HKT s
pe3yJrbrare
orJro)r(eHu.rr conefi
H, KaK
cIeAcTBHe,
CHI,I)KeHHe KOJIHTIeCTBa X(LIAKOCTH,
AO6bIBaeMOtO
CKBZDKI,I-
HaMH; BbTXOA
r,r3 CTpOr ury6r,rHHbrx
HacocoB npH MexaHH3HpoBaHHoM
cfioco6e
Ao6brqH;
HHTeHcHB]ryro
Koppo3Hro BHyrpeHHeft
noBepxHocrH
HKT u rpy6onponoAoB
CCH B Mecrax
JroKuurbHoro orcJrauBaHrfl
ocaA-
KoB.
B cBr3r,r
c ornM
Ar.s
o6ecne.{eHnr HopManbHofi pa6oru
o6opyAo-
Banus,
BUDKHo
BoBpeMr orIeHHTb Bo3MoxHocru ocaAxoo6pa3oBaHnfl
H
npllH.srb neo6xogunabre
Mep6r no ero npeAorBparqeHr,rrc.
,{na
nporHo3upoBaHnr BrrlaAeHur
B ocaAoK Toro HJrH
nHoto
TpyAHOpacTBOpHMOTO
COeAHHeHUT nOJrb3yrOTCr [apaMeTpOM
nepeobr-
IrIeHHr
pacrBopa
r{oHaMH, o6pasyroulnMu coJrb. flepecruqeuue pacrBo-
pa (II)
MaJropacrBopr,rMbrM BerrlecrBoM
Kt.Ann,
pacnaAaroquMcr
B
pac-
TBOpe
no
peaKrlr,rH
Kt^An,
<--+
mKt
*
nAn
(1.t7)
(
1.18)
paBHo
m*r,*,
l[A
Qp, OSn
-
IKTkIBHOCT6
KaTHOHa
H aHHOHa COOTB9TCTB9HHO;
ffPKr.Ar,
-
[pOH3BeAeHHe
pacTBopHMocTH
BeIIIecTBa.
Ecru
fI<1,
To
pacrBop
He HacsrlrleH
paccMarpuBaenaofi
coJrbro,
npu
II:l unaeeu HacbrrrleHHbrit, anpu
f[>l
-
nepecbrrrleHHrrfi
pacrnop
coJrH.
B noc.neAHeM
cJryqae
Bo3Mox(Ho BbrAeJreHr.Ie ocaAKa MirJropacrBopuMofi
coJrH. Ha npaKTr.rKe
qarrle
HcnoJrb3yror He BeJrHqHIry [epecbrrrreHnt
pacrBopa
fI, a ee
Aecrrr,IrrHblft
norapHoM,
rcoroprtfi HzBblBaerct HHAeK-
coM HacbruleHr.u
pacTBopa
n
o6osHarlaeTct
SI':
91
:
'n
[o*,]' [oo,I
"
IIPK,-A,"
(l.le)
|
.
--
-
A66perr.rarypa auuulcrnx
cros Saturation Index
-
HHAeKc HacrllrleHrrt
l7