US 20ll0l63259Al

( 1 2) Patent Application Publication ( 1 0) Pub. N o. : US 201 1 /01 63259 A1

( 1 9) United States
Ster z el ( 4 3) Pub. D ate: J ul. 7 , 201 1
( 54 ) HEAT TRAN SFER FLUID S AN D HEAT Publication C las s i? cation
STORAGE FLUID S FOR EXTREMELY HIGH ( 51 ) Int C l
TEMPERATURES BASED ON ' '
POLYSULFID ES C 09K 5/00 ( 2006. 01 )
( 7 5) Inv entor : Hans -J os ef Ster z el, ( 52) US. C l. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252/7 1
D anns tadt-Sch auem h eim ( D E)
( 7 3) As s ig nee: BASF SE, LudW ig s h afen ( D E) ( 57 ) ABSTRAC T
( 21 ) Appl. N o. : 1 2/98 4 , 7 35
( 22) Filed: J an. 5, 201 1
( 30) For eig n Application Pr ior ity D ata
J an. 5, 201 0 ( D E) . . . . . . . . . . . . . . . . . . . . . . . . . 1 0201 0004 0630
A com pos ition for th e tr ans por t and s tor ag e of h eat ener g y ,
W h ich com pr is es alk ali m etal poly s ul? des of th e for m ula
( Mel( l_ x ) , Me2x ) 2SZ , W h er e Mel and Me2 ar e s elected fr om
th e g r oup of alk ali m etals cons is ting of lith ium , s odium ,
potas s ium , r ubidium and ces ium , Mel is differ ent fr om Me2
and X is fr om 0 to l and Z is fr om 2. 3 to 3. 5.
US 201 1 /01 63259 A1
HEAT TRAN SFER FLUID S AN D HEAT
STORAGE FLUID S FOR EXTREMELY HIGH
TEMPERATURES BASED ON
POLYSULFID ES
[ 0001 ] Fluids for tr ans fer r ing h eat ener g y ar e us ed in m any
? elds of indus tr y . In inter nal com bus tion eng ines , m ix tur es of
W ater and eth y lene g ly col car r y th e W as te h eat of com bus tion
to th e r adiator . Sim ilar m ix tur es conv ey th e h eat fr om s olar
r oof collector s to h eat s tor ag es . In th e ch em ical indus tr y , th ey
conv ey th e h eat fr om h eating plants h eated electr ically or by
m eans of fos s il fuels to ch em ical r eactor s or fr om th e latter to
cooling appar atus es .
[ 0002] Accor ding to th e r eq uir em ents pr o? le, m any ? uids
ar e us ed. Th e ? uids s h ould be liq uid at r oom tem per atur e or
ev en at loW er tem per atur es and s h ould, ? r s t and for em os t,
h av e loW v is cos ities . W ater is no long er pos s ible for r elativ ely
h ig h us e tem per atur es ; its v apor pr es s ur e becom es too h ig h .
For th is r eas on, h y dr ocar bons W h ich us ually com pr is e ar o
m atic and aliph atic par ts of th e m olecule ar e us ed at tem per a
tur e of up to 250 C . Olig om er ic s ilox anes ar e als o fr eq uently
us ed for r elativ ely h ig h tem per atur es .
[ 0003] A neW ch alleng e to be m et by h eat tr ans fer ? uids is
th er m al s olar poW er s tations W h ich g ener ate electr ic ener g y
on a lar g e s cale. Such poW er s tations W er e h ith er to built W ith
an ins talled poW er of about 1 000 m eg aW att in total. In one
em bodim ent, th e s olar r adiation is focus ed by m eans of par a
bolically s h aped m ir r or g r oov es on to th e focal line of th e
m ir r or s . Th er e, th er e is a m etal tube W h ich is located W ith in a
g las s tube in or der to av oid h eat los s es , W ith th e s pace
betW een th e concentr ic tubes being ev acuated. A h eat tr ans fer
? uid ? oW s th r oug h th e m etal tube. Accor ding to th e pr ior ar t,
a m ix tur e of diph eny l eth er and biph eny l is us ually us ed h er e.
Th e h eat tr ans fer ? uid is h eated to a m ax im um of 38 0-4 00 C .
and a s team g ener ator in W h ich W ater is v apor iZ ed is oper ated
by m eans of th is . Th is s team dr iv es a tur bine and th is in tur n
dr iv es th e g ener ator as in a conv entional poW er s tation. Total
e? iciencies of about 20-23 per cent, bas ed on th e ener g y con
tent of th e incident s unlig h t, ar e ach iev ed in th is W ay .
[ 0004 ] Th er e ar e v ar ious pos s ible W ay s of concentr ating
th e s olar r adiation; apar t fr om par abolic m ir r or s , Fr es nel m ir
r or s W h ich lik eW is e concentr ate th e r adiation on a tube
th r oug h W h ich ? oW occur s ar e als o em ploy ed.
[ 0005] Both com ponents of th e h eat tr ans fer ? uid ( diph eny l
eth er and biph eny l) boil at about 256 C . under atm os ph er ic
pr es s ur e. Th e m elting point of biph eny l is 7 0 C . , and th at of
diph eny l eth er is 28 C . Mix ing of th e tW o s ubs tances loW er s
th e m elting point to about 1 0 C .
[ 0006] Th e m ix tur e of th e tW o com ponents ( diph eny l eth er
and biph eny l) can be us ed up to a m ax im um of 38 0-4 00 C . ;
at h ig h er tem per atur es , decom pos ition occur s , h y dr og en g as
is ev olv ed and ins oluble condens ation pr oducts depos it in
pipes and v es s els . Th e v apor pr es s ur e at th es e tem per atur es is
about 1 0 bar , a pr es s ur e W h ich is s till toler able in indus tr y .
[ 0007 ] To obtain total e? iciencies h ig h er th an 20-23 per
cent, h ig h er s team entr y tem per atur es ar e neces s ar y . Th e e? i
ciency of a s team tur bine incr eas es W ith th e tur bine inlet
tem per atur e. Moder n fos s il fuel-? r ed poW er s tations W or k at
s team entr y tem per atur es of up to 650 C . and th er eby ach iev e
e? iciencies of about 4 5%. It W ould be tech nically q uite pos
s ible to h eat th e h eat tr ans fer ? uid in th e focal line of th e
m ir r or s to tem per atur es of about 650 C . and th us lik eW is e
J ul. 7 , 201 1
ach iev e s uch h ig h ef? ciencies ; h oW ev er , th is is pr oh ibited by
th e lim ited h eat r es is tance of th e h eat tr ans fer ? uids .
[ 0008 ] Th er e ar e obv ious ly no or g anic s ubs tances W h ich
ar e able to W ith s tand tem per atur es abov e 4 00 C . ov er th e
long ter m ; at leas t, th er e ar e none k noW n to date. For th is
r eas on, attem pts h av e been m ade to us e inor g anic, m or e h eat
r es is tant liq uids ins tead. Th e pos s ibility k noW n fr om nuclear
tech nolog y of us ing liq uid s odium as h eat tr ans fer ? uid h as
been intens iv ely ex am ined. HoW ev er , th e fact th at s odium is
fair ly ex pens iv e, th at it h as to be pr oduced W ith h ig h ener g y
cons um ption by electr oly s is of s odium ch lor ide and th at it
r eacts W ith ev en tr aces of W ater to ev olv e h y dr og en and th us
r epr es ents a s afety pr oblem h av e s tood in th e W ay of pr actical
us e.
[ 0009] Th es e pr oblem s ar e ev en m or e acute in th e cas e of
th e eutectic alloy of s odium and potas s ium ( about 68 atom
per cent of potas s ium ) W h ich cr y s talliz es at 1 2 C .
[ 001 0] Anoth er pos s ibility is th e us e of inor g anic s alt m elts
as h eat tr ans fer ? uid. Such s alt m elts ar e pr ior ar t in pr oces s es
W h ich oper ate at h ig h tem per atur es . W or k ing tem per atur es of
up to 500 C . and cr y s talliz ation tem per atur es doW n to 1 00
C . ar e ach iev ed us ing m ix tur es of potas s ium nitr ate, s odium
nitr ate, th e cor r es ponding nitr ates and optionally fur th er cat
ions s uch as lith ium or calcium ( US. Pat. N o. 7 , 58 8 , 694 ) .
[ 001 1 ] Th e fer tiliZ er indus tr y is capable of pr oducing lar g e
am ounts of th e nitr ites and nitr ates . HoW ev er , tW o cons ider
able dis adv antag es of th e s alt m elts lead to th em being us ed
only tentativ ely in s olar th er m al poW er s tations : as nitr ates ,
th ey h av e a s tr ong ly ox idiZ ing effect on m etallic m ater ials ,
pr efer ably s teels , at elev ated tem per atur es , as a r es ult of
W h ich th eir m ax im um us e tem per atur e is lim ited to th e about
500 C . m entioned abov e. Secondly , th e th er m al s tability of
th e nitr ates is lim ited at elev ated tem per atur es . Th ey decom
pos e W ith elim ination of ox y g en to for m ins oluble ox ides .
OW ing to th eir cr y s talline m elting point, th e m inim um us e
tem per atur e is about 1 60 C . A fur th er loW er ing of th e m elt
ing point can be ach iev ed by addition of lith ium or calcium
s alts . HoW ev er , th e lith ium s alts r es ult in g r eatly incr eas ed
cos ts , and a pr opor tion of calcium incr eas es th e m elt v is cos ity
at loW tem per atur es in a dis adv antag eous W ay .
[ 001 2] At pr es ent, s alt m elts ar e us ed as h eat s tor ag e ? uid in
s olar th er m al poW er s tations . HoW ev er , biph eny l and diph e
ny l eth er m ix tur es continue to be m os tly us ed in th e s olar
? eld, as a r es ult of W h ich th e s tor ag e tem per atur e continues to
be lim ited to about 390 C .
[ 001 3] W h eth er W ater under an appr opr iately h ig h pr es s ur e
is s uitable as h eat tr ans fer ? uid h as lik eW is e been ex am ined.
HoW ev er , th e ex tr em ely h ig h v apor pr es s ur e of m or e th an 300
bar s tands in th e W ay of th is , s ince s uch a h ig h v apor pr es s ur e
W ould m ak e th e th ous ands of k ilom eter s of pipes in a lar g e
th er m al s olar poW er s tation uneconom ically ex pens iv e.
Steam its elf is uns uitable as h eat tr ans fer ? uid and h eat s tor
ag e ? uid becaus e of its com par ativ ely loW th er m al conduc
tiv ity and th e loW h eat capacity per unit v olum e com par ed to
a liq uid.
[ 001 4 ] A fur th er pr oblem ar is es becaus e it is des ir able als o
to oper ate a s olar th er m al poW er s tation at nig h t. For th is
pur pos e, cons ider able q uantities of h eat tr ans fer ? uid h av e to
be s tor ed in lar g e, th er m ally ins ulated tank s .
[ 001 5] If th e h eat content is to be s tor ed for fr om th ir teen to
four teen h our s for a poW er s tation h av ing an electr ic output of
about one g ig aW att, th is r eq uir es tank contents of th e or der of
a h undr ed th ous and cubic m eter s at 600 C . and an e? iciency
of 4 0% fr om th e h eat r es er v oir to th e outlet of th e g ener ator .
US 201 1 /01 63259 A1
Th is m eans th at th e h eat tr ans fer ? uid h as to be v er y inex pen
s iv e s ince oth er w is e th e capital cos t for s uch a pow er s tation
becom es uneconom ically h ig h . It als o m eans th at s u? icient
m ater ial of th e h eat tr ans fer ? uid h as to be av ailable, s ince
h undr eds of one g ig aW att units ar e r eq uir ed for s upply on a
lar g e s cale and to s ecur e th e bas e load.
[ 001 6] Th e s olution to th e econom ical s upply of s olar
ener g y on a lar g e s cale th er efor e ultim ately depends on
W h eth er th er e is a h eat tr ans fer ? uid W h ich can be us ed in th e
long ter m at tem per atur es of up to 650 C . , h as a v er y loW ,
econom ically m anag eable v apor pr es s ur e, pr efer ably beloW
1 0 bar , at th is tem per atur e, does not ox idativ ely attack th e ir on
m ater ials us ed and h as a v er y loW m elting point.
[ 001 7 ] At ? r s t g lance, th es e conditions couldm os t eas ily be
s atis ? ed by elem ental s ulfur . Sulfur is av ailable in s uf? ciently
lar g e q uantities ; th er e ar e v er y lar g e, h ig h -y ielding depos its
and s ulfur is obtained as W as te in th e des ulfur iZ ation of fuels
and natur al g as . At pr es ent, th er e ar e no pos s ible us es for
m illions of m etr ic tons of s ulfur .
[ 001 8 ] Th e m elting point of s ulfur ofj us t about 1 20 C . is
loW er th an th at of s alt m elts for us e as h eat tr ans fer ? uid and
th e boiling point of s ulfur of 4 4 4 C . is in th e cor r ect r ang e:
decom pos ition is v ir tually r uled out. At 650 C . , th e v apor
pr es s ur e of s ulfur is about 1 0 bar , a pr es s ur e W h ich is indus
tr ially m anag eable. At 1 20 C . , th e v is cos ity of s ulfur is only
about 7 centipois e ( 7 m Pas ) .
[ 001 9] Th e dens ity of liq uid s ulfur is on av er ag e about 1 . 6
k g /liter ov er a W ide tem per atur e r ang e, th e s peci? c h eat is
about 1 000 j oule per k g and deg r ee or about 1 600 j oule per
liter and deg r ee. It is th us beloW th at of W ater , v iZ . 4 000 j oule
per liter and deg r ee, but abov e th e s peci? c h eat of m os t
cus tom ar y or g anic h eat tr ans fer ? uids . ( Mater ials data; Hans
Gunth er Hir s ch ber g , Handbuch V er fah r ens tech nik and
Anlag enbau, pag e 1 66, Spr ing er V er lag 1 999, ISBN
354 0606238 ) .
[ 0020] A dis adv antag e of elem ental s ulfur for us e as h eat
tr ans fer ? uid or a s tor ag e ? uid could be its v is cos ity beh av ior :
[ 0021 ] In th e tem per atur e r ang e fr om about 1 60 to 230 C . ,
th e cy clic s ulfur m olecules under g o r ing -opening poly m er
iZ ation to for m v er y long ch ains . W h ile th e v is cos ity abov e
th e m elting r ang e is about 7 m Pas , it incr eas es at 1 60 C . to 23
m Pas and at tem per atur es in th e r ang e fr om 1 7 0 to 200 C . it
r each es m ax im um v alues of about 1 00 000 m Pas . Th e poly
m er iZ ation of s ulfur th us g ener ally br ing s about an incr eas e in
v is cos ity , s o th at th e nor m al pur i? ed s ulfur can in g ener al no
long er be pum ped in th is tem per atur e r ang e, W h ich is not v er y
s uitable for us e as h eat tr ans fer ? uid.
[ 0022] It W as an obj ect of th e inv ention to dis cov er a com
pos ition for th e tr ans por t and s tor ag e of h eat ener g y ( h er ein
after als o r efer r ed to as h eat tr ans fer m edium /h eat s tor ag e
m edium of th e inv ention ) , W h ich com pr is es s ulfur and does
not dis play th e dis adv antag es indicated abov e, for ex am ple
th e r elativ ely h ig h v apor pr es s ur e at elev ated tem per atur es
and es pecially th e v is cos ity incr eas e.
[ 0023] As a r es ult of th e dev elopm ents of th e s odium -s ulfur
batter y , s om e indus tr ially im por tant pr oper ties of poly s ul? de
m elts , as des cr ibed beloW , h av e becom e k noW n in th e pas t.
[ 0024 ] Melting point m inim a occur in th e binar y s y s tem s at
th e com pos itions N a2S3 at 235 C . and KZ SL4 4 at 1 1 2 C . ;
N a2S3 does not ex is t in th e m elt but ins tead a m ix tur e of
pr edom inantly N a2S2 and N a2S4 is pr es ent. Th e loW es t eutec
tic m elting point in th e ( calculated) ter nar y s y s tem
KiN aiS is dis play ed by a poly s ul? de of th e com pos ition
( KO_ 7 7 N aO_ 23) 2S3_ 7 4 at 7 3 C . ( Lindber g , D . , Back m an, R. ,
J ul. 7 , 201 1
Hupa, M. , C h ar tr and, P. , Th er m ody nam ic ev olution and
optim iz ation of th e N aiKiSi s y s tem in J . C h em . Th enn.
( 2006) 38 , 900-91 5) .
[ 0025] Som e r efer ences s tate th at s odium poly s ul? des ar e
uns table at th eir m elting points . Th e potas s ium poly s ul? des
ar e s aid to be m or e s table. Accor ding to th es e r efer ences ,
KZ S4 decom pos es under atm os ph er ic pr es s ur e at 620 C . into
KZ S3 and s ulfur ; KZ S3 decom pos es at 7 8 0 C . into KZ S2 and
s ulfur ( US. Pat. N o. 4 , 21 0, 526) .
[ 0026] Th e r ang es h av ing m olar s ulfur s pecies fr om S2 to
S3 ar e th us par ticular ly s table. If th e ph as e diag r am s of th e
binar y s y s tem s ar e ex am ined, a m elting point of, for ex am ple,
360 C . is found for N a2S2_ 8 , a m elting point of 250 C . is
found for K2S2_ 8 and a m elting point of about 27 0 C . is found
for th e ter nar y poly s ul? de N aKS2_ 8 .
[ 0027 ] Th e q uite h ig h m elting points do not pr ov ide m uch
encour ag em ent to look at alk ali m etal poly s ul? des for us e as
h eat tr ans fer m edium and h eat s tor ag e m edium .
[ 0028 ] Rath er , th e v is cos ity beh av ior of th e poly s ul? des
points aW ay fr om concentr ating on th is clas s of com pound: on
clos er ex am ination of th e m elts of alk ali m etal poly s ul? des it
h as been found th at th e alk ali m etal poly s ul? des h av e
incr eas ed v is cos ities at tem per atur es beloW 200 C . Th us ,
s odium poly s ul? des of th e for m ula N a2S3_ 4 h av e a v is cos ity
of about 1 0 centipois e at 4 00 C . ( Th e Sodium Sulfur Bat
ter y , J . L. SudW or th andA. R. Tilley , Univ . Pr es s 1 98 5, pag es
1 4 3-1 4 6, ISBN 04 1 2-1 64 90-6) .
[ 0029] Th is v alue doubles on loW er ing th e tem per atur e by
50 C . , i. e. to 20 cP at 350 C . , 4 0 cP at 300 C . , 1 60 cP at 200
C . , 320 cP at 1 50 C . and, ex tr apolated fur th er , 64 0 cP ifth e
poly s ul? de W as s till liq uid at 1 00 C . Th e latter v alue of 64 0
cP cor r es ponds to about h alf th e v is cos ity of g ly cer ol at r oom
tem per atur e ( 1 4 8 0 cP) . For com par is on, th e v is cos ity of W ater
is about 1 cP, th at of oliv e oil fr om about 1 00 to 200 cP. Th e
alk ali m etal poly s ul? des often s olidify in a v itr eous fas h ion
and for m h ig h -v is cos ity g las s es W h ich s loW ly cr y s talliz e ov er
a per iod of day s at r oom tem per atur e.
[ 0030] Finally , th e cor r os ion beh av ior of th e alk ali m etal
poly s ul? de m elts lik eW is e pr ov ides no encour ag em ent to
ex am ine th is clas s of com pounds for us e as h eat tr ans fer ? uid
and h eat s tor ag e ? uid. Th us , it is k noW n, for ex am ple, th at
alk ali m etal poly s ul? de m elts can r apidly dis s olv e ev en
m etallic g old to for m com plex s ul? des .
[ 0031 ] In th e folloW ing , Me r epr es ents th e g r oup of th e
folloW ing alk ali m etals of th e Per iodic Table of th e Elem ents :
lith ium , s odium , potas s ium , r ubidium and ces ium .
[ 0032] It h as noW s ur pr is ing ly been found th at alk ali m etal
poly s ul? des of th e com pos ition ( I) ( h er einafter als o r efer r ed
to as alk ali m etal poly s ul? des accor ding to th e inv ention )
( MMUMMPZ XBSX ( I)
W h er e Mel and Me2 ar e s elected fr om th e g r oup of alk ali
m etals cons is ting of lith ium , s odium , potas s ium , r ubidium
and ces ium , Me1 is differ ent fr om Me2 and x is fr om 0 to 1
and Z is fr om 2. 3 to 3. 5, ar e s till ? uid at tem per atur es doW n to
1 30 C . , i. e. h av e s ig ni? cantly loW er m elting points and v is
cos ities th an th os e to be ex pected fr om th e liter atur e.
[ 0033] Pr efer ence is g iv en to th e poly s ul? des de? ned abov e
in for m ula ( I) in W h ich Melr potas s ium and Me2: s odium ,
par ticular ly pr efer ably th e poly s ul? des de? ned abov e in for
m ula ( I) in W h ich x is fr om 0. 5 to 0. 7 and Z is fr om 2. 4 to 2. 9.
W ith par ticular pr efer ence being g iv en to th e poly s ul? des
de? ned abov e in for m ula ( I) in W h ich Melr potas s ium and
Me2: s odium and x is fr om 0. 5 to 0. 7 and Z is fr om 2. 4 to 2. 9.
US 201 1 /01 63259 A1
[ 0034 ] Fur th er par ticular pr efer ence is g iv en to th e poly s ul
? des ofth e for m ulae ( N aO_ 5_ O_ 65KO_ 5_ O_ 35) 2S2_ 4 _ 2_ 8 or ( N aO_ 6KO_
4 ) 2S2. 6
[ 0035] Th e m elting points obs er v ed W er e g ener ally m or e
th an 2000 C . low er th an th e liter atur e v alues .
[ 0036] Accor ding to th e pr es ent s tate of k now ledg e, th es e
ar e attr ibutable to th e differ ent m eth od of s y nth es is of th e
alk ali m etal poly s ul? des accor ding to th e inv ention com par ed
to th e liter atur e.
[ 0037 ] Th e alk ali m etal poly s ul? des accor ding to th e inv en
tion can be obtained by th e folloW ing pr oces s es .
[ 0038 ] For th e pur pos es of th e inv ention, v er y econom ical
s y nth etic r outes s h ould be em ploy ed. For th is pur pos e, con
centr ated aq ueous s olutions of th e cor r es ponding alk ali m etal
h y dr og ens ul? des ( MeHS) . for ex am ple s odium h y dr og ens ul
? de, N aHS, or potas s ium h y dr og ens ul? de, KHS, W h ich ar e
obtained by pas s ing h y dr og en s ul? de into th e aq ueous
h y dr ox ide s olutions of th e cor r es ponding alk ali m etals Me,
W er e r eacted W ith s ulfur accor ding to th e g ener al for m ula
2MeHS+z S >Me2S( Z +1 ) +H2S ( Me: alk ali m etal,
for ex am ple K, N a)
W ith one eq uiv alent of h y dr og en s ul? de being g iv en off. Th is
h y dr og en s ul? de can be r ecir culated and r eus ed for pr epar ing
th e alk ali m etal h y dr og en s ul? des .
[ 0039] Th e W ater of r eaction and th e s olution W ater W er e
pr efer ably dis tilled off q uick ly W ith th e tem per atur e being
incr eas ed to up to 500 C . to g iv e th e alk ali m etal poly s ul? des
accor ding to th e inv ention.
[ 004 0] In s cience, on th e oth er h and, attem pts ar e m ade to
pr epar e poly s ul? des W h ich ar e as pur e as pos s ible; th e eco
nom ics g ener ally play s no r ole. For th is r eas on, th e alk ali
m etals ar e r eacted W ith elem ental s ulfur , us ually in liq uid
am m onia by m eans of W h ich th e cons ider able h eat of r eaction
ev olv ed in th is r eaction is r em ov ed, in or der to pr epar e th e
pur e poly s ul? des .
[ 004 1 ] Accor ding to th e pr es ent s tate of k noW ledg e, th e
differ ent pr oper ties of th e alk ali m etal poly s ul? des accor ding
to th e inv ention ar e due to th e differ ent s y nth etic r outes :
[ 004 2] V er y pur e alk ali m etal poly s ul? des ar e obtained by
th e W ater -fr ee s y nth es is accor ding to th e pr ior ar t.
[ 004 3] In th e s y nth es is accor ding to th e inv ention, W ater
and h y dr og en s ul? de ar e g ener ally pr es ent. W ater and h y dr o
g en s ul? de par ticipate, accor ding to th e pr es ent s tate of
k noW ledg e, in th e r eaction in v er y com plex , tem per atur e
dependent eq uilibr ia and pr es um ably r es ult in oth er s tr uc
tur es and/or oth er m olar m as s dis tr ibutions th an in th e W ater
fr ee s y nth es is . V er y s m all r es idues of W ater and/or h y dr og en
s ul? de, h y dr og ens ul? des or s ulfane end g r oups W h ich ar e
? r m ly bound and im pos s ible to r em ov e under th e econom ical
pr oces s conditions accor ding to th e inv ention m ay pos s ibly
als o be r es pons ible for loW er ing m elting point and v is cos ity
of th e alk ali m etal poly s ul? des accor ding to th e inv ention.
[ 004 4 ] Th is obs er v ation leads to th e s olution to th e m elting
point and v is cos ity pr oblem s :
[ 004 5] A fur th er pr oces s for pr epar ing th e alk ali m etal
poly s ul? des of th e for m ula ( I) accor ding to th e inv ention or
th e abov e-des cr ibed pr efer r ed em bodim ents th er eof is th e
r eaction of alk ali m etal h y dr og ens ul? des W ith s ulfur in con
centr ated aq ueous s olution to for m th e alk ali m etal poly s ul
? des accor ding to th e inv ention and, pr efer ably , th e s ubs e
q uent s ubs tantial deW ater ing th er eof by dir ectly dis tilling off
th e W ater .
[ 004 6] It is als o pos s ible to pr epar e th e alk ali m etal poly s ul
? des accor ding to th e inv ention by r eacting th e alk ali m etal
J ul. 7 , 201 1
h y dr og ens ul? des W ith alk ali m etal h y dr ox ide to for m th e
alk ali m etal s ul? des accor ding to
and r eacting th e alk ali m etal s ul? des W ith fur th er s ulfur to
for m th e poly s ul? des .
[ 004 7 ] HoW ev er , th er e is a r is k in th is s y nth es is th at a h ig h
concentr ation of h y dr ox ide ions W ill be pr es ent in th e con
centr ated aq ueous s olution as a r es ult of th e h y dr oly tic back
r eaction; th es e can r eact in an undes ir able s econdar y r eaction
W ith th e s ulfur of th e s ubs eq uent r eaction s tep to for m h ig h
m elting and th er m ally uns table alk ali m etal th ios ulfate.
[ 004 8 ] Alk ali m etal th ios ulfates g ener ally incr eas e th e
m elting point, incr eas e th e m elt v is cos ity of th e alk ali m etal
poly s ul? des and decom pos e at elev ated tem per atur es by v ar i
ous r eaction r outes to for m fur th er s alts .
[ 004 9] D ecom pos ition pr oducts of th e th ios ulfates include
th e s ulfates of th e alk ali m etals W h ich g ener ally lik eW is e h av e
th e dis adv antag eous pr oper ties of h ig h m elting point and
v is cos ity as com ponents in th e poly s ul? de m elt.
[ 0050] Th e s y nth etic r oute accor ding to th e inv ention
av oids th is s econdar y r eaction; th er e ar e us ually no ex ces s
h y dr ox ide ions in an elev ated concentr ation.
[ 0051 ] In a fur th er v ar iant for pr epar ing th e alk ali m etal
poly s ul? des accor ding to th e inv ention, it is pos s ible to av oid
th e s econdar y r eactions and th us lik eW is e av oid ex ces s
h y dr ox ide ions by W or k ing W ith a s ubs toich iom etr ic am ount
of alk ali m etal h y dr ox ide in th e r eaction of alk ali m etal h y dr o
g ens ul? de W ith alk ali m etal h y dr ox ide. In th is cas e, a m ax i
m um of 0. 9 m ol of alk ali m etal h y dr ox ide is us ed per m ole of
alk ali m etal h y dr og ens ul? de. C or r es ponding to th e s ubs to
ich iom etr ic m olar am ount of alk ali m etal h y dr ox ide, a m ix
tur e of s ul? de and h y dr og ens ul? de is th en us ually pr es ent and
is r eacted W ith s ulfur to for m th e alk ali m etal poly s ul? des
accor ding to th e inv ention.
[ 0052] In a fur th er v ar iant for pr epar ing th e alk ali m etal
poly s ul? des accor ding to th e inv ention, it is pos s ible, ins tead
of r eacting th e concentr ated aq ueous s olutions of th e alk ali
m etal h y dr og ens ul? des and optionally th e s ul? des in a m ix
tur e W ith h y dr og ens ul? des W ith s ulfur and deW ater ing th e
poly s ul? des , ? r s tly to deW ater th e alk ali m etal h y dr og ens ul
? des , optionally in th e m ix tur e W ith s ul? des , befor e r eaction
W ith th e s ulfU r and r eact th e deW ater ed h y dr o g ens ul? des and
any s ul? des pr es ent th er ein W ith th e s ulfur in a s econd s tep.
[ 0053] Th is v ar iant g ener ally r es ults in th e h ig h -m elting
dr y s ubs tances being obtained in th e deW ater ing of th e h y dr o
g ens ul? des or th e s ul? des pr es ent in adm ix tur e W ith th e
h y dr og ens ul? des , W h ich m ak es th e pr epar ation s om eW h at
m or e com plicated.
[ 0054 ] HoW ev er , th es e pr oces s v ar iants g iv e alk ali m etal
poly s ul? des accor ding to th e inv ention W h os e s olidi? cation
tem per atur e is about 1 0-200 C . beloW th at of alk ali m etal
poly s ul? des accor ding to th e inv ention h av ing th e s am e com
pos ition obtained by th e ? r s t and pr efer r ed pr oces s v ar iant.
[ 0055] Pr efer ence is g iv en to us ing th e alk ali m etal poly s ul
? des accor ding to th e inv ention h av ing Z : 2. 3-3. 5. C ontr ar y to
W h at is indicated in th e liter atur e, th e pur e alk ali m etal
poly s ul? des , pr efer ably s odium poly s ul? des , accor ding to
th e inv ention h av ing th es e s ulfur contents pr ov e to be
ex tr em ely th er m ally s table up to about 7 000 C .
[ 0056] Th e h ig h th er m al s tability of th e alk ali m etal
poly s ul? des , pr efer ably s odium s ul? des , accor ding to th e
inv ention is par ticular ly appar ent at v alues of Z of les s th an 3.
US 201 1 /01 63259 A1
Sulfur contents W ith v alues of Z g r eater th an 3. 5 g ener ally
g iv e dis adv antag eous ly incr eas ed v is cos ities .
[ 0057 ] Th e dens ities of th e alk ali m etal poly s ul? des
accor ding to th e inv ention at 3500 C . ar e g ener ally in th e
r ang e fr om 1 . 8 to 1 . 9 g /cm 3.
[ 0058 ] Of cour s e, th e us e of ces ium or r ubidium as alk ali
m etal is als o s uitable for th e alk ali m etal poly s ul? des accor d
ing to th e inv ention. Th es e alk ali m etals us ually for m poly s ul
? des up to th e h ex as ul? des .
[ 0059] Accor ding to th e pr es ent h y poth es es , th e s iZ e of th e
ions in? uences th e v is cos ity of th e alk ali m etal poly s ul? des
accor ding to th e inv ention. Th us , th e lar g er potas s ium ions
g ener ally g iv e s om eW h at loW er v is cos ities th an th e s m aller
s odium ions .
[ 0060] Addition of fur th er s alts , for ex am ple alk ali m etal
th iocy anates , to th e alk ali m etal poly s ul? des accor ding to th e
inv ention in or der to r educe th eir m elting points is pr efer ably
av oided. Th e th er m al s tability or th e cor r os ion beh av ior ( par
ticular ly at h ig h tem per atur e) of th e alk ali m etal poly s ul? des
accor ding to th e inv ention canbe alter ed in a dis adv antag eous
W ay as a r es ult.
[ 0061 ] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention us ually com pr is e th e alk ali m etal poly s ul? des
accor ding to th e inv ention in a s ubs tantial am ount up to a
m ax im um of v ir tually 1 00% by W eig h t, for ex am ple in th e
r ang e fr om 20% by W eig h t to v ir tually 1 00% by W eig h t or
fr om 50% by W eig h t to v ir tually 1 00% by W eig h t.
[ 0062] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention ar e us ually pr otected ag ains t intr us ion of m ois
tur e dur ing pr oduction, s tor ag e, tr ans por t and us e. In g ener al,
th e h eat tr ans fer m edium /h eat s tor ag e m edium of th e inv en
tion ar e th er efor e us ed in a clos ed s y s tem of pipes , pum ps ,
r eg ulating dev ices and v es s els .
[ 0063] Th e loW v is cos ity of th e h eat tr ans fer m edium /h eat
s tor ag e m edium of th e inv ention is par ticular ly adv antag eous
becaus e a loW v is cos ity pr om otes h eat tr ans m is s ion and th e
ener g y r eq uir ed for pum ping th e liq uid th r oug h th e pipes is
r educed. Th is can in m any cas es be m or e im por tant th an a
br oadening of th e tem per atur e r ang e in a doW nW ar d dir ection.
[ 0064 ] Th e neg lig ibly loW v apor pr es s ur e of th e h eat tr ans
fer m edium / h eat s tor ag e m edium of th e inv ention contr ibutes
by m eans of r educed W all th ick nes s es of pipes and appar a
tus es to loW er capital cos ts and av oids s ealing pr oblem s .
[ 0065] Th e oper ation of plants , pr efer ably plants for ener g y
g ener ation, at tem per atur es up to 7 00 C . us ing th e h eat
tr ans fer m edium /h eat s tor ag e m edium of th e inv ention g en
er ally r eq uir es m ater ials W h ich ar e s table to s ul? ding at h ig h
tem per atur es . As m entioned at th e beg inning , it is k noW n
fr om th e liter atur e th at s odium poly s ul? de m elts ar e able to
dis s olv e m etallic g old in th e for m of com plex s ul? des .
[ 0066] It h as been found th at th e h eat tr ans fer m edium /h eat
s tor ag e m edium of th e inv ention do not h av e a par ticular ly
g r eat cor r os ion potential W h en th ey com pr is e v er y little v ola
tile W ater W h ich is capable of being dis tilled off.
[ 0067 ] W ell-s uited m ater ials for th e h eat tr ans fer m edium /
h eat s tor ag e m edium of th e inv ention, par ticular ly at elev ated
tem per atur e, ar e th e folloW ing :
[ 0068 ] Par ticular ly cor r os ion-r es is tant m ater ials ar e alum i
num and in par ticular alum inum -com pr is ing alloy s , for
ex am ple h ig h ly h eat-r es is tant alum inum -com pr is ing s teels .
[ 0069] Such ir on m ater ials h av e fer r itic m icr os tr uctur es
and ar e fr ee of nick el. N ick el s ul? des for m loW -m elting
ph as es W ith ir on. Th e m os t effectiv e alloy ing cons tituent is
alum inum , W h ich for m s an im per m eable, pas s iv ating ox ide
J ul. 7 , 201 1
lay er and/or s ul? de lay er on th e s ur face of th e m ater ial. A
r elativ ely old m ater ial of th is ty pe h av ing 22% by W eig h t of
ch r om ium and 6% by W eig h t of alum inum , a m ater ial W h ich
is us ed as h eat conductor , h as becom e k noW n under th e nam e
Kanth al.
[ 007 0] Ir on alloy s W h ich ar e m or e r es is tant to s ul? ding
com pr is e les s ch r om ium and m or e alum inum , as des cr ibed,
for ex am ple, in EP 0 652 297 A. Th er e, alloy s h av ing th e
com pos ition: fr om 1 2 to 1 8 atom % of alum inum , fr om 0. 1 to
1 0 atom % of ch r om ium , fr om 0. 1 to 2 atom % of niobium ,
fr om 0. 1 to 2 atom % of s ilicon, fr om 0. 01 to 2 atom % of
titanium and fr om 0. 1 to 5 atom % of bor on ar e des cr ibed.
N iobium , bor on and titanium s er v e to alloW a ? ne-g r ained
ir on alum inide ( Fe3Al) to pr ecipitate, as a r es ult of W h ich an
incr eas ed toug h nes s W ith elong ations abov e 3% and
im pr ov ed pr oces s ability ar e obtained.
[ 007 1 ] A par ticular ly g ood com bination of r es is tance to
s ul? ding W ith g ood pr oces s ability by cas ting , h ot for m ing ,
cold for m ing and g ood ductility at r oom tem per atur e W ith
elong ations at br eak of about 20% is g iv en by an alloy com
pos ition com pr is ing fr om 8 to 1 0% by W eig h t of alum inum ,
fr om 0. 5 to 2% by W eig h t of m oly bdenum , balance ir on.
Silicon s h ould not be pr es ent in th e alloy s ince it decr eas es th e
ductility at r oom tem per atur e. Pr opor tions of ch r om ium ar e
lik eW is e not adv antag eous ; ch r om ium s ul? de is dis s olv ed in
th e m elts . Alloy ing -in of in each cas e up to 2% by W eig h t of
y ttr ium and/or Z ir conium als o r es ults in for m ation of Z ir co
nium ox ide and/or y ttr ium ox ide in th e pr otectiv e alum inum
ox ide lay er , g r eatly incr eas ing th e ductility of th e alum inum
ox ide and th us m ak ing th e pr otectiv e lay er par ticular ly s table
ag ains t s pelling and m ech anical s tr es s es in th e ev ent of tem
per atur e ? uctuations . Z ir conium ox ide in par ticular incr eas es
th e ductility of th e alum inum ox ide lay er in an adv antag eous
W ay .
[ 007 2] Th e incr eas ed ductility of th e bas e m ater ial and th e
pr otectiv e ox ide lay er g iv es r es is tances to s ul? ding W h ich ar e
com par able to th os e of alloy s h av ing h ig h er alum inum con
tents . N o m icr ocr ack s ar e for m ed in th e ev ent of tem per atur e
ch ang es and th e alloy s ar e not s ens itiv e to h y dr og en.
[ 007 3] Ir on alloy s h av ing s till h ig h er alum inum contents
s h ould be ev en m or e s table to poly s ul? de m elts , but th ey can
no long er be W or k ed cold. Th ey ar e ex tr uded or r olled at
elev ated tem per atur es . Such alloy s , W h ich ar e alloy s com pr is
ing Fe3Al ph as es , com pr is e 21 atom % of alum inum , 2 atom
% of ch r om ium and 0. 5 atom % of niobium or 26 atom % of
alum inum , 4 atom % of titanium and 2 atom % of v anadium
or 26 atom % of alum inum and 4 atom % of niobium or 28
atom % of alum inum , 5 atom % of ch r om ium , 0. 5 atom % of
niobium and 0. 2 atom % of car bon ( EP 04 55 7 52 A) . Th e
ch r om ium content s h ould be k ept as loW as pos s ible; it is bes t
to dis pens e W ith ch r om ium as alloy ing elem ent.
[ 007 4 ] A v er y h ig h m oly bdenum content, in s o far as it does
not r educe th e r oom tem per atur e ductility , s h ould als o s up
pr es s s ul? ding . Moly bdenum is r ecom m ended in addition to
alum inum as h ous ing m ater ial for s odium -s ulfur batter ies .
[ 007 5] Accor ding to th e liter atur e, th e cor r os iv ity of alk ali
m etal poly s ul? des decr eas es W ith decr eas ing s ulfur content.
[ 007 6] Th e m ech anical s tr eng th of ir on alloy s h av ing a h ig h
alum inum content is s uf? ciently h ig h at tem per atur es of up to
7 000 C . for us e W ith th e h eat tr ans fer m edium /h eat s tor ag e
m edium of th e inv ention.
US 201 1 /01 63259 A1
[ 007 7 ] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention can be pr oduced inex pens iv ely fr om ch eap
inter m ediates by th e conv entional lar g e-s cale pr oces s es of th e
ch em ical indus tr y .
[ 007 8 ] Th e alk ali m etal poly s ul? des accor ding to th e inv en
tion can, for ex am ple, be pr epar ed in th e cas e of s odium or
potas s ium by pr epar ing th e cor r es ponding h y dr ox ides fr om
s odium ch lor ide and potas s ium ch lor ide by ch lor oalk ali elec
tr oly s is .
[ 007 9] Th e h y dr og en for m ed at th e s am e tim e is adv anta
g eous ly r eacted W ith liq uid s ulfur to for m h y dr og en s ul? de.
In addition, th e ch em ical indus tr y h as dev eloped v er y eleg ant
econom ical pr oces s es W h ich oper ate continuous ly and at
atm os ph er ic pr es s ur e, as a r es ult of W h ich th e s tor ag e of a
lar g e am ount of h y dr og en s ul? de is s uper ? uous ( e. g . W O
2008 /08 7 08 6) . It is pr oduced in th e m as s ? oW W h ich is j us t
r eq uir ed by th e nex t s tag e.
[ 008 0] Of cour s e, it is als o pos s ible to utiliZ e th e. h y dr og en
s ul? de for m ed in des ulfur iZ ation plants in th e h y dr og enation
s tag es .
[ 008 1 ] Th e h y dr og en s ul? de is g ener ally r eacted W ith th e
alk ali m etal h y dr ox ides to for m th e alk ali m etal h y dr o g ens ul
? des and th es e ar e s ubs eq uently r eacted W ith s ulfur to for m
th e poly s ul? des .
[ 008 2] It is als o pos s ible to pr epar e th e alk ali m etal poly s ul
? des accor ding to th e inv ention by r eacting concentr ated
aq ueous s olutions of am m onium s ul? de ( N H4 ) 2S or am m o
nium h y dr og ens ul? de N H4 HS or m ix tur es of am m onium
s ul? de and am m onium h y dr og ens ul? de W ith th e cor r es pond
ing alk ali m etal h y dr ox ides W ith elim ination of am m onia to
g iv e th e cor r es ponding alk ali m etal h y dr og ens ul? des .
Am m onia is r ecir culated to th e s y nth es is of th e am m onium
s ul? des .
[ 008 3] In g ener al, th is s y nth etic r oute can be car r ied out
W h en am m onium s ul? de and/ or am m onium h y dr og ens ul? de
ar e av ailable inex pens iv ely fr om anoth er pr oces s , for
ex am ple fr om th e s cr ubbing of h y dr og en s ul? de fr om g as es .
[ 008 4 ] If th e copr oduction of ch lor ine by ch lor oalk ali elec
tr oly s is is to be av oided, it is pos s ible to conv er t loW -ch lor ide
potas s ium s ulfate or s odium s ulfate h av ing ch lor ide contents
of les s th an 0. 01 % by W eig h t into th e s ul? des by m eans of
r educing ag ents .
[ 008 5] Potas s ium s ulfate in par ticular is pr oduced by th e
fer tiliZ er indus tr y In am ounts of m illions of m etr ic tons per
y ear . Econom ical pr oces s es for r educing th e ch lor ide content
of potas s ium s ulfate, e. g . by tr eatm ent of th e s alts W ith W ater ,
ar e k noW n ( D E 2 21 9 7 04 ) . If h y dr og en is us ed as r educing
ag ent, it is pos s ible to W or k at tem per atur es of fr om 600 to
7 000 C . in th e s olid s tate in a r otar y tube fur nace and obtain
v er y clean s ul? des ( U. S. Pat. N o. 20, 690, 958 , D E 590 660) .
As cataly s ts for th e r eduction, us e is g ener ally m ade of fr om
1 to 5% by W eig h t of alk ali m etal car box y lates . for ex am ple
th e for m ates or th e ox alates .
[ 008 6] HoW ev er , th e m os t effectiv e cataly s ts appear to be
alk ali m etal poly s ul? des W h ich h av e to be m ix ed into th e
alk ali m etal s ulfate only at th e beg inning of th e r eduction.
[ 008 7 ] It is als o pos s ible to br ing about th e r eduction of th e
alk ali m etal s ulfates Me2S04 dir ectly by m eans of natur al g as
accor ding to th e folloW ing eq uation:
J ul. 7 , 201 1
[ 008 8 ] Th e s ul? des ar e adv antag eous ly dis s olv ed in W ater
and conv er ted into th e h y dr og ens ul? des by intr oduction of
h y dr og en s ul? de g as : in concentr ated aq ueous s olution, th e
eq uilibr ium
is es tablis h ed.
[ 008 9] W h en h y dr og en s ul? de g as is intr oduced, th is r eacts
W ith th e h y dr ox ide and th e s ul? de is conv er ted into h y dr o
g ens ul? de accor ding to
H2S+MeOH - - - >MeHS+H2O
Th is g iv es th e ov er all r eaction:
Me2S+H2S - - - >2MeHS
[ 0090] Th is s y nth es is accor ding ly r eq uir es natur al g as to
pr oduce th e h y dr og en, for ex am ple in th e s team r efor m ing
pr oces s , and only inex pens iv e m iner al r aW m ater ials as
ener g y car r ier s and als o th e v er y inex pens iv e s ulfur .
[ 0091 ] In th is ty pe of pr oces s , h y dr og en s ul? de is cir culated
and th us r eq uir ed in only s m all am ounts , s o th at a s epar ate
pr oces s s tep for pr oducing h y dr og en s ul? de is g ener ally
s uper ? uous .
[ 0092] Her e too, com plete conv er s ion of th e s ul? des into
th e h y dr og ens ul? des is g ener ally not neces s ar y . It is us ually
s uf? cient for th e for m ation of th e alk ali m etal h y dr ox ides to
be s uppr es s ed by addition of h y dr og en s ul? de and a m ix tur e
of alk ali m etal s ul? des and alk ali m etal h y dr og ens ul? des
h av ing a v er y loW concentr ation of alk ali m etal h y dr ox ide to
be pr es ent in or der to ach iev e conv er s ion into th e alk ali m etal
poly s ul? des accor ding to th e inv ention.
[ 0093] An adv antag e of th e alk ali m etal poly s ul? des
accor ding to th e inv ention is th at th ey can be pr epar ed in an
inex pens iv e continuous pr oces s : th e indiv idual r eaction s teps
pr oceed v er y q uick ly and ex oth er m ally . Th e r eactants can
th er efor e How q uick ly th r oug h s m all r eaction v olum es .
[ 0094 ] A W ell-s uited pr oces s is car r ied out as folloW s .
[ 0095] Hy dr og en s ul? de is pas s ed W ith intens iv e cooling
into concentr ated aq ueous s olutions of th e alk ali m etal
h y dr ox ides or alk ali m etal s ul? des h av ing a concentr ation of
fr om 4 0 to 60% by W eig h t. Th e r eaction tem per atur e is k ept
beloW 8 0 C . Subs eq uently , optionally after a s tep of concen
tr ating th e r eaction s olution to v alues of fr om about 50 to 8 0%
by W eig h t by r apid dis tillation, th e concentr ated alk ali m etal
h y dr og ens ul? de s olution is r eacted W ith th e pr es cr ibed
am ount of liq uid s ulfur . Her e, th e h eat of r eaction ev olv ed can
be us ed to v apor iZ e W ater . Th e W ater com pr is ed in th e r eac
tion m ix tur e is s ubs eq uently v apor iZ ed q uick ly W ith an
incr eas e in tem per atur e up to 4 500 C . , optionally W ith us e of
r educed pr es s ur e. Th e s tr eam of h y dr og en s ul? de for m ed,
m ix ed W ith W ater v apor , is cooled and th e h y dr og en s ul? de is
r ecir culated tog eth er W ith th e h y dr og en s ul? de-com pr is ing
W ater to th e s tag e of th e h y dr og ens ul? de s y nth es is . In g en
er al, no by -pr oducts W h ich h av e to be dis pos ed of occur .
[ 0096] All r eaction s teps ar e car r ied out under iner t condi
tions . Ox y g en is g ener ally ex cludedbecaus e it can ox idiZ e th e
poly s ul? des to undes ir able th ios ulfates W h ich incr eas e th e
m elting point of th e liq uid and ar e us ually uns table, s ul? tes
and h ig h -m elting s ulfates .
US 201 1 /01 63259 A1
[ 0097 ] As r eaction appar atus es , us e is adv antag eous ly
m ade of r eaction m ix ing pum ps follow ed by r es idence s ec
tions in or der to com plete th e r eactions . Th e r eaction tim es of
th e indiv idual r eactions ar e in th e r ang e fr om 0. 1 to 1 0 m in
utes . As appar atus es for r em ov ing th e W ater , appar atus es s uch
as falling ? lm ev apor ator s or th in ? lm ev apor ator s ar e g ener
ally us ed.
[ 0098 ] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention g ener ally m ak e it pos s ible to oper ate s olar th er
m al poW er s tations W ith th e e? iciencies of fos s il fuel-? r ed
poW er s tations , adv antag eous ly alloW ing th em to be oper ated
day and nig h t W ith out inter r uption by m eans of appr opr iately
dim ens ioned s tor ag e tank s for th e h ot liq uid. OW ing to th e
incr eas ed e? iciency , th e capital cos ts per k iloW att h our ar e
g ener ally r educed by a factor of 1 . 5 com par ed to th e pr ior ar t.
[ 0099] Th e s olidi? cation point abov e r oom tem per atur e
can be counter ed s tr uctur ally W ith little outlay by er ecting th e
m ir r or s and th e abs or ber tubes W ith a s lig h t fall and dr aining
th e h eat tr ans fer m edium /h eat s tor ag e m edium of th e inv en
tion fr om th e pipes into a collection tube s h or tly befor e s un
doW n and s tor ing th em in th er m ally ins ulated buffer tank s in
th e liq uid s tate at a feW deg r ees abov e th e s olidi? cation point
for oper ation on th e nex t day .
[ 01 00] HoW ev er , th e h eat tr ans fer m edium /h eat s tor ag e
m edium of th e inv ention can als o be dr aW n off by s uction into
th e th er m ally ins ulated tank s W ith out a s ig ni? cant s tr uctur al
fall. W h en car e is tak en in th e cons tr uction of th e plants to
ens ur e th at no m ov eable appar atus es s uch as pum ps or v alv es
ar e pr es ent in th e plant par ts W h ich becom e cold, r es idues of
th e h eat tr ans fer m edium /h eat s tor ag e m edium of th e inv en
tion can als o fr eeZ e W ith out dis adv antag es in th es e par ts and
be r em elted later .
[ 01 01 ] It is adv antag eous to k eep m ov ing par ts s uch as
pum ps or r eg ulating v alv es abov e th e m elting point of s ulfur
by additional h eating . HoW ev er , it is s im ples t to pum p th e h eat
tr ans fer m edium / h eat s tor ag e m edium of th e inv ention s loW ly
th r oug h th e s olar ? eld after s undoW n and th us alloW th eir
tem per atur e to dr op to 1 50-2000 C . Th e pipes g ener ally h av e
to be v er y W ell ins ulated th er m ally ag ains t h eat los s es s o th at
th e los s es by th er m al conduction ar e loW , s ig ni? cantly loW er
th an dur ing day tim e oper ation. At th e com par ativ ely loW
tem per atur es , th e r adiation los s es th r oug h th e abs or ber tubes
located in a v acuum ar e lik eW is e g ener ally q uite loW . Sh ould
th e tem per atur e of th e cir culating h eat tr ans fer m edium /h eat
s tor ag e m edium of th e inv ention dr op too far , s m all am ounts
of th e h ot h eat tr ans fer m edium /h eat s tor ag e m edium of th e
inv ention fr om th e appr opr iate s tock tank ar e m ix ed into
th es e. Th e h eat tr ans fer m edium /h eat s tor ag e m edium of th e
inv ention ar e adv antag eous ly us ed as h eat tr ans fer ? uids in
com bination W ith abs or ber tubes W h ich bear a coating W h ich
alloW s a h ig h abs or ption capability for s olar r adiation com
bined W ith a loW em is s ion of h eat r adiation in th e tem per atur e
r ang e fr om 1 50 to 2500 C .
[ 01 02] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention als o m ak es com bination W ith anoth er h eat
tr ans fer ? uid pos s ible. Th us , for ex am ple, th e h eat s tor ag e( s )
of a s olar th er m al poW er s tation W ith its s m all am ounts of
s tor ag e m edium can be oper ated us ing a v er y inex pens iv e
s ulfane-com pr is ing and th us loW -v is cos ity s ulfur under
s uper atm os ph er ic pr es s ur e as s tor ag e m edium W h ile on th e
oth er h and oper ating th e s olar ? eld W ith its abs or ber tubes
under atm os ph er ic pr es s ur e us ing th e s m aller am ounts of th e
J ul. 7 , 201 1
h ig h er -pr iced alk ali m etal poly s ul? des accor ding to th e
inv ention. Th e ener g y is in th is cas e tr ans fer r ed v ia an inter
m ediate h eat ex ch ang er .
[ 01 03] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention ar e j us t as s uitable for a fur th er ty pe of cons tr uc
tion of s olar th er m al poW er s tations v iZ . th e toW er tech nolog y .
as for th e par abolic g r oov e cons tr uction.
[ 01 04 ] Subs eq uent m ir r or s g uide th e s olar r adiation to th e
top of a toW er W h er e it im ping es on th e r eceiv er and h eats th e
h eat tr ans fer ? uid in th e r eceiv er to h ig h tem per atur es . Th e
h eated liq uid is utiliZ ed to g ener ate s team and, fcir th e pur
pos es of s tor ag e, conv ey ed to a lar g e-v olum e tank for nig h t
oper ation. At s undoW n, th e liq uid is s im ply alloW ed to r un
doW nW ar d fr om th e r eceiv er into a s tor ag e tank . Ev en W h en
W ater is v apor iZ ed dir ectly in th e r eceiv er and a th er m al
eng ine is oper ated th is W ay . th er e r em ains th e pr oblem of
oper ating th e plant at nig h t. For th is r eas on, a h eat s tor ag e
? uid is g ener ally als o indis pens ible for s uch ty pes of poW er
s tation.
[ 01 05] HoW ev er , th e h eat tr ans fer m edium /h eat s tor ag e
m edium of th e inv ention can als o be us ed for all oth er us es in
th e ? elds of h eat tr ans por t and h eat s tor ag e in indus tr y W h ich
r eq uir e an ex tr em ely br oad tem per atur e r ang e of th e liq uid
ph as e and h ig h tem per atur es . Th e v apor pr es s ur e of th e
m edium is neg lig ibly s m all for indus tr ial pur pos es .
[ 01 06] Th e h eat tr ans fer m edium /h eat s tor ag e m edium of
th e inv ention ar e als o par ticular ly s uitable for th e tr ans por t of
h eat ener g y fr om th e fuel elem ents of a nuclear r eactor in a
pr im ar y cir cuit W h ich can be oper ated at v ir tually atm o
s ph er ic pr es s ur e and th us s afely up to tem per atur es of 7 00 C .
Th is W ould m ak e a s afe, r adiation-r es is tant h eat tr ans fer
m edium av ailable. Th e s team tem per atur es in th e s econdar y
cir cuit can be incr eas ed cons ider ably and th e e? iciency of
nuclear poW er s tations can th us be incr eas ed cor r es ponding ly .
[ 01 07 ] Th e m ax im um tem per atur es at W h ich th e h eat tr ans
fer m edium /h eat s tor ag e m edium of th e inv ention can be us ed
is lim ited only by th e s tability of th e m ater ials of cons tr uction
us ed.
[ 01 08 ] In th e ev ent of los s of containm ent of pr oduct due to
an accident, th e h eat tr ans fer m edium / h eat s tor ag e m edium of
th e inv ention ar e far les s of a s afety h aZ ar d or h aZ ar d to th e
env ir onm ent th an or g anic liq uids .
[ 01 09] If th er e is a los s of containm ent of a s m all am ount of
h eat tr ans fer m edium /h eat s tor ag e m edium accor ding to th e
inv ention, th is is g ener ally ox idiZ ed by atm os ph er ic ox y g en
to for m m iner al s ulfates W ith in a feW day s . At elev ated tem
per atur es , th e poly s ul? des can ig nite in m ois t air becaus e th e
ig nition tem per atur e of th e h y dr og en s ul? de for m ed by
h y dr oly s is is 27 00 C .
[ 01 1 0] Th e poly s ul? des bur n W ith a ? am e W h ich g iv es off
little lig h t to for m s ulfur diox ide. Apar t fr om s ulfur diox ide,
no env ir onm entally tox ic pr oducts ar e for m ed. Sulfur diox ide
and th e s ulfur tr iox ide for m ed th er efr om by ox idation by
atm os ph er ic ox y g en ar e not k noW n as g r eenh ous e g as es .
[ 01 1 1 ] Bur ning alk ali m etal poly s ul? des can eas ily be
ex ting uis h ed by m eans of W ater becaus e th eir dens ity is
g r eater th an th at of W ater . Th e v apor iZ ing W ater q uick ly cools
th e poly s ul? de m elt and th e s team for m ed at th e s am e tim e
binds s ulfur diox ide.
[ 01 1 2] Sulfur diox ide can be abs or bed by m eans of W ater ,
and th e poly s ul? des r eadily dis s olv ed in W ater .
[ 01 1 3] Poly s ul? de r es idues adh er ing to plant com ponents
can eas ily be W as h ed off com pletely W ith W ater W ith out leav
ing any encr us tations .
US 201 1 /01 63259 A1
[ 01 1 4 ] Poly s ul? des dis s olv ed in W ater ar e lik ew is e ox i
diz ed by atm os ph er ic ox y g en, us ually for m ing s ulfur and
s ulfates . Both th e poly s ul? des and s ulfur can be ox idiz ed to
s ulfates in th e s oil by s ulfur bacter ia.
[ 01 1 5] Th e deg r adation of th e poly s ul? des is g r eatly accel
er ated by neutr aliz ation of a poly s ul? de s olution W ith dilute
acids , pr efer ably s ulfur ic acid, becaus e not only th e s ul? des
Me2S but als o s ulfur is im m ediately liber ated accor ding to
[ 01 1 6] Th e liber ated s ulfur is , as far as k now n, env ir onm en
tally neutr al.
EXAMPLES
Gener al Pr ocedur e
[ 01 1 7 ] Th e s y nth es is accor ding to th e inv ention of th e
poly s ul? des W as car r ied out us ing s m all am ounts in tes t tubes
in or der to dem ons tr ate its s im plicity .
[ 01 1 8 ] For th is pur pos e. com m er cial s odium h y dr og ens ul
? de in a concentr ation of 7 6% by W eig h t ( balance: W ater ) and
s ulfur in com m er cial pur ity W er e us ed.
[ 01 1 9] Potas s ium h y dr og ens ul? de W as pr epar ed by pas s
ing h y dr og en s ul? de into 1 1 2 g r am of a com m er cial 50%
s tr eng th by W eig h t aq ueous potas s ium h y dr ox ide s olution,
cor r es ponding to one m ole, W h ile cooling until th e s olution
W as s atur ated. A tem per atur e of 50 C . W as not ex ceeded
dur ing th is r eaction. Th e m as s of th e s olution incr eas ed by 34
g r am , cor r es ponding to one m ole of h y dr og en s ul? de. Th is
g av e an aq ueous s olution of potas s ium h y dr og ens ul? de in a
concentr ation of 4 9 per cent by W eig h t.
[ 01 20] After W eig h ing out th e alk ali m etal h y dr og ens ul? de
and th e s ulfur , th e atm os ph er ic ox y g en W as dis placed by
ar g on and th e m ix tur e W as h eated under a blank et of ar g on
fr om r oom tem per atur e to fr om 1 00 to 1 30 C . Th e s ulfur
m elted and th e r eaction to for m poly s ul? de com m enced at th e
s am e tim e. Th e tem per atur e incr eas ed adiabatically W ith in a
feW s econds to v alues of 1 30 C . -1 50 C . W ater m ix ed W ith
h y dr og en s ul? de dis tilled off.
[ 01 21 ] After a s h or t tim e, th e tem per atur e W as incr eas ed
fur th er to v alues of about 500 C . ov er a per iod of fr om 2 to 5
m inutes in or der to v apor iz e th e W ater as com pletely as pos
s ible.
[ 01 22] Th e tem per atur e of th e r eaction pr oduct W as s ubs e
q uently m aintained for about 2 m inutes m or e. Th e tem per a
tur es W er e m eas ur ed electr onically by m eans of a th er m o
couple. Th e loW er us e tem per atur e m eas ur ed dur ing cooling
W as r epor ted as th at tem per atur e at W h ich th e m elt j us t beg an
to dr aW th in th r eads W h en th e th er m ocouple h av ing a diam
eter of 1 . 5 m illim eter s W as tak en out of th e m elt. Th e cor r e
s ponding v is cos ity W as about 200 cP.
Ex am ple I
[ 01 23]
[ 01 24 ] 0. 04 m ol of s odium h y dr og ens ul? de ( 2. 95 g r am , 7 6
per cent s tr eng th by W eig h t) and 0. 036 m ol ( 1 . 1 5 g r am ) of
s ulfur W er e W eig h ed into a tes t tube and r eacted accor ding to
th e pr ocedur e des cr ibed. Th e r es ulting r ed liq uid h av ing th e
com pos ition N a2S2_ 8 W as ? uid. On cooling , it beg an to dr aW
th r eads at 1 4 0 C . On cooling fur th er , it s olidi? ed W ith cr y s
talliz ation.
J ul. 7 , 201 1
[ 01 25] Th e liq uid W as h eated to 7 00 C . in th e tes t tube. Th e
color ch ang ed to black and feW g as bubbles W er e for m ed at
th e beg inning . As far as th e ey e could dis cer n, no s ulfur W as
liber ated. On cooling , th e r ed color r etur ned and th e pr oper
ties h ad not ch ang ed.
[ 01 26] An analog ous ly pr epar ed s odium poly s ul? de h av
ing th e com pos ition N aS3 h ad a s om eW h at h ig h er v is cos ity . It
beg an to dr aW n th r eads at 1 50 C . dur ing cooling and on
fur th er cooling s olidi? ed W ith out cr y s talliz ation to for m a
v itr eous s olid.
[ 01 27 ] Th e s odium poly s ul? de N a2S3 W as pr epar ed once
m or e, but, in contr as t to th e ? r s t pr ocedur e, by deW ater ing
s odium h y dr og ens ul? de in one s tep by h eating to about 350
C . In th e s econd s tep. th e s ulfur W as added and th e m ix tur e
W as h eated W h ile s h ak ing . Th e poly s ul? de obtained in th is
W ay beg an to dr aW th r eads at 1 35 C . dur ing cooling .
Ex am ple 2
[ 01 28 ]
2KHS+2. 4 S - - - >K2S3_ 4 +H2S
[ 01 29] In a m anner analog ous to ex am ple 1 , 0. 04 m ol of
potas s ium h y dr og ens ul? de ( 5. 8 8 g r am , 4 9 per cent s tr eng th
by W eig h t) W as r eacted W ith 0. 04 8 m ol ( 1 . 54 g r am ) of s ulfur .
[ 01 30] On cooling , th e r ed liq uid h av ing th e com pos ition
K2S3_ 4 beg an to dr aW th r eads at 1 50 C . It cr y s talliz ed on
fur th er cooling . On h eating to about 7 50 C . , it becam e dar k .
Sig ns of decom pos ition W er e not obs er v ed. W h en cooled, it
becam e r ed ag ain and beg an to dr aW th r eads at 1 50 C . , W h ich
s h oW s th at it ex per ienced no ch ang e on h eating to 7 50 C .
Ex am ple 3
[ 01 31 ]
[ 01 32] 0. 02 m ol of s odium h y dr og ens ul? de, 0. 02 m ol of
potas s ium h y dr og ens ul? de and 0. 034 m ol of s ulfur W er e
r eacted W ith one anoth er in a m anner analog ous to ex am ple 1 .
Th is g av e a r ed loW -v is cos ity liq uid h av ing th e com pos ition
( KO_ 5N aO_ 5) 2S2_ 7 W h ich on cooling dr eW th r eads at 1 25 C .
and cr y s talliz ed on fur th er cooling . Th e liq uid W as h eated to
7 00 C . , r es ulting in it becom ing dar k . After cooling , it once
ag ain h ad th e pr oper ties as befor e h eating .
Ex am ple 4
[ 01 33]
5H2S
[ 01 34 ] Us ing a m eth od analog ous to ex am ple 1 , 0. 06 m ol of
potas s ium h y dr og ens ul? de, 0. 02 m ol of s odium h y dr og en
s ul? de and 0. 08 8 m ol of s ulfur W er e r eacted W ith one anoth er
and deW ater ed. Th is g av e a r ed liq uid h av ing th e com pos ition
( KO_ 7 5N aO_ 25) 2S3_ 2 W h ich on cooling beg an to dr aW th r eads at
1 25 C . and s olidi? ed to for m a v itr eous s olid on fur th er
cooling . Th e liq uid W as h eated to 7 00 C . and th en alloW ed to
cool ag ain. After cooling , it beg an to dr aW th r eads at 1 25 C .
Ex am ple 5
[ 01 35]
US 201 1 /01 63259 A1
[ 01 36] 0. 032 m ol ( 1 . 28 g r am ) of 1 00% s tr eng th s odium
h y dr ox ide W as dis s olv ed W h ile h eating in 0. 04 m ol of 4 9%
s tr eng th potas s ium h y dr og ens ul? de s olution ( 5. 8 8 g r am ) ,
cor r es ponding to 8 0% of th e m olar am ount of s odium
h y dr ox ide neces s ar y to conv er t th e potas s ium h y dr og ens ul
? de com pletely into s ul? de. 0. 08 8 m ol of s ulfur ( 2. 8 2 g r am )
W as W eig h ed into th e h om og eneous s olution and th e r eaction
m ix tur e W as , after th e ex oth er m ic r eaction h ad abated and
W ater and h y dr og en s ul? de h ad dis tilled off, h eated to about
600 C . Th e r ed liq uidbeg an to dr aW th r eads at 1 35 C . dur ing
cooling . W h en th e tem per atur e W as loW er ed fur th er , th e liq
uid s olidi? ed to for m a v itr eous s olid.
[ 01 37 ] In a fur th er ex per im ent, th e poly s ul? de h av ing th e
abov e com pos ition W as pr epar ed ag ain but th is tim e by deW a
ter ing th e r eaction m ix tur e of th e potas s ium h y dr og ens ul? de
and th e s odium h y dr ox ide. In th e s econd s tep, th e deW ater ed
h y dr og ens ul? de/ s ul? de m ix tur e W as r eacted W ith s ulfur . Th e
r es ulting r ed poly s ul? de beg an to dr aW th r eads at 1 1 5 C .
dur ing cooling , and on fur th er cooling it s olidi? ed to for m a
v itr eous s olid.
Ex am ple 6
[ 01 38 ]
[ 01 39] Us ing a m eth od analog ous to ex am ple 4 , 0. 024 m ol
( 1 . 66 g r am ) of 8 1 % s tr eng th potas s ium h y dr ox ide W as dis
s olv ed in 0. 04 m ol of 4 9% s tr eng th potas s ium h y dr og ens ul
? de W h ile h eating .
[ 01 4 0] Th e am ount of potas s ium h y dr ox ide cor r es ponded
to 60% of th e th eor etical am ount of potas s ium h y dr ox ide for
com plete neutr aliz ation of th e h y dr og en s ul? de. 0. 054 4 m ol
( 1 . 7 4 g r am ) of s ulfur W as W eig h ed into th is s olution and th e
r eaction m ix tur e W as , after th e ex oth er m ic r eaction h ad
occur r ed W ith W ater and h y dr og en s ul? de being dis tilled off,
h eated to about 600 C .
[ 01 4 1 ] On cooling , th e r ed liq uid beg an to cr y s talliZ e at
1 90 C .
[ 01 4 2] Th e folloW ing r elations h ips W er e der iv ed fr om a
num ber of ex per im ents :
[ 01 4 3] Incr eas ing potas s ium contents pr om ote cr y s talliZ a
tion. Th e m elt v is cos ity is incr eas ed by incr eas ing s ulfur
contents to a g r eater deg r ee th an in th e cas e of a h ig h er s odium
content.
[ 01 4 4 ] Th e th er m al s tability is pr om oted by v er y s m all
s ulfur contents .
[ 01 4 5] Accor ding to th e liter atur e, th e cor r os iv ity of th e
alk ali m etal poly s ul? des is r educed by loW s ulfur contents , as
indicated abov e.
[ 01 4 6] Th e optim al com pos ition is th us a com pos ition h av
ing th e h ig h es t pos s ible s odium content at th e loW es t pos s ible
s ulfur content. HoW ev er , a pr opor tion of potas s ium is
r eq uir ed in or der to s uppr es s cr y s talliZ ation, and th is is all th e
m or e im por tant th e loW er th e s ulfur content.
[ 01 4 7 ] Optim al com pos itions ar e in th e r ang e
( N a O. 5* O. 65KO. 5* O. 35) 28 24 7 2. 8
[ 01 4 8 ] One of th es e alk ali m etal poly s ul? des h av ing th e
com pos ition
( N a O. 6KO. 4 ) 2S2. 6
does not decom pos e at tem per atur es up to 7 00 C . and on
cooling continuous ly h as a loW v is cos ity and does not dr aW
th r eads doW n to about ll0-ll5 C . , its m elting r ang e.
J ul. 7 , 201 1
[ 01 4 9] Accor ding to th e calculated N a2SiK2SiS ph as e
diag r am in th e cited liter atur e ( Lindber g et. al) , th is com po
s ition s h ould h av e a m elting r ang e of about 360-3 8 0 C .
1 . A com pos ition for th e tr ans por t and s tor ag e of h eat
ener g y , W h ich com pr is es alk ali m etal poly s ul? des of th e for
m ula ( Mel( 1 _ x ) Me2x ) 2SZ , W h er e Mel and Me2 ar e s elected
fr om th e g r oup of alk ali m etals cons is ting of lith ium , s odium ,
potas s ium , r ubidium and ces ium , Mel is differ ent fr om Me2
and x is fr om 0 to l and Z is fr om 2. 3 to 3. 5.
2. Th e com pos ition accor ding to claim 1 , W h er ein Mel is
potas s ium and Me2 is s odium .
3. Th e com pos ition accor ding to claim 1 , W h er ein x is fr om
0. 5 to 0. 7 and Z is fr om 2. 4 to 2. 9.
4 . Th e com pos ition accor ding to claim 1 h av ing th e for
m ula ( N 31 0. 5-0. 65K0. 5-0. 35) 2S2. 4 -2. s or ( N aO. 6KO. 4 ) 2S2. 6'
5. Th e com pos ition accor ding to claim 1 , W h er ein th e alk ali
m etal poly s ul? des can h e obtained by r eacting concentr ated
aq ueous s olutions of alk ali m etal h y dr og ens ul? des W ith s ul
fur .
6. Th e com pos ition accor ding to claim 1 , W h er ein th e alk ali
m etal poly s ul? des can be obtained by r eacting alk ali m etal
h y dr og ens ullides W ith a m olar ex ces s of alk ali m etal h y dr ox
ides to for m alk ali m etal s ul? des m ix ed W ith alk ali m etal
h y dr og ens ul? des and r eacting th es e W ith s ulfur to conv er t
th em com pletely into alk ali m etal poly s ul? des and, option
ally under r educed pr es s ur e, dis tilling off th e W ater at tem
per atur es up to 500 C .
7 . Th e com pos ition accor ding to claim 1 , W h er ein th e alk ali
m etal poly s ul tides ar e pr epar ed by deW ater ing aq ueous s olu
tions of alk ali m etal h y dr og ens ul? des or aq ueous s olutions of
alk ali m etal h y dr o g ens ul? des W h ich h av e been r eacted W ith a
m olar ex ces s of alk ali m etal h y dr ox ides to for m alk ali m etal
s ul? des m ix ed W ith alk ali m etal h y dr og ens ul? des , optionally
under r educed pr es s ur e, and, in a s econd s tep, r eacting th e
deW ater ed alk ali m etal h y dr og ens ul? des /alk ali m etal s ul? des
W ith liq uid s ulfur to for m th e alk ali m etal poly s ul? des .
8 . Th e com pos ition accor ding to claim 6, W h er ein a m ax i
m um of 0. 9 m ol of alk ali m etal h y dr ox ide is us ed per m ole of
alk ali m etal h y dr og ens ul? de.
9. Th e us e of th e com pos ition as de? ned in claim 1 in th e
pr es ence of alum inum -com pr is ing m ater ials .
1 0. Th e us e of th e com pos ition as de? ned in claim 1 in th e
pr es ence of ir on-bas ed m ater ials .
1 1 . Th e us e accor ding to claim 1 0, W h er ein th e ir on-bas ed
m ater ials com pr is e fr om 6 to 28 per cent by W eig h t of alum i
num and les s th an 3 per cent by W eig h t of m oly bdenum and up
to 2 per cent by W eig h t of each of Z ir conium and/or y ttr ium .
1 2. Th e us e of th e com pos ition as de? ned in claim 1 as
m edium for th e tr ans por t and/ or s tor ag e of h eat ener g y .
1 3. Th e us e of th e com pos ition as de? ned in claim 1 for th e
tr ans por t and/ or s tor ag e of h eat ener g y in s olar th er m al poW er
s tations or in th e pr im ar y cir cuit of nuclear poW er s tations .
1 4 . Th e us e of th e com pos ition as de? ned in claim 1 as h eat
tr ans fer ? uid, W h er ein th e h eat ener g y th er eof is tr ans fer r ed to
anoth er m edium as h eat s tor ag e.
1 5. Th e us e accor ding to claim 1 4 , W h er ein th e oth er
m edium is s ulfane-com pr is ing loW -v is cos ity s ulfur .
1 6. A plant for g ener ating ener g y , W h ich com pr is es a com
pos ition as de? ned in claim 1 .
1 7 . Th e plant accor ding to claim 1 6, W h ich com pr is eS a
com pos ition as de? ned in any of claim s 1 to 8 as h eat tr ans fer
m edium and/or h eat s tor ag e m edium .
1 8 . Th e com pos ition accor ding to claim 1 W h er ein x is
fr om 0. 5 to 0. 7 and Z is fr om 2. 4 to 2. 9.
US 201 1 /01 63259 A1 J ul. 7 , 201 1
1 9. Th e com pos ition accor ding to claim 2 h av ing th e for
m ula ( N aQ S-O. 65KO: 5: O. 35) 2S2. 4 -? . 8 or ( N ao. 6K0. 4 ) 2S_ 2. 6
20. Th e com pos ition accor ding to claim 3 h av ing th e for
m ula ( N aos -o. 65K0. 5-4 . 35) 2S2. 4 -2. s or ( N aO. 6KO. 4 ) 2S2. 6'
* * * * *