Supe c i ical wa e p ocesses: u u e p ospec s
Ma ía José Coce o.
High P essu e P ocesses esea ch g oup. Depa men o Chemical Enginee ing and
En i onmen al Technology. Valladolid Uni e si y. 47011 Valladolid (Spain).
mjcoce [email protected] a.es
Abs ac s
This con ibu ion examines he challenges aced by supe c i ical wa e p ocesses o
indus ial de elopmen . As an al e na i e, he in ensi ica ion o he supe c i ical wa e
p ocesses is p esen ed in o de o educe he size o he equipmen needed and o
acili a e he scaling up o he p ocess. The pe spec i e o de eloping mic o
combus o s using hyd o he mal lames as he in e nal hea sou ce could open up an
al e na i e o he in-si u ene gy gene a ion in bio e ine ies, o example. The
undamen al s udies abou supe c i ical wa e hyd olysis using ul a as eac o s has
enabled ex emely high selec i i y in he biomass ac iona ion p ocesses, and in he
p oduc ion o C2 and C3 building blocks om key componen s. The high-ene gy
consump ion o his p ocess is ano he issue ha limi i s comme cializa ion. In he
examples p oposed, he ene gy, wo k eco e y and ene gy in eg a ion allows he
educ ion o he o al ene gy consump ion and, in some p ocesses, he a ailabili y o
ex a ene gy as hea and wo k.
Key Wo ds: P ocess in ensi ica ion, mic o combus o s, oxida ion, hyd olysis, sha
wo k, ene gy in eg a ion.
1 Cu en S a e
Supe c i ical wa e (SCW) has been used as coolan in nuclea eac o s o many
yea s. In addi ion, geo he mal s udies abou he wa e inside he ea h’s c us ha e
con ibu ed knowledge o he hyd o he mal p ocesses [1]. Modell had he ision o
de elop indus ial p ocesses based on he use o wa e a supe c i ical condi ions a e
he p elimina y s udies abou he o al miscibili y o hyd oca bons in SCW [2]. His
companies Moda inc and Modell we e a key poin in he de elopmen o he
supe c i ical wa e oxida ion p ocesses o en i onmen al applica ions [3].
In i s o igin, he p ocess a oused a g ea in e es among he p ocess indus ies o in
public o ganisms as being a solu ion o ecalci an was e ea men p oblems.
Companies such as Gene al A omics o Fos e and Wheele we e in ol ed in he
de elopmen o he supe c i ical wa e anspi ing wall eac o . They made ele an
con ibu ions, wo king in p ojec s o public USA o ganisms, o he de elopmen o
injec o s o achie e good mixing [4].
In Eu ope, F anck signi ican ly imp o ed he a ailable in o ma ion ega ding SCW
p ope ies [5-7]. Companies such as Chema u buil he i s sludge SCWO pilo plan
wi h a ea men capaci y o 200 kg/h, in 1998 [8]. In Spain, he EMGRISA public
company suppo ed Valladolid Uni e si y’s esea ch o de elop he i s cooled wall
eac o in a pilo plan wi h a ea men capaci y o 30 kg/h in 1994, and a
demons a ion plan wi h a ea men capaci y o 200 kg/h in 2002 [9].
The main indus ial de elopmen associa ed wi h sludge ea men has in ol ed ubula
eac o s [10-12]. Con en ional eac o s a e hin ubes abou hund ed me e s long, wi h
mixing p oblems ha o ce hem o wo k wi h g ea excesses o oxygen and wi h
e iden plugging p oblems due o solid p ecipi a ion. In p ac ice, indus ial plan s wo k
wi h wo eac o s, one unde ope a ion and he o he unde aking he cleaning o
deposi ed solids [13-15]. In some applica ions, he changeo e o he eac o s akes
o e 30 minu es. Fu he mo e, cleaning is a highly ene gy- and ime-consuming s ep.
I s indus ial de elopmen has no p og essed due o he lack o con ol o co osion
and sal p ecipi a ion p ocesses, he high eac o su ace exposed o co osion and he
small diame e ha a o s plugging p oblems, in addi ion o he high p ocessing cos
[16-18].
A well-known p oblem o SCW oxida ion is he ene gy equi emen , which can be e y
high, pa icula ly, i simple plug- low ubula eac o s a e used, inasmuch as hese
designs equi e he p ehea ing o he in luen up o supe c i ical wa e empe a u e. The
co ec use o he ene gy p oduced by he oxida ion is a c ucial s ep in o de o make
SCWO p ocesses economically iable [19-21].
SCW gasi ica ion is ano he echnology o which impo an esea ch e o s ha e been
de o ed, bu i has no been possible o p og ess. Only one demons a ion indus ial
scale plan Hyd ome hans AG is in Swi ze land [22]. K use concluded in a ecen
e iew ha he main eason why a SCW gasi ica ion p ocess is no a ac i e o
indus y oday is due o he high p ocessing cos s [23]. Only biomass wi h high disposal
cos s a e conside ed o be in e es ing eeds ock, such as sewage sludge. K use
iden i ied he same p oblems ound in he SCWO: plugging, co osion, eac o design
and ma e ial selec ion. As possible u u e de elopmen s, K use p oposed hyd o he mal
gasi ica ion as pa o a bio- e ine y. Du ing hyd o he mal lique ac ion, a a y oil and an
aqueous phase a e p oduced. So, I was hen p oposed o gasi y he o ganic
compounds in he aqueous e luen , and use he hyd ogen o up-g ade he oil [23-25].
Mo e ecen ly, ma e ial syn hesis in SCW is a echnology which is app oaching he
ma ke . Adschi i has p oduced di e en ma e ials o new indus ial de elopmen s [26].
Lee had a demons a ion plan unde ope a ion which syn hesized nanopa icles by
using SCW [27]. In ecen yea s, Les e has coo dina ed he Shyman EU p ojec o he
de elopmen o a 1000 on/yea demons a ion plan p oducing nanoma e ials [28-29].
Again, his echnology has no eached he indus ial de elopmen ha i could achie e,
due o he high p ocessing cos . In addi ion o he ene gy consump ion, he e luen
pa icle concen a ion is e y low, and he wa e has o be elimina ed, so he
downs eam p ocessing could equi e a lo o bo h, ime and ene gy. In he cases o
many ma e ials ha ha e been de eloped, he cos is much highe han he same
ma e ials ha a e p oduced by con en ional echnologies. The oppo uni y, now, lies in
de eloping new ma e ials ha can no be p oduced by con en ional echnologies, o
ha would be mo e expensi e o p oduce con en ionally.
In his special issue, Adschi i [30] and Aymonie [31] illus a e he in e es o his
echnology o he p oduc ion o ad anced nanos uc u ed ma e ials and o de eloping
new nano echnology applica ions.
The pe ochemical companies a e s udying he upg ading o hea y oil by SCW. This
p ocess akes ad an age o he low dielec ic cons an o wa e , which allows
hyd oca bons’ solubili y. In addi ion, empe a u e and p essu e can be manipula ed o
adjus he wa e ’s ionic p oduc c ea ing a highly ionic medium, wi h high [H+]
concen a ion ha could imp o e he hyd olysis [32]. Al hough many s udies ha e no
been published, ele an manusc ip s abou he modynamics, kine ics, and
expe imen al and heo e ical de elopmen s on he phase equilib ia o ele an wa e –
hyd oca bon sys ems a e a ailable [33-35]. The ad an age o his p ocess o e o he
upg ading echnologies is he high p ocess in ensi ica ion ha can be achie ed by he
use o SCW.
Rega ding ene gy p oduc ion, powe plan s wi h SCW s eam gene a o s as he Benson
ype a e con en ional. [36-37]. Also no el SCW eac o s a e conside ed mo e e icien
eac o s o nuclea plan s [38].
2 SCW p ocesses Challenges
The s ong ea u es o he supe c i ical wa e p ocesses lie in he knowledge o he
p ocesses undamen als suppo ed by he abundan esea ch SCW. Speci ically: he
SCW p ope ies and i s mix u es; he modynamic and kine ic s udies; he modynamic
modelling; and he compu a ional luid dynamic model designed o imp o e he
hyd odynamic eac o s beha io . Ope a ion a high empe a u e could mean as
eac ion kine ics, which could allow ex emely as p ocesses o be de eloped.
The weak ea u es include he high p ocessing cos , in addi ion o he ope a ional
p oblems associa ed wi h plugging, co osion, eac o design, dilu ion o he e luen s,
and high ene gy consump ion. The p ocesses ha e high cos s, and his in u n has an
impo an impac on he high cos o p oduc s.
F om my poin o iew, he main challenges conce ning SCW indus ial implemen a ion
a e:
 To educe he cos o he p ocesses, by educing he cos o equipmen .
 To educe he ope a ion cos by imp o ing he hea and wo k eco e y and he
in eg a ion o he ene gy, o educe he o e all ene gy consump ion.
 To imp o e echnical issues ega ding ope a ions wi h solids a a high
empe a u e and p essu e, pumping highly concen a ed solid suspensions,
minimizing he ab asion o al e s ems, and imp o ing he solid ou pu om
SCW eac o s.
 To implemen downs eam p ocesses in o de o achie e ma ke able p oduc s.
3 SCW p ocess pe spec i es.
One way o educe equipmen cos s is o ake ad an age o he SCW p ocess’s as
kine ics o educe eac ion ime, which will educe he eac o size. By educing he
esidence ime om 10 minu es o milliseconds, i is possible o change con en ional
eac o olumes o m3 o eac o s wi h olumes o dm3. Tha means educing he
eac o size, hus acili a ing he scale-up o he p ocess as well as he eac o con ol.
In some applica ions, i is possible o imp o e he eac o ’s design o educe he
p oblems associa ed wi h ope a ions in ol ing solids a a high p essu e and
empe a u e.
I is possible o educe he ope a ion cos by imp o ing he ene gy and wo k eco e y,
o example, by eco e ing he wo k associa ed wi h he dep essu iza ion, and
implemen ing ene gy in eg a ion [39].

The p ocesses should be ocused on ob aining p oduc s ha a e close o he ma ke .
As he e is much in o ma ion abou p ocess undamen als, he esea ch should be
o ien ed o de elop “p oduc s close o he ma ke ”. I i is he case ha he p ocess
undamen als a e no ye well known, ou i s s ep is o imp o e ou knowledge o he
p ocess undamen als in o de o achie e a as e way o de eloping new p ocesses
and new p oduc s.
In his sec ion, he pe spec i es o he de elopmen o h ee supe c i ical wa e
p ocesses a e p esen ed. These p ocesses can ope a e wi h esidence imes o
milliseconds, which could achie e a high le el o p ocess in ensi ica ion. The ene gy
and wo k eco e y, as well as he ene gy in eg a ion, a e aken in o accoun in o de o
minimize ene gy consump ion o e en p oduce ne ene gy as hea and sha wo k.
3.1 Mic o-combus o s ope a ing on he in ensi ica ion o he supe c i ical wa e
oxida ion p ocess, using hyd o he mal lames as he in e nal hea sou ce.
In 1988, Schilling and F anck achie ed he o ma ion o a di usion lame in
homogenous supe c i ical aqueous luids. The combus ion o 30% me hane wi h
oxygen in he homogenous supe c i ical phase was in es iga ed, and s a iona y
di usion lames we e gene a ed up o p essu es o 2000 ba and empe a u es o 500
ºC [40]. A ha ime his was a conside ed a scien i ic cu iosi y, bu nowadays he e ec
o ope a ion condi ions on he igni ion empe a u e has been s udied in o de o
achie e s able mixing and di usional hyd o he mal lames [41-44].
Usually a lame is de ined as he isible pa o he combus ion eac ion and consis s o
a su ace whe e eac ion occu s. This su ace sepa a es he oxidan om he uel (in
he case o di usion, non-p emixed, lames) o i sepa a es he eagen s om he
eac ion p oduc s (in case o p emixed lames). The su ace mo es owa ds he
eagen s wi h a lame on eloci y. I his eloci y is he same as he luid eloci y, he
lame will emain s a iona y. I low eloci y is highe o lowe han lame on eloci y,
he lame will be blown away om he ube o i will mo e agains he low, esul ing in
back i e, espec i ely [45]. See igu e 1 o simula ion con ou s o a hyd o he mal
lame.
I is possible o ope a e wi h igni ion empe a u es o be ween 400 and 500ºC, and
esidence imes be ween 10-100 ms. The lame igni ion is a ec ed by uel, oxidan ,
a io o uel/oxidan and he geome y o he injec ion sys em [46-50], and i is possible
o de elop p ocesses ha suppo hyd o he mal lames as he hea sou ce [36,41].
Al hough he eac o e luen ene gy can be eco e ed by a Rankine Cycle, he p ocess
is s ill highly ene gy demanding. Addi ionally, oxygen is he mos commonly used
oxidan in o de o educe he ai comp esso ene gy consump ion. The implemen a ion
o hyd o he mal lames as he in e nal hea sou ce in he supe c i ical wa e oxida ion
p ocesses opens up he oppo uni y o he SCWO o achie e an ene ge ically sel -
su icien p ocess, and o p oduce ene gy [51].
Figu e 1. Flame simula ion con ou s o new cooled wall eac o wi h wo ou le s: (a)
IPA mass ac ion, (b) eac ion a e [52].
The SCWO p ocesses wi h hyd o he mal lames ha e a numbe o ad an ages o e
he lameless p ocesses. Some o hese ad an ages could o e come he adi ional
challenges ha make a success ul and p o i able comme cializa ion o SCWO
echnology di icul . The ad an ages include he ollowing [52]:
• The educed esidence imes (in he o de o milliseconds) encou age he
cons uc ion o smalle eac o s (mic o-combus o s).
• I is possible o ca y ou he eac ion wi h eed injec ion empe a u es nea o oom
empe a u e when using essel eac o s [48,53]. This a oids p oblems such as
plugging and co osion in he p ehea ing s ep, which is an ad an age om he
pe spec i e o ope a ion and ene gy in eg a ion.
• Highe ope a ion empe a u es imp o e ene gy eco e y.
The ex emely low esidence ime allows mic o eac o s o be de eloped as an
al e na i e o he long ubula eac o s. The s ong educ ion o he igni ion empe a u e
wi h p essu e will allow he ope a ion a empe a u es o 600-650ºC. A hose
condi ions he SCW oxida ion achie es a highe e iciency han a lowe empe a u es.
The ope a ion empe a u e can be e en highe i he wo k eco e y equi ed a apo a
a highe empe a u e.
As he eac o size dec eases signi ican ly, he ope a ion wi h ai as he oxidan could
be a mo e economical al e na i e. On an indus ial scale, i could also be possible o
implemen oxida ion wi h ai , as opposed o he con en ional SCW acili ies ha
ope a e wi h c yogenic oxygen [51].
When di ec expansion o he e luen is used, he ene ge ic e iciency is much highe
han when he e luen is used o hea an auxilia y luid o a Rankine o B ay on cycle.
We ha e calcula ed ha i is possible o ope a e wi h ai as he oxidan , o o use
en iched ai h ough he di ec expansion o he e luen in a u bine, and hus p oduce
ne ene gy [51-53].
Figu e 2. UVa wo-ou le eac o o ene gy p oduc ion. De ails o cons uc ion can be
ound in li e a u e [53].
Figu e 3. SCWO scheme, designed o ope a e wi h a di ec e luen eac o expansion
in a u bine.
E en when he op ion o di ec expansion o he e luen is, by a , he mos
ene ge ically e icien , i will be no applicable in he sho e m. This is mainly due o
he ac ha he composi ion o he e luen (50-80 % mol o wa e , ca bon dioxide and
ni ogen i ai is used as oxidan ) makes i unsui able o expansion in a con en ional
u bine. This composi ion places he e luen somewhe e be ween he pu e wa e used
in he s eam u bine, and he lue gases, which a e p oduc s o combus ion used in gas
o de elop he downs eam p ocesses o concen a ing/sepa a ing he e luen , hus
p oducing he inal p oduc s.
The SCW hyd olysis o biopolyme s, such as cellulose, opens a new ou e o
de eloping new p oduc s ha canno be ob ained by he con en ional acid o alkaline
hyd olysis. Biomass wi h a high cellulose concen a ion could be a aw ma e ial o
p oducing cellulose wi h di e en molecula weigh and p ope ies, wi h new ma ke
oppo uni ies.
Al hough esea ch is needed o imp o e he undamen al knowledge o biomass SCW
hyd olysis, he i s SCW hyd olysis p ocess, called he Plan ose p ocess, de eloped
by Renma ix, is unning in a demons a ion scale in Geo gia, USA [69].
3.3 Supe c i ical wa e as a eac ion media o p oduce building blocks
The SCW can be used as a eac ion medium o p oduce chemical compounds wi h
high selec i i y. The selec i i y is imp o ed by con olling he ion concen a ion in o de
o a oid ionic eac ions. This has been p esen ed in he case o cellulose hyd olysis.
The glucose and uc ose kine ic and eac ion mechanism s udies ha e allowed us o
de e mine eac ion pa hs o ob aining he selec ion o glycolaldehyde (building block
compound made up o wo ca bons) o py u aldehyde (building block compound made
o h ee ca bons). The eac ions we e assumed o ollow he eac ion pa hway shown
in igu e 6.

Figu e 6. Reac ion pa hway o glucose and uc ose hyd olysis in supe c i ical wa e .
This eac ion pa hway was buil ollowing he schemes de eloped in e e ence [70].
The eac ion o glucose isome iza ion occu s h ough ing opening and ke o–enol
au ome ism. These eac ions o m ansi ion s a es wi h OH- o H+ ions. Also, uc ose
dehyd a ion o ms ansi ion s a es inco po a ing H+ ions (one pe H2O molecule los )
[71]. The p oduc ion o glycolaldehyde was enhanced a supe c i ical condi ions
because he OH-/H+ concen a ion is highly dec eased and so is he concen a ion o
uc ose and i s de i ed p oduc s. F uc ose can ollow wo main eac ion pa hways:
uc ose dehyd a ion o e oaldol condensa ion and a second eac ion o o m
glyce aldehyde as he main p oduc om uc ose [65, 66].
Resul s show ha uc ose can be selec i ely ans o med in o py u aldehyde, a 400ºC
and 23 MPa wi h a yield o 89% w·w-1 wi hou using any ca alys , and wi h a esidence
ime o 0.7 s [72].
The hyd olysis o glucose o glycolaldehyde was achie ed a 400ºC and 23 MPa wi h a
esidence ime o 3 s; glycolaldehyde selec i i y a hose condi ions was 75% w·w-1
[73]. The eac ions o uc ose we e analyzed in combina ion wi h glucose. I was
de e mined ha di e en e o-aldol condensa ion p oduc s can be ob ained depending
on he s a ing ma e ial. F uc ose p oduces mainly C-3 molecules (py u aldehyde) and
glucose p oduces mainly C-2 molecules (glycolaldehyde). The isome iza ion o
uc ose o glucose is negligible, and so is he p oduc ion o C-2 when he s a ing
ma e ial is uc ose. The non-ionic medium induced a supe c i ical wa e condi ions
signi ican ly imp o es he selec i i y, a o ing he e o-aldol condensa ion o glucose
ins ead o isome iza ion o dehyd a ion.
O ganic chemis y has de eloped sys ema ic mechanisms o p oduce many chemical
p oduc s om oil. These eac ions a e ounded on simple molecules, such as e hene,
p opene o benzene, wi h he addi ion o unc ional g oups. In he oil indus y, chemical
p ocesses equi e mul iple s eps, he use o sol en s, ca alys s and excessi e ene gy,
which ha e en i onmen al incompa ibili ies. In he bio-based chemical indus y, key
compounds a e mo e complica ed molecules wi h highly unc ional g oups, such as
glucose o example. Now, a new sys ema iza ion o o ganic chemis y o he emo al
o ea angemen o he unc ional g oups has o be de eloped. The chemical
p ocesses mus include simpli ied s eps and imp o ed p ocess in ensi ica ion in o de
o achie e a sus ainable p ocess om biomass.
4 Concluding ema ks, and iden i ica ion o he esea ch needed o he
de elopmen o he in ensi ica ion o he sus ainable supe c i ical wa e
p ocesses.
The SCW p ocesses ha e been de o ed o impo an , ma ke able esea ch e o s, bu
i has no been possible o achie e he indus ial de elopmen ha was expec ed.
Among he easons o his p oblem a e he high p ocessing cos , and he di icul y o
ope a ing wi h solids a a high p essu e and empe a u e. Taking in o accoun he SCW
p ope ies as he eac ion media, he SCW p ocess in ensi ica ion is p esen ed as an
al e na i e o de eloping an ul a as p ocess ha allows a educ ion in he eac o
cos . Wo k eco e y, hea in eg a ion and hea and sha wo k p oduc ion a e
conside ed o minimize ene gy consump ion o e en p oduce ne ene gy.
The in ensi ica ion o he SCW oxida ion p ocess by using hyd o he mal lame as an
in e nal hea sou ce is p esen ed as an al e na i e o de eloping mic o combus o s.
The expansion o he e luen in a u bine could be he way o p oduce in-si u ene gy
o bio e ine y de elopmen . Ou p elimina y esul s conce ning he SCW oxida ion
eac o wi h he hyd o he mal lame as he in e nal hea sou ce indica ed ha i would
be possible o p oduce ene gy by expanding he SCW oxida ion eac o e luen in a
u bine. To de elop his p ocess, some esea ch needs could be summa ized as
ollows:
 New s udies o de elop s able hyd o he mal lames om di e en compounds,
mainly biomass om di e en o igins, and o es ablish he me hodology o
calcula ing hem.
 To imp o e he eac o ’s design and educe he plugging p oblems, aking in o
accoun i s ope a ion wi h solids a a high p essu e and empe a u e, and o
de elop new cons uc ion ma e ials o con ol he co osion and educe he
equipmen cos s.
 The wo k and ene gy eco e y ha e a key ele ance, due o he high
empe a u es and p essu e e luen s and he p ocess high ene ge ic
consump ions. The e o e i is necessa y o de elop new u bines ha can
ope a e wi h he SCW oxida ion e luen s o eco e he wo k.
 To s udy echnical issues conce ning he expansion o wo phase s eams in
o de o implemen he di ec expansion e luen s.
The SCW ul a as hyd olysis is p esen ed as an al e na i e o de eloping sus ainable
bio e ine ies. The SCW media p ope ies allow i o ope a e mainly by ionic eac ion
mechanisms a subc i ical wa e , and by adical eac ions mechanism a SCW. The
ope a ion wi h ul a as mic o eac o s has ema kably inc eased he selec i i y. The
undamen al knowledge abou he eac ion mechanism and he e ec o SCW
p ope ies a e a key poin in achie ing his selec i i y.
 This implies ha u u e esea ch abou he eac ion mechanism mus be ca ied
ou in con inuous eac o s in o de o ob ain accu a e da a. The hea ing and
cooling s eps should be aken in o accoun o a oid deg ada ion, and o con ol
he esidence ime. The ope a ion wi h solids a a high p essu e and
empe a u e has o be conside ed in all he p ocess s eps.
 In he same way, high p essu e iew-cells used in solubili y and phase beha io
s udies on biomass hyd o he mal eac ion equi e ha he p ehea ing ime be
a oided, since he dissolu ion/hyd olysis s ep could be ex emely as and hus
ake place du ing he p ehea ing. The e o e, con inuous low cells, o hose
p o ided wi h a sys em o solid injec ion, will be he mos widely used.
 The applica ion o he SCW in ensi ied p ocess equi ed comme cial equipmen
o ope a e con inuously wi h low esidence imes. In ac , he comme cial
equipmen i sel , e en a lab scale comme cial suspension pump equipped wi h
al es ha a oid plugging due o suspension pa icles, is needed. Technicians
wi h he expe ience o implemen his comme cial equipmen in he esea ch lab
a e also needed.
 In addi ion, e en when he componen s o biomass a e alike, each biomass
p esen s i s own peculia i ies. Thus, one mus s udy new local biomass sou ces
o achie e speci ic chemicals and ene gy.
Knowledge mechanisms based on SCW hyd olysis, such as he SCW ul a as
hyd olysis, a e p oposed in o de o ob ain selec i e building blocks. Two examples o
p oducing highly selec i e C2 and C3 building blocks om uc ose and glucose a e
p esen ed as an al e na i e o he p oduc ion o selec i e chemicals by he in ensi ied
SCW hyd olysis p ocess.
 Resea ch equi es o ganic chemis y o allow he elimina ion and
ea angemen o unc ional g oups om he building blocks p oduced, whe eas
chemical enginee ing enables he de elopmen o simpli ied and compac
p ocesses, aking in o accoun ene gy eco e y and p ocess in eg a ion,
con ibu ing as a whole o he de elopmen o he Bioeconomy.
Acknowledgemen s
The au ho hanks he Minis e io de Economía y Compe i i idad, Jun a Cas illa y León
and FEDER p og am o hei inancial suppo o ou Bioeconomy P ojec s CTQ2013-
44143-R, CTQ2016-79777-R, and VA040U16.
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