M O L T O X ~ CHEMICAL AIR SEPARATION SYSTEM - APROGRESS REPORT

Donald C. Er1ckson
Energy Concepts Co.
Annapo11s, Maryland
W111iam R. Brown and Br1an R. Dunbobb1n
A1r Products and Chem1ca1s, Inc.
Allentown, Pennsy1van1a
Robert G. Massey
U.S. Department of Energy
Wash1ngton, D.C.
ABSTRACT
Anew low energy route to tonnage oxygen
product1on, the O L T O X ~ system, 1s now
commenc1ng p110t plant test1ng. The process,
1ts h1story, and potent1a1 app11cat10ns will be
descr1bed, 1n add1t1on to recent results of the
p110t plant test program. Future development
needs and plans for commerc1a11zat10n w111 be
outlined.
INTRODUCTION
More than 300,000 TID of large tonnage
cryogen1c oxygen plant capac1ty was bu11t 1n the
1960's and 1970's. The two-th1rds st111
operating w111 consume about $20 b11110n (1985
$) of electr1cal energy 1n the next decade. The
HOLTOX
m
chem1ca1 a1r separat10n system 1s
being developed as a cryogen1c oxygen plant
replacement wh1ch w111 use energy at less than
one-half of th1s rate.
A1r separation by cryogen1c d1st111at10n was
1ntroduced 90 years ago by Carl von L1nde of
Germany and cont1nues to be the choice for
tonnage oxygen production. Current des1gns
requ1re 25% less energy than plants built in the
1960's and 1970's. The HOLTOX chemical air
separat10n system is being developed to offer a
lower cost oxygen a1ternat1ve for new oxygen
requ1rements by revolutionary rather than
evo1ut1onary development. The process requires
up to 40% less energy use than today's
commerc1al oxygen technology. This translates
into a five to th1rty percent reduct10n in
oxygen cost. This 1ncludes both cap1tal and
energy costs.
In 1979, Donald C. Er1ckson of Energy Concepts
Company received the first of several U.s.
patents for a chemical a1r separation process
for tonnage oxygen product10n.(1) Th1s new
method of produc1ng oxygen uses a molten m1xture
* HOlTOX 1s a trademark of A1r Products and
Chemicals Inc.
of a1ka11 n1trates and nitr1tes to chem1ca11y
react w1th oxygen 1n compressed a1r. Heat1ng or
depressur1zation then releases oxygen of greater
than 99.8% pur1ty 1n a revers1ble react10n. The
major port10n of the energy used to compress or
heat the a1r 1s recovered from the waste
nitrogen exhaust.
With support from the U.S. Department of
Energy, Mr. Er1ckson proved his concept 1n a
bench-scale unit that produced 6 liters per
m1nute of oxygen.(2) In 1982 Air Products
and Chem1cals, Inc., in a cost-shar1ng,
cooperative agreement w1th the U.S. Department
of Energy, undertook the cont1nu1ng development
of the process, now known as the MOlTOX oxygen
system. Dur1ng Task 1, laboratory support
stud1es provided technical 1nformat10n on molten
nitrate/n1tr1te chem1stry and on the corros10n
res1stance of mater1a1s of construct10n.(3)
In January 1985, the dec1s10n was made to
proceed w1th Task 2, the construct10n and
operat10n of a 0.25 ton per day oxygen p110t
plant. This $6 m11110n, four-year project 1s
enter1ng 1ts f1na1 year w1th commencement of
p110t plant test1ng. The twelve month p110t
plant exper1menta1 plan first calls for 'Proof
of Concept' operat1onal confirmation and then
for acquisition of engineer1ng design data for
scale-up and optimization for the next
development phase.
PROCESS DESCRIPTION
The MOLTOX system is based on the reversible
react10n of oxygen with sod1um and potassium
nitrite to form nitrate. This reaction can be
used in one or both of two HOLTOX system salt
loop types, Pressure Swing Absorption (PSA) and
Thermal Swing Absorpt1on (TSA). The basic
operating modes are:
ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986
--
1.PSA - (PRESSURE SWING ABSORPTION)
1. Pure Pressure Swing - For 1ntegrat10n w1th
the pressur1zed gases
of gas turb1ne power
plants.
2. Pure Thermal Swing - For 1ntegrat10n with
the heat recovery and
steam generation
section of industrial
and utility steam
boilers.
2.TSA- (TEMPERATURESWING ABSORPTI0r-N,"-)--+-_"",
3. Combined Pressure For any application
and Thermal Swing in wh1ch heat and
pressure energy are
avallable.
Simplified process diagrams of the two salt
loop types are shown 1n F1gure 1. These
d1agrams show the absorber and desorber salt
flows, the gaseous a1r and product flows, and
the integrat10n of the salt loop w1th external
processes. For e1ther type of MOlTOX system
I
salt loop, dry, C02 free a1r enters the
I
absorber at a temperature of 783 to 922K (950 to
I(950F)
1200F) and a pressure of 0.41 to 1.2 MPa (60 to I
186 ps1a) and 1s contacted with the molten
= INTEGRATION I
O
MEANS WITH ...--c;;z-joABSORBER
salt. The oxygen reacts chem1cally w1th the
EXTERNAL
salt (N02 + 1/202 N03) and 1s removed w1th
PROCESS
the salt from the bottom of the absorber. The Figure 1
n1trogen and 1nert gases, along with some Integrated System Salt loop
unreacted oxygen, are removed from the top of
the absorber at essentially the same pressure
EXISTING
and temperature as they entered. The molten 500 CRYOGENIC
salt from the absorber flows to the desorber
0,PLANT(S)
where the chem1cal reaction 1s reversed
(N03 N02 + 1/202), and gaseous oxygen is
released from the salt and removed as product.
400
The reversal of the chemical reaction in the
<" NEW
desorber requires either pressure reduct10n iii
Q. J--CRYOGENIC
(PSA) or temperature 1ncrease (TSA).
0,PLANT Il)
CD
For the TSA salt loop, the temperature of
@
300
the molten salt from the absorber 1s 1ncreased 0
z -
across the salt heater. The salt 1s heated to
t:::.
--
""-
-
-
-
--
""-
:r
922K (1200F) and then enters the desorber where

--
""-
- ""-
the gaseous oxygen 1s released and removed from
l!.
-
-
200
M
the salt. The 922K (1200F) salt 1s withdrawn
c
w
-
--
""-
LANT 0,
from the bottom of the desorber and 1s cooled to
a:
783K (950F) 1n the salt cooler before enter1ng 0
5
w
the absorber for recontact with the hot a1r. a:
>
The salt 1s c1rculated around th1s TSA loop by a
Cl 100
a:
pump operat1ng at the 783K (950F) salt LU
temperature.
z
LU
For the PSA salt loop, the pressure of the
o
molten salt from the absorber is reduced across
the pressure letdown valve before the salt
HEATEXPORT(MM BTU/TN 0,)
enters the desorber. The pressure of the
desorber is controlled by the gaseous oxygen
"'---MOLTOXPROCESS TYPE---
pressure through a vacuum oxygen compressor.
PRESSURE THERM L
The salt 1s removed from the desorber by a salt. SWING SWING
pump and rec1rculated back to the absorber at F1gure 2 - Energy Advantage for Integ ated
the necessary pressure for recontact with Cases vs. Cryogen1c Plants
compressed a1r.
497
ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986
l1mlted heat aval1abl11ty for certaln TSA
HOlTOX process app11catlons led to the
deve10pmentof des1gns for ccimblned
PSA/TSA and. TSA/PSA HOlTOX systems/:F1gure 2
graph Ically summar1 zes the "des 19n flex1bll ltyof
these HOllOX systems by show1ng the total energy
requIred per ton.of oxygen versus the heat
1nput/output for the var10u( desIgns. The
thermal slo/1ng HOllOX system ut1l1zes the least
net energy and cogenerates steam. Th1s f1gure
also shows that the net energy requ1red for
HOlTOX system oxygen production 1s substant1a11y
below that for the cryogen1c process. Exlst1ng
plants were largely bul1t 1n the 1960 to 1973
perlod and requlre ln excess of 450 KWH per ton
of oxygen, whl1e new oxygen cryogen1c plants can
be deslgned for about 350 KWH per ton of
oxygen.
POTENTIAL HARKETS
Electrlc power ls forecast to cost 7.5t/kwh
(1985 $) ln the U.S. ln the mld-1990's, when the
MOLT OX system will be commercialized. The
MOlTOX oxygen system ls projected to be most
competitive wheresignlficant process heat
lntegration can be achleved. for most
app11cations, a 30 to 40% reduction ln total
energy 1s anticlpated, compared to new e1ectrlc
drlve cryogenlc plants. Slnce 65% of the cost
of oxygen from cryogenic plants 1s energy
related, use of the HOlTOX system results 1n a
projected 12 to 23% improvement over new
cryogenIc plants. This HOlTOX system oxygen
cost improvement ls shown graphically in
Figure 3.
70
60
i="

l-
SO
0
C/l
U
Z
UJ
Cl
>- 40
x
0
30
20
2
4 6 B 10 12
ELECTRIC ENERGY COST (/kwh)
Flgure 3 - Oxygen Cost Comparison -
$600 psia, Purity
(l)New 1000 T/o Plant; ..
15 Year, 100% Capacity, 340 o/Yr
498
Figure 3 also shows oxygen from
ex1st1ng (circa 1960/73) fUlly depreclated
cryogenlc oxygen plants. Replacement of
exlsting cryogenlc p1antsservlng the
steel and chem.iea 1 1ndustries represents one
1mportant market opportunity .. A good example ls
lntegrat10n with-blast furnace off-gas boilers
at integrated steel mi11s.(4) Twenty percent
of the offgas to the existlng bol1ers ls
dlverted to a new steam/salt heater bol1er at
the HOlTOX oxygen plant. The remaining 80% is
burned in the existing bol1ers, whlch results ln
lower stack temperature and more steam
generation. Thls HOlTOX plant could supply
approximately half of an lntegrated steel ml11's
oxygen requirements, whl1e reduclng the ml11 's
electrical energy consumptlon.

;.:
Emerging new oxygen markets also are
candidates for MOLTOX process lntegratlon.
Several applications (oxygen enrichment of coal
for furnaces and bol1ers, refinery fluidized
cat-cracker catalyst regenerators, sulfur
recovery plants, and oxygen secondary reforming)
have sufficient heat available to provide the
entire energy requirements for a HOlTOX TSA
plant. New applications with very large oxygen
requirements (coal gaslficatlon for synfuels
and/or combined cycle power generation; and
coal-based direct smelting of iron) have enough
available heat to provide for a combination
HOlTOX TSA/PSA plant.
PILOT PLANT
In January 1985 the declsion was made to
proceed with Task 2, for the construction and
operation of the pilot plant. The areas of
technical uncertalnty to be addressed by pl10t
plant operation include:
TSA/PSA and TSA modes of operatlon
Salt losses (vapor, corrosion, salt
stabllay)
Absorption/desorption kinetics
Salt loop equipment designs
Adequacy of materials of construction
Long-term operability, and
Gas purity, impurities, and
by-products.
Consideration of the above objectives led to
the p110t plant depleted in the slmp11fled
process flow diagram shown in Flgure 4. Thls
flowsheet includes a slngle absorber, a slng1e
desorber, a salt pump, a salt cooler, and a
salt/salt heat exchanger. Thls equtpment ls
sufflcient to test all key parts of the thermal
swing HOLTOX process.
The materials of constructlon for the pilot
plant were selected based on corroslon test
results from Task 1.(3,5) Our estlmate of the
maximum use temperature for common engineering
alloys is given below.
ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986
Alloy Maximum Use Temperature
Carbon Steel 840F
316 SS 1150F
Incoloy 800 1250F
Inconel 600 1300F
The p110t plant s1mp11f1ed flow d1agram
shows expected operat1ng temperatures along w1th
the recommended mater1als.
The p110t plant w111 allow further study of
the corros1veness of the salt. The corros10n
w111 be mon1tored w1th v1sual and ultrason1c
thickness measurements of vessels and p1p1ng;
1nstallat10n of corros10n coupon racks and
corros10n probes; and 1nstallat10n of p1pe
spools of test mater1als. The mater1als be1ng
tested are those that can w1thstand hot,
oxid1zing cond1tions and 1nclude sta1nless
steels and h1gh nickel alloys wh1ch have shown
good performance in ear11er bench scale
corros10n tests. Bulk n1ckel alum1n1de alloy,
developed by Oak R1dge Nat10nal Laboratory, and
FECRALLOY steels, developed by Harwell 1n the
U.K., are both cons1dered strong cand1dates for
serv1ce 1n the h1gher corros10n areas of the
un1t. Ceramics, such as h1gh dens1ty fused
alum1na and z1rcon1a, are also under study, as
are var10us coat1ng techn1ques. Of part1cular
interest are alum1niz1ng, MCrA1Y and N1-Al
coatings. The p110t plant w11l allow tests
under salt flow cond1t10ns that resemble
commerc1al operations. Salt samples w111 be
taken per10d1cally to mon1tor salt chem1stry and
corrosion product accumulat10n.
The proposed t1metable for the f1rst twelve
months of p110t plant operat10n 1s shown on the
Exper1mental Plan (F1gure 5). Th1s t1metable 1s
broken into three phases. Phase A, Proof of
Concept, w111 demonstrate steady-state operat10n
of the absorber/desorber comb1nat10n at a s1ngle
cond1tion for a long per10d of t1me (durab111ty
run). This w11l also ver1fy the des1gn 02
production rates, product pur1t1es, and energy
consumpt10n; and w111 determ1ne the rate of
corros10n 1n various parts of the
absorber/desorber system. Phase B,
Opt1m1zat10n, w111 probe the poss1b111ty of
1mproved process economlcs at more severe
operat1ng cond1t10ns. Phase C, Parametr1c
Stud1es, w111 def1ne the effects of the major
process var1ables, 1nclud1ng absorber pressure,
desorber pressure, absorber 1nlet temperature,
and molten salt circulat10n rate/a1r feed rate;
and prov1de the eng1neer1ng data needed for
scaleup and des1gn of the sem1works plant.
PILOT PLANT RESULTS
The p110t plant started up 1n March 1986.
The 1nstrumentat10n and mechanical operat10n
were checked and the Run I absorber column
hydrau11c tests showed that the column could
operate successfully at des1gn cond1t10ns
w1thout flooding the column.
Sod1um perox1de catalyst was added to t e
salt and the low temperature oxygen generat on
tr1als of Run II began. The plant ach1eved 0.12
T/D of oxygen product10n with 99.9% 02
purity. Th1s Is 92% of the theoret1cal
(equ111brum) 02 recovery for the 1130F
desorber and 930F absorber operat1ng
temperatures.
The un1t performed well for 4 days, at
t1me the 316 sta1nless steel centr1fugal
fa11ed due to corrosion, cav1tation or a i
comb1nat10n of these processes. A redes1gned
pump with a low cavitat10n potent1al impellrr
and Inconel 600 mater1als of construct10n WpS
ordered, and an exper1mental program was '
developed to separate the effects of
and corros10n 1n the pump. This program was
undertaken and completed 1n May 1986. I
As of May 28 1986, the p110t plant 1s
undergoing a planned two week turnaround.
old salt charge 1s being replaced and
corros10n spool p1eces are be1ng 1nstalled Wor
test1ng at actual salt flow cond1t10ns.
base case des1gn and durab11ity run will i
commence 1n early June.
i
DEVELOPMENT PLAN If
In parallel with pilot plant operation,
separate laboratory and bench-scale f
exper1mentation will address salt losses, '
k1net1cs, a1r pur1f1cat10n, alternative salts,
and better mater1als of construction. Pro ess
heat 1ntegration and optimization will be
addressed by further engineer1ng stud1es a ter
the 'Proof of Concept' p110t plant operat1jn.
Results from these laboratory and eng1neer ng
studies will be 1ncorporated into future plot
plant operation plans. The p110t plant ha been
designed for easy modif1cat10n, so that th se
future process improvements can be tested nd
confirmed.
Support by the DOE for the MOLTOX proc ss
development w111 end after complet10n
of the 1n1tial twelve month p110t plant
operation. The next phase of development 111
requ1re construct10n and operat10n of a no 1nal
50 ton per day semi-works plant, as well a
continued p110t plant and laboratory work. Air
Products will seek development support fro
partners who are e1ther oxygen users or
suppliers of oxygen us1ng technology and w 0 can
also prov1de high temperature metallurg1ca
expert1se. The areas of technical uncerta nty
to be addressed by the semi-works plant ar
plant scaleup and process heat 1ntegrat10n at an
oxygen us1ng host site.
ACKNOWLEDGMENTS
The authors would 11ke to thank Air Pr ducts
and Chem1cals, Inc. and the U.S. Departmen of
Energy for perm1ss10n to pub11sh th1s pape
ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986
0783
SALT
__ SEPARATOR
('200'"
.- ...... 20 PSIAI
I I I
07.02 I ~
DESQRBER T
07.80 I
r - ...L - , FLUIDIZED
SALT
, 1215F , SAND HEATER I SEPARATOR
Ii II IIII
I
11111111
I
11111111
11111111 I
I
I
I
~ t
I
tTl
i
0540
SALT/SALT EXCHANGER
10.30 05.41
SALT PUMP SALT COOLER
05.09
AlA/01
EXCHANGER
AlA
05.10
AIRIN,
EXCHANGER
FIGURE 4
MOLTOX'M PILOT PLANT FLOW DIAGRAM
c.w
LEGEND
CARBON STEEL
316SS OR 304SS
INCOLOY 800H
~ INCONEL 600
to ~ O.
~ ~ N
':?......':.-.:....
ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986
EXPERIMENTAL PLAN
REFERENCES
PILOT PLANT
1. Er1ckson. D. C. of Oxygen rom
OVERALL
Gaseous H1xtures W1th Mo,t@n Alka11 Met 1
SCHEDULE
OBJECTIVES S,alj:,s" U.S. Patent 4.132.766; 2 Janu ry
12 STEPS TO SUCCESSFUL ENERGY PROJECT 4.2B7.170;
A. Anderlon. SC.. ..
. 'Oxygen Product1on by he
RESPONSE F1nal
H. Grant Company, Bixlon, February
1983. -
Steady state of operat1on
FUEL 1100F desorber. Close
3. Archer. R. A. and Dunbobb1n. B. R "Pllot
-- --mater1aland energy balance
Plant Development of AChem1cal A1r
Seuion cwtftaat'gefl. .. Konlanto
Process." F1nal Task I DOE
Report DE-AC07-82CE40544; May 1985.
4 Months
FUEl. Douglas M. Jewel,
Center, '8'.''R' 'B"r"o\on, .
pur1tles. and energy Cassano. A. A. and Massey. R. G.
THE SYSTEM, Root __ Integrat10n for The i
John(,nOeMtlluo.iI.rtaren A. Trimble, Gas aniHeam." AICh
Chicago, IL....... lIugust 1985. ...
Durab1l1ty run. Long term
,oiLeOltU. IN. REFINERIES W. T1tcomb. J. B.
PLANt8}acrili;Allllt".naddtlred Roach, Los H. T. and B.. ,
National Laboratory, LOl Alamos, NK Salts"
B. Opt1m1zat1on _ Journal of Metals - July 1985.
r
PLANNING ACOMMERCIAL FUEL CELL INSTALLATION, Ji..ie R.
Inc., San
. glJt1ty.aod..
633
energy use for Base Case B
DEMONSTRATIONS OF FUEL CELL APPLICATIONS,
JOleph M. Anderlon, Fuel Cell Association, Lake
2 Months
643
1
tQn
at more severe operat1ng
cond1t1ons (1250F
HEAT RECOVERY
ho.. &.raRleJ:f,w.l<.1n8#okeS!iei Electric
Stud1es Corporation, Orrville, OB
ssmlm SItA_*'TI-GAS STACK EMISSION
1Qfb1ft!L. Nehon. WesUnghoule
OH
process. to the extent that such
James T. Barriz and
Waterland, Viar &Associates, Inc.,
655
6 Months
LOW OXYGEN (02) IN COAL FUELED UTILITY BOILERS
1US11 Hopkins, Southwestern
PUb! TX.and Thomas M.
Dow Siegler. Inc., Inglewood, CO 661
2. s8rber Temperature
CONSIDERATIONS FOR PROCESS BEATERS AND BOILERS,
Alh Shreveport, LA, 666
4. A6sor5er Pressure
5. Desorber Pressure
Am>
Sess\on A. Mozzo, Jr., Aaerican Inc.,
pallcU'Tar NY
concentrat1on '
COGENERATION AT IOWA METHODIST MEDICAL CENTER. Cabot Thunem,
and Steve Schebler, Stanley ConsultanU, Inc., Muscatine, IA
and Glenn Love, Iowa Methodist Medical Center, Des Moinel, IA 677
APPLICATION, Martin A. Mozzo, Jr.,
American Standard. Inc., New York. NY............................. 684

ESL-IE-86-06-78
Proceedings from the Eighth Annual Industrial Energy Technology Conference, Houston, TX, June 17-19, 1986