Industrial gases in

the chemical industry

22
Together w ith optim um supply of a
com plete selection of gases, Linde
provides the chem ical industry w ith
com prehensive know -how and
extensive supporting services:
Process consulting, econom ic
feasibility studies
Advice on safety issues
Process design calculations
Experim ental investigations
D evelopm ent of technological
and engineering solutions
Im plem entation and start-up
Financing, rental and operation of
gas production and distribution
facilities.
Linde industrial gases
partners to the chemical industry
Industrial gases find vast and versatile
application in the chem ical industry.
They serve as feed m aterials for syn-
thesis processes, they ensure and
im prove the econom y of processes
and plants, they enhance product
quality and plant safety, and they help
to protect the environm ent.
Supply of gases m ust be m atched
specifically to the diversity of pro-
ducts, processes and production
capacities. Essential factors in this
are dependability, econom y and
w ide-ranging applications solutions.
Q uality, safety and environm ental
protection are key ingredients in all of
Lindes w ork. O ur integrated Q SE
m anagem ent system based on D IN
EN ISO 9001, D IN EN ISO 14001
and SC C assures consistently high
quality and safety of our products
and services as w ell as environm en-
tal com patibility in the application
of industrial gases and their disposal
w here required.
3
Industrial gases
components for synthesis processes
Applications in general
In the chem ical industry industrial
gases are used principally
as chem ical reactants
for assuring plant safety
for protection of the environm ent
in analytical chem istry
for industrial service.
O xygen, hydrogen, carbon m onoxide,
carbon dioxide and synthesis gas
are reactants in a large num ber of
im portant synthesis processes. The
accom panying charts sum m arize
com m on reactions w orking w ith oxy-
gen, hydrogen, carbon m onoxide
and carbon dioxide.
3
Carbon dioxide Metal hydroxides
Hydrocarbons
Sodium phenolate
Urea
Salicylic acid
Carbonates,
hydrocarbonates
Esters
Alkylene carbonates,
polyalkylene carbonates
Ammonia
Alkylene oxides
Hydrogen
Ammonia
Methanol
Short-chain and desulphurized
petroleum products
Hydrogenated
hydrocarbons
Aldehydes
Hydroxylammonium sulphate
Metals
Hydrogen peroxide
Air (anthraquinone
process)
Carbon monoxide,
carbon dioxide
Hydrocarbons
Metal oxides
Nitrogen
Petroleum products
CO +olefins
NO +sulphuric acid
Methanol
Aldehydes, alcohols
Hydrogen
Olefine Olefins
Chlorine
Carbon monoxide
Metals
Hydrocarbons
Carboxylic acids
Phosgene
Metal carbonyls
Oxygen
Paraffins, olefins
Paraffins, olefins
Olefins
Olefins, aldehydes
Petroleum refining residues
Hydrogen sulphide Sulphur
Synthesis gas
Carboxylic acids
Epoxides
Alcohols
Aldehydes
Reactions with carbon monoxide
Reactions with oxygen
Reactions with carbon dioxide
Reactions with hydrogen
4
30
25
20
15
10
5
0
20 22 24 26 28 30
Oxygen concentration in vol%
C
a
p
a
c
i
t
y

i
n
c
r
e
a
s
e

i
n

%
90% H
2
S 70% H
2
S 30% H
2
S 50% H
2
S
Central supply pipeline
On-site oxygen plant
Tank
Air
Gas distributor
Air and
oxygen to
Claus plant
Claus plant process
control system
Controller
Measuring
and
control
unit
Vaporizer
Oxygen
Oxygen for oil refineries
O xygen is used at oil refineries for the
partial oxidation of petroleum resi-
dues, to regenerate catalysts in FC C
plants, and to im prove the perfor-
m ance of C laus plants.
In the C laus process, hydrogen
sulphide is converted to elem ental
sulphur. R em oval of sulphur com -
pounds is required in the processing
of petroleum , natural gas and coal
to m otor fuels, synthesis gas and
fuel gas.
Its purpose is to ensure com pliance
w ith both the em ission levels stipu-
lated under environm ental law s and
the m axim um concentrations of
sulphur com pounds im posed by
technological constraints.
At present, the oxygen content of
atm ospheric air is prim arily utilized for
the oxidation of hydrogen sulphide.
Adding oxygen to the air or using
pure oxygen results in a num ber of
benefits:
Increased plant capacity
H igher oxidation tem peratures
R educed load on off-gas treat-
m ent system s due to low er
concentration of inert nitrogen
N ew plants can be built sm aller.
Gases for oil refineries
greater efficiency,
cleaner environment
Claus plant
Capacity increase
through oxygen enrichment
Schematic diagram of oxygen enrichment
5
Left:
Production of syn-
thesis gas and
methanol from oil
refining residues
Linde hydrogen plant
Above:
Gasification of oil
residues with oxygen
Hydrogen for oil refineries
An oil refinery is both a producer and
a consum er of hydrogen, the volum es
consum ed usually exceeding those
internally produced.
H ydrogen is needed as a reactant in
hydrorefining and hydrocracking.
Since refineries are shifting their out-
put to larger quantities of low -sulphur,
low -arom atics and brighter products,
dem and for hydrogen w ill continue
to grow .
The m ain processes for production
of hydrogen are:
Steam reform ing of m ethane
G asification of oil refining residues
and recovery from synthesis gas
R ecovery from refinery off-gases.
6
Oxidation of ammo-
nia for production of
nitrogen monoxide
Product Feed Air Oxygen Enriched air
Acetaldehyde Ethylene b b b
Benzoic acid Toluene b
Cyclohexanone Cyclohexane b b
Acetic acid Acetaldehyde b b
Ethylene oxide Ethylene b
Propylene oxide Propylene b b
Nitrogen monoxide Ammonia b
Terephthalic acid p-Xylene b b
Vinyl acetate Ethylene, acetic acid b
Vinyl chloride Ethylene, hydrogen chloride b
Hydrogen peroxide Hydrogen b b
Oxygen:
Improving economy reducing
investment costs
Increasing use is being m ade of in-
dustrial oxygen in oxidation processes
for the m anufacture of oxides, alde-
hydes, and also acids and alcohols.
It can greatly im prove the econom y
of existing plants and reduce capital
expenditure for new plants. The m eth-
ods used are oxygen enrichm ent of
the oxidizing air, adding oxygen to the
feed stream and substituting pure
oxygen for air.
The benefits of oxygen are:
Larger throughput in the sam e
size of plant by low ering the
concentration of inert nitrogen
H igher tem peratures in the
reacting stream
Accelerated reactions due to
higher oxygen concentration
H igher selectivity of the oxidation
process in parts
Sm aller off-gas flow s
Low er energy consum ption.
Oxidation processes using oxygen
Economical reactants for production of
basic chemicals and intermediates
Hydrogenation
of phenol to
cyclohexanone
Production of
epoxy resins
using carbon
dioxide
Carbon dioxide:
reactant, solvent,
pH control agent
C arbon dioxide is used, for exam ple,
in the m anufacture of urea, salicylic
acid, carbonates and polyalkylene
carbonates, and in several other or-
ganic chem istry synthesis processes.
Supercritical carbon dioxide is a
prospective replacem ent for environ-
m entally hazardous solvents as
currently required in a num ber of
chem ical synthesis reactions and
is capable of im proving the properties
of som e products m ade by poly-
m erization.
B eyond that, carbon dioxide is w idely
used for pH -value control and neu-
tralization of liquids.
7
Liquid Solid
10
3
10
2
10
1
10
-1
173 223 273 323 373
P
r
e
s
s
u
r
e
,

p
,

i
n

b
a
r
Temperature, T, in K
p, T diagram
Critical
point
Triple point
Gaseous
Supercritical
Hydrogen:
Basic chemicals, hydrogenation,
catalyst production
H ydrogen is a reactant in the m anu-
facture of basic chem icals and
interm ediates as w ell as specialty
chem icals and pharm aceuticals.
Synthesis gas, a m ixture of hydrogen
and carbon m onoxide, is em ployed
above all for synthesis of m ethanol and
in the hydroform ylation of olefins to
aldehydes and alcohols. Am m onia is
m anufactured from a different syn-
thesis gas m ixture of hydrogen and
nitrogen.
Another process of considerable im -
portance is hydrogenation, w hich
involves the hom ogeneous or
heterogeneous catalytic addition of
hydrogen to organic com pounds.
Exam ples are:
H ydrogenation of adipic acid
dinitrile to hexam ethylene diam ine
H ydrogenation of benzene
to cyclohexane
H ydrogenation of phenol to
cyclohexanone.
Industrial hydrogen is also used in
the m anufacture of catalysts for
reducing m etal oxides to the active
m etallic form and to regulate chain
length in the polym erization of pro-
pylene to polypropylene and in the
m anufacture of polyethylene.
Phase diagram for CO2
Neutralization of alkaline
effluents with carbon dioxide
(SOLVOCARB

process)
B efore alkaline effluents from an in-
dustrial plant can be discharged
to the m unicipal sew age system ,
they m ust be neutralized.
C arbon dioxide has several advan-
tages over m ineral acids in neutralizing
alkalies. To begin w ith, it is not classi-
fied as a m aterial w hich is hazardous
to w ater. M oreover, it is not associated
w ith high salt loads, w hich m ay be
penalized by special charges, and the
flat neutralization curve excludes
risk of over-acidification.
N eutralization of w astew ater w ith
carbon dioxide is carried out w ith the
Linde SO LVO C AR B

process.
8
Neutralization with
a SOLVOCARB

reactor in a
chemical plant
Oxygenation of
wastewater using the
SOLVOX

-B process
Environmental protection
and resource recovery
reliable, efficient, economical
Oxygen for wastewater treatment
(SOLVOX

process)
M any problem s occurring in the
treatm ent of w astew ater are due to
a deficit of oxygen. In the chem ical
industry especially, w here effluents
are usually heavily contam inated, this
can cause considerable trouble such
as degraded treatm ent perform ance
or appreciable odor nuisance due to
anaerobic decom position processes.
Industrial oxygen is often capable of
rem edying such situations.
The necessary oxygen is injected into
the w astew ater by the Linde SO LVO X

process. Particular advantages of

this process are its low investm ent
costs and flexible adjustm ent of oxy-
genation to actual needs.
9
Clinker
Spent sulphuric acid,
solvent
Primary air +O
2
Planetary cooler
(secondary air)
Gypsum,
fly ash (Al, Si, Fe),
coal
Exhaust gas
Processing spent
sulphuric acid in
rotary kiln
Cleaning acetone-
contaminated waste gas
by cryocondensation
with liquid nitrogen
Raw gas, 0C
40 g/m
3
of acetone
Clean gas, approx. 20C
<0.15 g/m
3
acetone
Primary condenser
cooled by clean gas
Cryocondenser cooled
by liquid nitrogen
Nitrogen gas
Liquid
nitrogen
Condensed
acetone
Raw gas, 60C
<5 g/m
3
of acetone
Condensed
acetone
Clean gas, <95C
<0.15g/m
3
of acetone
Recovery of valuable organic ma-
terials and waste air purification
by cryocondensation
C ryocondensation w orks w ith liquid
nitrogen as a low -tem perature
refrigerant. The polluted air stream is
cooled in heat exchangers to below
dew point tem perature, causing con-
tam inants or recoverable m aterials
present in vapor form to condense.
Liquid nitrogen achieves condensing
tem peratures w ell below those
attainable w ith conventional refriger-
ating m achines.
Benefits
C onvenient adjustm ent of process
tem perature to changed conditions
R egulation of condensation
perform ance over a broad range
Treatm ent of highly
contam inated w aste air stream s
R eduction of residual contam inant
levels to parts per m illion.
Oxygen in processing of spent
sulphuric acid
M ineral w astes and spent sulphuric
acid can be processed in rotary kilns.
For exam ple, gypsum is processed in
these rotary kilns jointly w ith spent
sulphuric acid and coke, follow ed by
conversion of sulphur dioxide to
sulphuric acid.
Enriching the air supplied to the kiln
w ith oxygen achieves the follow ing
benefits:
Increased processing capacity
C om bustion of solvents
containing higher levels of w ater.
Flowsheet for cryocondensation
Rotary kiln supplied with oxygen-enriched air
10
Nitrogen
Heat exchanger
Inert gas grid
Pump
Coolant
return
Coolant
supply
Reactor
Reactors cooled with
liquid nitrogen
Inerting in storage of
chemical products
Inerting in chemical processes
Low ering oxygen concentrations to
a safe level by inert gases (nitrogen
and carbon dioxide) is a proven
m ethod of preventing oxidation, fires
and explosions.
A cushion of inert gas is frequently
placed over liquids in storage tanks.
Silos are purged w ith inert gas as a
precaution against dust explosions.
Another im portant application is for
explosion protection on reactors in
w hich oxidation takes place in the
liquid phase. D ue to the risk of an
explosive m ixture form ing in the head
of the reactor, it m ust be purged
continuously w ith inert gas so as to
dilute the gas m ixture below its ex-
plosion lim it.
Cooling vessels and reactors
C ontrol of tem perature is often
vital to achieving high yield and good
quality of chem ical com pounds
m anufactured by synthesis. Liquid
nitrogen enables low -tem perature
synthesis of chem ical and pharm a-
ceutical products to be carried out
conveniently at -80 C or such other
tem perature as m ay be required.
C ooling can be perform ed by three
m ethods:
Injecting liquid nitrogen directly
into the reactor.
C ooling the reactor contents by
nitrogen flow through an external
jacket or an internal cooling coil.
Indirect cooling by a secondary
circuit.
The benefits of liquid nitrogen cooling
are:
C ooling capacity variable over a
w ide range
Low investm ent and operating
costs
Absence of environm entally
dam aging refrigerants or noise
nuisance .
Safe inerting and
efficient cooling
Reactor cooling by secondary circuit
11
Catalytic reactor for
deoxygenation of
boiler feedwater
SOLVOGEN

control panel
Laboratory in the
chemical industry
Gas and equipment supply for
laboratories and pilot plants
U ltra-pure gases, gas m ixtures and
calibration gases are required by
laboratories and pilot plants in the
chem ical industry for analytical
and m easuring applications and test
operation.
Linde has a stock range of standard
gas m ixtures.
C alibration gases precision gas
m ixtures of custom er-specified
com position and certified analysis for
use in calibrating m easuring and
analytical instrum ents are supplied
in pressure cylinders.
G ases of high-grade quality are
essential for reliable and accurate
operation of gas analyzers. Linde
supplies operating gases for gas
chrom atography, flam e photom etry,
chem ilum inescence, spark spec-
troscopy, EC D analysis and atom ic
absorption, and filling gases for
counter tubes.
Linde designs and builds com plete
gas supply system s for laboratories
and pilot plants as either standard
or custom ized units.
Deoxygenation of boiler
feedwater (SOLVOGEN

process)
B ecause it corrodes piping and ves-
sels, oxygen m ust be rem oved from
boiler feedw ater, hot w ater system
recirculating flow s and chem ical
process w ater. The SO LVO G EN

process has been designed for this

purpose.
The process is based on converting
dissolved oxygen w ith hydrogen over
a palladium catalyst at am bient
tem perature.
Linde supplies SO LVO G EN

system s
to treat w ater flow s as sm all as
10 m
3
/h in the food industry or as
large as 1000 m
3
/h in pow er stations.
Other gas applications
for the chemical industry
12
Pig trap and
nitrogen feeding
point in Rongellen,
Switzerland
All of the com prehensive services and
service processes available from
Linde are designed to m inim ize the
tim e required for inspection and
m aintenance of com plete system s,
equipm ent and com ponents.
They also satisfy increasingly stringent
environm ental dem ands. All gases
em ployed are non-flam m able, non-
toxic and non-corrosive. M oreover
they reduce fire and explosion risks,
perm itting safe start-up of equipm ent.
Services available are:
Piping and pipeline cleaning by
the Sandjet

process
This is a blast cleaning m ethod using
nitrogen to force the abrasive through
the piping system . The abrasive is
recovered for re-use.
Leak testing
A nitrogen-helium gas m ixture is used
for leak testing of com plete system s
or individual com ponents at operating
pressure.
System drying
D rying of pipings, com plete produc-
tion system s or individual com ponents
is carried out w ith nitrogen, w hich
m ay be heated to relatively high tem -
peratures as required.
Reactor cooling
R apid cooling of reactors is achieved
by controlled injection of liquid nitrogen
to prepare them for servicing. Tim e
saved for cooling greatly reduces the
duration of system shutdow n.
Service processes
quicker inspections, reduced fire risk,
environmentally compatible
Leak test on piping
assembly for
hydrogen plant
13
Cleaning molds
used in production
of polyurethane
foam
Agitator used in
paint manufacture
prior to being
cleaned
Agitator after
being cleaned by
the CRYOCLEAN

process
Pigging and pipeline renewal
A pig is a m echanical device forced
through a pipeline system by intro-
ducing nitrogen at high pressure,
displacing the oil or other fluid into
a receiving tank and cleaning the
pipe. At the sam e tim e the pipeline is
inertized by the nitrogen. C leaning
can be com bined w ith rem ote visual
inspection by video cam era.
Mobile natural gas supply
Long-distance or regional gas pipe-
lines have to be taken out of service
w hen m odernization, rerouting or
repairs becom e necessary. For the
chem ical industry this m ay norm ally
necessitate tem porary shutdow n of
production facilities. D uring such
tim es, continuous supply of gas can
be m aintained w ith Linde m obile nat-
ural gas stations, self-contained units
operating at a high level of safety and
reliability.
Blast cleaning with dry ice
In the C R YO C LEAN

process, dry ice

pellets frozen to -78 C are propelled
at high velocity onto the surfaces of
w ork to be cleaned. O n im pact, the
dry ice im m ediately vaporizes, rem ov-
ing dirt and im purities w hile leaving
the cleaned surface clear of grit or
sludge residue. Typical applications
in the chem ical industry are for clean-
ing heat exchangers, piping and
agitators.
14
Tanker delivering
liquid hydrogen
Gas cylinders
in various sizes
W ith our tightly knit production, sales
and distribution netw ork w e can
guarantee fast, reliable and econom -
ical supply of gases to users by
facilities ranging from tw o-litre steel
cylinders to on-site units, from
75,000-litre liquid tanks to direct
pipelines.
Gas cylinders
U pw ards of four m illion gas cylinders
displaying the Linde nam e are in
circulation in Europe. They are deliv-
ered to users by road truck or trailer,
depending on the quantities required.
To enable custom ers to m aintain a
running inventory of gases, Linde pro-
vides the LIB AS

cylinder tracking
system , w hich continuously m onitors
m ovem ent of all cylinders.
Liquefied gas tanks
C ustom ers w hose requirem ents
exceed the capacity of cylinder deliv-
eries are supplied w ith liquefied
gases transported by tanker truck and
stored for use in tanks installed on
their prem ises.
Linde furnishes vaporizers and all
other associated equipm ent together
w ith the storage tanks and assum es
responsibility for the entire installation,
m aintenance and inspection w ork.
Electronic rem ote m onitoring of tank
level ensures that an adequate
supply of gases is available at all tim es.
ECOVAR

on-site units
Above a certain consum ption rate,
supply of gases by road tanker is
not a satisfactorily econom ical prop-
osition. In such instances w e
recom m end installation of a plant
for on-site production.
Gas supply
complete and functional
ECOVAR

-M plant
ECOVAR

-A plant
ECOVAR

-C plant
Merseburg
Buna
Halle
Dessau
Bitterfeld
Leipzig
Leuna
Rodleben
Hydrogen
Nitrogen
Oxygen
Plesteritz
15
Pipeline supply is particularly eco-
nom ical in industrial regions w here
several users are linked to a supply
grid served by a central production
facility.
Linde is w ell positioned for pipeline
business. Through its Process Engi-
neering and C ontracting D ivision the
com pany has access to an extensive
range of equipm ent. Air separation
plants are designed and built for pipe-
line supply of oxygen and nitrogen
as w ell as plants for production of
hydrogen, carbon m onoxide and
synthesis gas.
The EC O VAR

supply concept
com bines an on-site production unit
and liquid storage tank for supply
of nitrogen or oxygen. B asic dem and
is covered by the capacity of the
production unit w ith a reserve supply
available in the storage tank to m eet
peak consum ption and em ergency
situations. C ustom ers can choose
am ong three alternatives according
to the required product, purity and
production capacity: EC O VAR

-C
(cryogenic process), EC O VAR

-A
(adsorption process) or EC O VAR

-M
(m em brane process). All three types
are m arked by high reliability of supply,
econom ical production cost and a
high level of flexibility.
Pipeline grid
D irect delivery by pipeline from one
of our production centers is the m ost
econom ical form of supply for com -
panies using large tonnages of gases.
A grow ing num ber of high-volum e
users have endorsed this option by
reason of its obvious advantages.
Linde puts up the capital for new
plants, invests its m any years of
experience acquired in operation of
num erous com parable facilities,
and m oreover guarantees reliable
supply in tim es of peak dem and
or em ergencies through its backup
resources of large tank farm s and
extensive distribution capabilities.
Steam reformer producing
hydrogen in Milazzo, Sicily
Linde pipeline sys-
tem in Germany
totalling more than
400 kilometres
supplies hydrogen,
nitrogen, carbon
monoxide and oxy-
gen to high-tonnage
users
Performance on site
Linde Industrial Gases
Linde AG
W erksgruppe Technische G ase
Export H ead O ffice
Seitnerstrae 70
82049 H llriegelskreuth/G erm any
Phone: + 49/89/74 46 -0
Fax: + 49/89/74 46 -12 30
http://w w w .linde.com /linde-gas
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Linde industrial gases are encountered in
applications as varied as w elding, freezing,
propulsion, heating, industrial cleaning, res-
piration or testing.They im prove the
quality of life and they help to secure the
future by m aking production operations
m ore efficient and econom ical.
Supply of the gases them selves is supported
by expert counselling and know -how , custom -
ised hardw are, custom -application testing,
and the com plete handling associated w ith
industrial gases.
G ases can be supplied in any form appropri-
ate to custom ersrequirem ents: in cylinders
or m ulti-cylinder batteries, from liquefied gas
tanks, through EC O VAR

on-site production
units, by pipeline.
Industrial cleaning
Metalworking
Food industry
Fuel and power
Applications
and supply
equipment
On-site servicing
Qualified and
comprehensive advice
Metallurgical and
chemical industries
Microelectronics
Environmental engineering
Pipelines
ECOVAR

on-site
production
units
Air separation plants
Gas cylinders
Site tanks
Medicine
Glass industry
Know-how
Suppl y
Counsel l i ng
Producti on
Servi ce
Appl i cati ons
Your local supply center: