chemistry e brochure17 6956

8/11/2019 Chemistry e Brochure17 6956

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Industrial gases inthe chemical industry


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Together w ith optim um supply of acom plete selection of gases, Lindeprovides the chem ical industry w ithcom 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 technologicaland engineering solutions

Im plem entation and start-up

Financing, rental and operation of

gas production and distributionfacilities.

Linde industrial gasespartners to the chemical industry

Industrial gases find vast and versatileapplication in the chem ical industry.They serve as feed m aterials for syn-thesis processes, they ensure and

im prove the econom y of processesand plants, they enhance productquality and plant safety, and they helpto protect the environm ent.

Supply of gases m ust be m atchedspecifically to the diversity of pro-ducts, processes and productioncapacities. Essential factors in thisare dependability, econom y andw ide-ranging applications solutions.

Q uality, safety and environm entalprotection are key ingredients in all ofLindes w ork. O ur integrated Q SEm anagem ent system based on D IN

EN ISO 9001, D IN EN ISO 14001and SC C assures consistently highquality and safety of our productsand services as w ell as environm en-tal com patibility in the applicationof industrial gases and their disposalw here required.


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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 desulphurizedpetroleum products

Hydrogenatedhydrocarbons

Aldehydes

Hydroxylammonium sulphate

Metals

Hydrogen peroxideAir (anthraquinone process)

Carbon monoxide,carbon dioxide

Hydrocarbons

Metal oxides

Nitrogen

Petroleum products

CO + olefins

NO + sulphuric acid

Methanol

Aldehydes, alcohols

Hydrogen

OlefineOlefins

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


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4

30

25

20

15

10

5

020 22 24 26 28 30

Oxygen concentration in vol%

Capacityincreasein%

90% H2S 70% H2S 30% H2S50% H2S

Central supply pipeline

On-site oxygen plant

Tank

Air

Gas distributor

Air andoxygen toClaus plant

Claus plant processcontrol system

Controller

Measuringand

controlunit

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 erconcentration 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


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Lef t :

Product ion of syn-

thesis gas and

methanol f rom oi l

ref in ing res idues

Linde hydrogen plant

Above:

Gasif icat ion of oi l

res idues w i th 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 residuesand recovery from synthesis gas

R ecovery from refinery off-gases.


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Oxidat ion of amm o-

nia for product ion of

ni t rogen monoxide

Product Feed Air Oxygen Enriched air

Ac eta ld ehyd e Et hy le ne

B enzo ic a c id To lue ne

C y clo he xa n on e C yc lo he xa n e

Ac etic a c id Ac eta ld ehyd e

E thylene ox ide Ethy lene

Propylene oxide P ropylene Nitrogen monoxide Ammonia

Terephthalic acid p-Xylene

Vinyl a ce ta te Ethy lene , a ce t ic a c id

Vinyl chloride Ethylene, hydrogen chloride

Hydrogen peroxide Hydrogen

Oxygen:Improving economy reducinginvestment costs

Increasing use is being m ade of in-

dustrial oxygen in oxidation processesfor 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 theconcentration 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 ofbasic chemicals and intermediates


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Hydrogenat ion

of phenol to

cyclohexanone

Product ion 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, salicylicacid, 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 idelyused for pH -value control and neu-

tralization of liquids.

7

LiquidSolid

103

102

10

1

10-1

173 223 273 323 373

Pressure,p,

inbar

Temperature, T, in K

p, T diagram

Criticalpoint

Triple point

Gaseous

Supercritical

Hydrogen:Basic chemicals, hydrogenation,catalyst production

H ydrogen is a reactant in the m anu-

facture of basic chem icals andinterm ediates as w ell as sp ecialty

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 inthe 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


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Neutralization of alkalineeffluents with carbon dioxide(SOLVOCARBprocess)

B efore alkaline effluents from an in-

dustrial plant can be dischargedto 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 ithcarbon dioxide is carried out w ith the

Linde SO LVO C AR Bprocess.

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Neutra l izat ion w i th

a SOLVOCARB

reactor in a

chemical plant

Oxygenat ion of

wastew ater using the

SOLVOX-B process

Environmental protectionand resource recovery reliable, efficient, economical

Oxygen for wastewater treatment(SOLVOXprocess)

M any prob lem s occurring in the

treatm ent of w astew ater are due to

a deficit of oxygen. In the chem icalindustry 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 entcosts and flexible adjustm ent of oxy-

genation to actual needs.


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ClinkerSpent sulphuric acid,solvent

Primary air + O2

Planetary cooler(secondary air)

Gypsum,fly ash (Al, Si, Fe),coal

Exhaust gas

Processing spent

sulphur ic acid in

rotar y ki ln

Cleaning acetone-

contam inated waste gas

by cryocondensat ion

wi th l iqu id ni t rogen

Raw gas, 0C40 g/m3of acetone

Clean gas, approx. 20C


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Nitrogen

Heat exchanger

Inert gas grid

Pump

Coolantreturn

Coolantsupply

Reactor

Reactors cooled wi th

l iquid ni t rogen

Iner t ing in storage of

chemical products

Inerting in chemical processes

Low ering oxygen concentrations to

a safe level by inert gases (nitrogen

and carbon d ioxide) is a proven

m ethod of preventing oxidation, firesand 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 todilute 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. Liquidnitrogen 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 noisenuisance .

Safe inerting andefficient cooling

Reactor cooling by secondary circuit


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Cataly t ic reactor for

deoxygenat ion of

boi ler feedwaterSOLVOGEN

contro l panel

Laboratory in the

chemical indust ry

Gas and equipment supply forlaboratories and pilot plants

U ltra-pure gases, gas m ixtures and

calibration gases are required by

laboratories and pilot plants in thechem 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 boilerfeedwater (SOLVOGENprocess)

B ecause it corrodes piping and ves-

sels, oxygen m ust be rem oved from

boiler feedw ater, hot w ater systemrecirculating flow s and chem ical

process w ater. The S O LVO G EN

process has been designed for this

purpose.

The process is based on converting

dissolved oxygen w ith hydrogen over

a pallad ium 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 applicationsfor the chemical industry


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Pig t rap and

n i t rogen feed ing

point in Rong el len,

Swi tzer land

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 bythe Sandjetprocess

This is a blast cleaning m ethod usingnitrogen 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 pip ing

assembly for

hydrogen plant


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Cleaning m olds

used in product ion

of polyurethane

foam

Agi tator used in

paint manufact ure

pr ior to being

cleaned

Agi tator af ter

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 p ressure,

displacing the oil or other fluid intoa 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. During 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 CRYO 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.


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Tanker d el ivering

l iqu id hydrogen

Gas cyl inders

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 trackingsystem , 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 andstored 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 unitsAbove 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 p lan t

ECOVAR-A plant

ECOVAR-C plant


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Merseburg

Buna

Halle

Dessau

Bitterfeld

Leipzig

Leuna

Rodleben

HydrogenNitrogenOxygen

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

prod uction capacity: EC O VA R -C

(cryogenic process), EC O VA R -A

(adsorption process) or EC O VA R -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 p uts up the cap ital for new

plants, invests its m any years of

experience acquired in operation of

num erous com parable facilities,and m oreover guarantees reliab le

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

hydrog en in M ilazzo, Sici ly

Linde pipel ine sys-

tem in Germany

tota l l ing more than

400 ki lomet res

suppl ies hydrogen,

n i t rogen, carbon

monoxide and oxy-

gen to high- ton nage

users


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Performance on site

Linde Industrial Gases

Linde A G

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

8785/8

0

899-

1.3m

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ubjecttoalteration.P

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bleachedpaper.

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 VARon-site production

units, by pipeline.

Industrial cleaning

MetalworkingFood industry

Fuel and power

Applicationsand supplyequipment

On-site servicing

Qualified andcomprehensive advice

Metallurgical andchemical industries

Microelectronics

Environmental engineering

Pipelines

ECOVAR

on-siteproduction

units

Air separation plants

Gas cylinders

Site tanks

Medicine

Glass industry

Know-how

Supply

Counselling

Production

Service

Applications

Your local supply center:

chemistry e brochure17 6956

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