Industrial Solutions

Hydrogen – Key to any RefineryFor high quality gasoline, diesel or jet fuel

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Thepoweroftrueefficiency

The Business Area Industrial Solutions of thyssenkrupp is a world leaderforplanning,constructionandserviceinthefieldofindustrialplants and systems. Together with our customers we develop solutionsatthehighestlevelanddeliverefficiency,reliabilityandsustainabilitythroughouttheentirelifecycle.Ourglobalnetwork,witharound19,000employeesat70locations,enablesustoprovi-deturnkeysolutionsworldwidewhichsetnewbenchmarkswiththeirhigh productivity and particularly resource conserving technologies.

We are at home in many different industries. Along with chemical, fertilizer,coking,refinery,cementandotherindustrialplants,ourportfolio also includes equipment for open-cast mining, ore proces-sing and transshipment, as well as associated services. In the naval sector,wearealeadingglobalsystemsupplierforsubmarinesandsurface vessels. As an important system partner to our customers intheautomotive,aerospaceandbatteryindustries,weoptimizethevalue chain and improve performance.

Contents04 Introduction 05 At a glance the advantages

of Uhde's Hydrogen Technology

06 The Uhde Hydrogen Concept

- The Uhde process

07 - Feed preparation

- Feed gas desulphurisation

- Pre-reforming (optional)

08 - Steam reforming

09 - Cold outlet manifold system

10 - Convectionbankdesign

11 - Process gas cooler

12 - Shift conversion

- Heat recovery and process condensate recycle

- Synthesisgaspurification

14 What we offer our customers

- Value improvement process (VIP) andCapex/Opexoptimisation

- Health, safety and environment

15 - Research and development

- thyssenkrupp Industrial Solutions´ services

- Low maintenance requirements

- Training programmes

4

Introduction

There is a growing demand for cleaner, lighter fuel products at a time when oil resources (feedstocks) arebecomingheavier.Thishascreatedahugedemand for hydrogen worldwide and thus the need to increase hydrogen capacities.

Therearevariousfeedstockswhichcanbeusedforhydrogen production, including products which are not particularly attractive, such as heavy residue or coke. However, the most efficient option for hydrogen productionissteamreformingofhydrocarbonsatalow energy consumption.

5

thyssenkrupp Industrial Solutions (formerly knownasthyssenkruppUhde)hasbeenbuildingreformerssince1962.Overthisperiod of more than 50 years, thyssenkrupp Industrial Solutions has continuously im-proved the design of the steam reformer to achievehighefficiencyandreliability,opti-misedCapexandOpex-values,lowemis-sions and excellent manufacturing quality.

• top-fired design with a minimum num-berofstate-of-the-artburners(lowNO

X

guaranteed)andmaximumtubewallcooling where heat flux is high

• modularised concept for easy transpor-tation and more economical construction

• reformerboxdesignthatassureseasyaccess and requires minimum plot space

• proven long lifetimes for the reformer tubes

• unique proprietary cold outlet manifold system with shop testing of all critical weldsformaximumreliability

• advanced modularised shop-tested convective zone

Avarietyofbenefits,includinglowercapitalinvestment and operating costs, reduced energy consumption, maintenance costs and emissions, increased efficiency and on- stream time, and improved safety and re-liabilityhavebeencreatedbysuccessfullycombiningthefollowingfeatures:

• proven process gas cooler design with steam-cooledinternalby-passflap

• in-situ recovery of process condensate, thusavoidingitbeingexportedtobatterylimitsandpreventingemissionsofVOCsto the atmosphere

• nocontaminationofboilerfeedwaterorexport steam from process side through separation of process/export steam via environmentallycleanbi-sectionalsteamsystem

• highreliabilityandmaximumavailabilitydue to validated simulation tools

• maximumautomationtominimiselabourrequirements and facilitate operation.

At a glance the advantages of Uhde's Hydrogen Technology

Feed

Hydrogen

Steam (optional)

Power (optional)

CO2 (optional)

Fuel

Natural Gas

LPG

Naphtha

Offgas

Hydrotreating

Hydrodesulfurization

Hydrocracking

Activation/ Regeneration of Catalysts

Site network

Methanol

Urea

Enhanced Oil Recovery

Beverages

Natural Gas

LPG

Naphtha

Offgas

Hydrogen Plant

6

The Uhde Hydrogen Concept

Simplifiedflowsheme:

The Uhde process

Ourprocessforproducinghydrogenfromlighthydrocarbonsinvolvesthefollowingprocess steps:

• feed desulphurisation• pre-reforming (optional)• steam reforming• shift conversion• synthesis gas purification (PSA)• heat recovery and steam production.

Each plant concept is tailored to the specific needs of our clients.

Additionalprocesssteps,suchasCO2

removalcanalsobeincluded.

Availability and reliability

On-streamtimehigherthan99.5% (10-year average)

Continuous operation of up tosix years in accordance with turnaround cycles

Shift

conversionSteam reforming

Feed

desulphurisation

Pre-reforming

(optional)

Feed

BFW / Demin Export steam

Fuel

H2

PSA

Heat recovery

NesteOilOyj,Porvoo,Finland

Capacity:153,500Nm3/h of hydrogen

Hydrogen

Pressureswing

adsorption

HT shift

Fuel

Steam export

Feed

De-

Combustion air

BFW

reformerSteam drum

Steam drum

Process gas cooler

sulphurisation

Steam

Feed preparation

thyssenkrupp Industrial Solutions offers flexibilityinthefeedstocksandfuelswhichcanbeused.Theseincludenaturalgas,naphtha, LPG and/or offgases.

Feed gas desulphurisation

Feed gas desulphurisation is normally carried out in two steps: • hydrogenation of organic sulphur compounds into H

2S

• absorptionofH2S on zinc oxide

Due to the lead and lag configuration of the two desulphurisation reactors, the absorbentinonereactorcanbereplacedwhile the plant is running at full capacity.

Pre-reforming (optional)

The principle of the pre-reformer involves thepartialconversionofhydrocarbonsin

anadiabaticreactorlocatedupstreamofthe steam reformer. The reactor is filled withNi-basedcatalystandoperatesattem- peraturesbetween450-540°C.

Allheavyhydrocarbonsareconvertedtomethaneandcarbonoxidesinthepre- reformer. This allows optimum process parameterstobeselectedinthesteam reformer, especially in naphtha and LPG-basedplants,whichwouldotherwisenot bepossible.

Integration of the pre-reformer in the overall process achieves the following:

• lower overall feed and fuel consumption• alternate feed operation (from natural

gastonaphtha/LPG)possible• reduced reformer size• lower emissions (flue gas)• lower steam export• higher reformer inlet temperature

possible.

7

SimplifiedflowschemeofUhde'shydrogenplant

Steam reforming

Duringsteamreforminghydrocarbonsreactwith steam to produce mixtures of hydrogenandcarbonoxides.Thereactiontakesplaceinreformertubesofthebox-typesteamreformer.Thesetubesarecentrifugallycastfrom micro-alloy material and are filled withaNi-basedcatalyst.Sincetheoverallreac-tion is strongly endothermic, external heatis required. The heat for the overall endo-thermicreactionissuppliedbyburnerswhichare positioned at the top of the steam re-former, thus ensuring optimum uniformity of the skin temperature profile along the reformertubes.

Thebasicprincipleofsteamreformingisrepresentedbythehydrocarbonconversionreaction (eq. 1) and the water-gas shiftreaction (eq. 2).

CH4 + H

2O <=> CO + 3H

2 (eq. 1)

CO+ H2O <=> CO

2 + H

2 (eq. 2)

Inlet manifold

Reformertubes

Burners

Cold outletmanifold system

Steam reformer

The Uhde reformer

Uniform temperature profile over the entire reformer

Uniformtubewalltemperatures

Lowestnumberofburnersamongst all types of reformer designs

Micro-alloytubematerial

8

Bayernoil

Neustadt/Donau,Germany

The Uhde Hydrogen Concept

9

Refractory

Feed/steam

Furnace arch

Reformer tube

Fire box

Catalyst grid

Furnace bottom

Bellow

Gas conducting tube

Shop weld

Field weld

Carbon steel

Outlet manifol

Metal liner

d

Skin temperature [°C]300 600 900

Cold outlet manifold system

Cold outlet manifold system

The reformed gas from the steam reformeris collected in a refractory-lined manifold.The cold manifold system conveys the steam reformer effluent to the process gas cooler.

In Uhde´s cold outlet manifold system thenumberofcriticalelementshasbeenre-duced to the minimum as hot pigtails andhotmanifoldshavebeeneliminated.Theskin temperature of the manifold systemdropsrapidlytobelow250°C.

Cold outlet manifold system

Unique patented design

Many decades of experience withtrouble-freeandhighlyreliableoperation

Nooutletpigtailsnecessary

Separates high pressure from hot temperatures

All critical welds shop-made and fully tested

Onlycarbonsteelweldingrequired at site

Long lifetime

10

Convection bank design

Thefluegasesflowfromthebottomofthereformerradiantboxthroughfluegastunnelslocatedbetweentherowsoftubesto the reformer convection section. These gases have a temperature of approxi-mately1000-1050°C.

The heat is utilised for evaporating pro-cess condensate, superheating steam and preheatingcombustionairandfeed/steammixtures.

The flue gas exits the system via the flue gas fan at temperatures selected to prevent potential condensate formation of the flue gasandsubsequentcorrosionofthefluegas duct and/or equipment.

Convection bank design

Optimisedaccessibility

Modularised and pre-fabricated

Minimised construction costs

The Uhde Hydrogen Concept

11

Process gas

To steam generator ofconvectionbank

Process gas cooler

with steam drum

Process gas

Steam

Process gas cooler

Internalbypasswithsteam-cooleddamperbladesfortemperature control

Metallicorceramictubeinletferrules to limit heat flux

Double-layerrefractory liningofinletchamberand, ifnecessary,ofoutletchamberwithhigh-dutybricksonhotsurface

Completelyprefabricated

Process gas cooler

The process gas cooler is a horizontal fire-tubeboilergeneratingsteam.Itisdesignedfor natural circulation and is connected to thesteamdrumbyrisersanddowncomers.

Intensive research and development, strict design requirements for critical parts (such asferrulesandthebypasssystem),aproper

selection of materials and in-house thermal designarethebasisforthehighreliabilityand extremely long lifetime of our process gas coolers. Features of this design are:

• flexibletubesheets• fullpenetrationtube-to-tubesheetwelds• safe natural water circulation

11

12

from convection section

to convection section

PSA

SimplifiedUhde´sdirectprocesscondensatereusesystem

Shift conversion

AhigherconversionofCO(water-gasshift)to H

2andCO

2obviouslyreducesthefeed

demand and simultaneously reduces the calorificvalueofthefuelavailablefromthepressure swing adsorption (PSA). This, in turn, means an increase in import fuel. The differentoptionsfortheCOconversionarehigh-temperature (HT) shift, medium-tem-perature(MT)shiftoracombinationofhigh-temperature and low-temperature (LT) shift.All shift conversions are exothermic.

Adding an LT shift reactor achieves the following results:

• a reduction in feed and an increase in fuel, resulting in a marginal increase ofcombined'feed&fuel'

• an increase in steam export

• areductioninabsorbedheatduty

Therefore in case of an expensive feed and a cheap fuel, the additional investment in-volved in supplementing the HT shift with anLTshiftisjustified.TheaboveresultscanalsobeachievedbyreplacingtheHTandLT shift with a MT shift.

Heat recovery and process condensate recycle

The Uhde design incorporates efficient heat recovery in the process gas cooling train and in the flue gas duct. Part of the steam produced in the processgas cooler and flue gas duct is used asprocesssteamandthebalanceisexported.

A special feature of the Uhde technology isthattheprocesscondensateobtainedfromunconverted surplus steam is directly uti-lised to generate part of the process steam.

Thisisdonebycollectingthecondensateinthe cooling train downstream of the shift con- verter, then preheating and evaporating it.

The steam produced is used exclusively as process steam. This totally eliminates the need to return process condensate to aboilerfeedwatertreatmentunit(e.g.strip-per) and reduces the amount of volatile organiccomponents(VOCs).

Synthesis gas purification

Pressure swing adsorption (PSA) is a well-establishedpurificationstepusedtoobtainhigh-purity hydrogen (99.9% and higher). It uses an adsorption system where gaseous impuritiessuchasCO,CO

2 and CH

4 are ad-

sorbedathighpressureanddesorbedatlowpressure. The PSA unit is supplied as a package unit.

Process condensate recycle

Direct reuse of process con- densate to generate process steam

Nostripperrequiredandthere- forenoemissionsofVOC's

Clean export steam from demineralised water

Successful operation for more than two decades

The Uhde Hydrogen Concept

1313

Praxair Inc., USA

14

What we offer our customers

Value improvement process (VIP)and Capex/Opex optimisation

We at thyssenkrupp Industrial Solutions placeparticularimportanceoncollaborat-ing with our customers at an early stage to combinetheirambitionwithourexperiencein a special value improvement process. This results in tailor-made design solutions jointly worked out with our customers to achieve an optimum CAPEX/OPEXbalance.For example, the modularisation of key componentsandcompletelyprefabricatedmodules minimises site works and construc- tion costs, maximises supply quality and ensures easy transportation. Moreover, the

• unit cost of feedstock• unit cost of fuel• steam export credit

are important factors which also need to betakenintoaccountinprocessconfigu-ration and hence process optimisation considerations.

Health, safety and environment

In awareness of our environmental respon-sibility,Uhdehydrogenplantsaredesignedfor minimised environmental emissions.

Take,forexample,theburnersusedinourreformers. We install only special down-firingforced-draughtburnersofwell-provendesign from the world's leading manufac-turers.Theseensureextremelystableandcompletecombustion,allowthepropermix-

ing of air and fuel even at higher excess air levels and have defined flame profiles over a wide range of fuels. The proper mixing of air and fuel, the recirculation of flue gas and airandfuelstagingensurelowNO

X levels.

The complete in-situ reuse of process con-densate also ensures that environmental emissions are minimised and uncontami- natedHPsteamcanbeexported.There-fore, no process condensate stripping is needed and there is no venting of dissolved gases to atmosphere.

Moreover, to ensure the safety of operating personnel, we offer special training pro-grammes.

PDVSA PetrocedeñoS.A.,JoseRefinery,Venezuela

Thetwo-trainplanthasacapacityof196,000Nm3/h H2

and is integrated into a large crude oil upgrader complex.

Research and development

In order to prepare thyssenkrupp Industrial Solutions for the future, we place great em- phasis on research and development to further improve its technologies. Using in-house simulation tools to improve the existing technology and design. The accu-racy of our simulations and process design arebackedbythemanyreformerswehavedesignedandbuilt.

Inrecentyears,catalystsandburnerde-signs as well as heat and condensate recovery,amongstothers,haveallbeenimproved.

thyssenkrupp Industrial Solutions´ services

thyssenkrupp Industrial Solutions provides the entire spectrum of services associated with an EPC contractor, from the initial fea-sibilitystudyandprojectmanagementrightup to the commissioning of units and grass-rootsplants.Ourlargeportfolioofservicesincludes:

• feasibilitystudies/technologyselection• project management• arranging financing schemes• financialguidancebasedonan

intimate knowledge of local laws, regulations and tax procedures

• environmental studies• basic/detailengineering• utilities/offsites/infrastructure• procurement/inspection/transportation

services• construction work• commissioning• training of operating personnel• plant operation/maintenance.

At thyssenkrupp Industrial Solutions we are dedicated to support the success of our customersintheirlineofbusinessandtoprovide them with a wide range of services toensuresustainableinvestments.

Withthisinmindweliketocultivateourbusi- ness relationships and our after-sales service includes regular consultancy visits which

keeptheownerinformedaboutthelatest developmentsorrevampingpossibilities.

Low maintenance requirements

There are no components in an Uhde steam reformerthathavetobereplacedorthatneed metallurgical checks on a frequent basis,e.g.hotpigtailsorhotmanifolds.Thefollowingdesignfeaturesbasedonyearsof experience have reduced the amount of maintenance work required to a minimum:

• lessburnerscomparedtoside-firedreformers

• box-typedesignwithflatwallsthatreducethenumberofcriticalareaswithregard to the refractory lining

• onereformerboxonly,evenforlargecapacities

• maintenance-freetubeandinlet suspension system

• pigtailsdesignedforfullflexibility• cold outlet manifold system.

There is no other design which has suc-cessfullycombinedlonglife,simplicity,maintainability,operability,safety,reliability,and cost effectiveness.

Training programmes

As part of our services, thyssenkrupp Industrial Solutions also offers training pro-grammes to enhance the skills of the plant operating crew.

The policy of the thyssenkrupp Industrial Solutions group and its affiliates is to en-sure utmost quality in the implementation ofourprojects.Ourheadofficeandaffili-ates worldwide work to the same quality standard, certified according to DIN/ISO9001/EN29001.

Uhde hydrogen technology stands for tailor-made concepts and international com- petence. For more information contact one of the thyssenkrupp Industrial Solutions offices near you or visit:www.thyssenkrupp-industrial-solutions.com

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InfracorOxeno,

Marl, Germany

Reality meets design: Thermal

image of an outlet manifold system

Koch-Glitsch A.S.,

Novopolotsk,Belarus

Capacity:39,000Nm3/h H2

Industrial Solutions Fertilizer and Syngas Technologies

thyssenkrupp Industrial Solutions AG Friedrich-Uhde-Straße 15 44141 Dortmund Germany P: +49 231 547 0 F: +49 231 547 10 www.thyssenkrupp-industrial-solutions.com

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