ABSTRACT.KUNMING SEMINAR

HYDROGEN PRODUCTION VIA REFORMING AND ITS ECONOMICS

By

Sergio Martinez MSc. Chem. Eng.

President of Pan American Enterprises Inc

ABSTRACT

The process, equipment and key plant project of the production of pure hydrogen via steam reforming of feedstock hydrocarbons like natural gas, LPG, methanol etc., is presented in this paper. An overview of the economics of hydrogen production is provided as reference and comparison with high pressure gas purchases and standard electrolytic processes.

1.0 PROCESS MECHANISM

OVERALL SUMMARY

Hydrogen is generated by a Steam/Hydrocarbon Reforming process, which consists of a catalytic reaction of a hydrocarbon stream, with water steam at high temperatures (between 1450°F (787oC) and 1550°F (843oC)), in a direct-fired furnace. Additional Hydrogen is generated by passing the reformed gas stream through a subsequent high temperature shift conversion process, which consist of a catalytic reaction of carbon monoxide and excess water at approx. 700°F (371oC).

The reformed gas impurities (such as CO, CO2, H2O, N2 and CH4) are removed in a hydrogen purification unit (HPU) employing fixed bed adsorbers, producing ultra high purity hydrogen.

Fuel for the reformer furnace will be vent gas recovered from the HPU, supplemented by feed stock gas.

The steam required for the process is generated by waste heat recovered from various locations in the hydrogen plant, making the plant self sufficient. Export steam can be generated when economics permits.

The plant is highly automated, suitable for semi-unattended operation, with a control panel locally installed on the skid or with an optional control from a remote central control system.

The process description can be followed by referring to the attached process flow diagram. The process steps for the production of hydrogen may be summarized as follows:

1. Feed stock Desulfurization

2. Steam/Hydrocarbon Reforming

3. Carbon Monoxide Shift Conversion

4. Gas Cooling

5. Hydrogen Purification (by Fixed Bed

Adsorption)

6. Off Gas Recovery as Fuel

7. Steam Generation

1.1 FEED DESULFURIZATION

The Hydrocarbon gas feedstock may contain sulfur compounds (H2S, R-SH,COS), which are a poison to both the reformer and shift conversion catalyst and thus must be removed prior to reforming. The f irst step in the feed stock preparation is to remove the sulfur compounds to less than 0.2 ppm. (v) by reaction with zinc oxide which adsorbs the sulfur compounds.

ZnO (s) + H2S (g) + Heat -------> CO2 (g) + H2 (g)

The feedstock is preheated to approximately 750°F (399oC) by heat exchange with the HTS effluent and passed over a bed of zinc oxide, which reacts with any hydrogen sulfide that is present. The bed is sized to provide protection for at least one year without replacement of the zinc oxide.

1.2 STEAM HYDROCARBON REFORMING

The desulfurized hydrocarbon on flow control is mixed with steam and is heated to approximately 700°F (371oC) in the Steam/Gas Preheat Coil located in the convection section of the reformer. The mixture is then passed through catalyst; the feedstock reacts with steam to produce hydrogen and carbon oxides by the following symbolic equations:

CnHm(g)+H2O(g)+Heat----> nCO (g) + (m/2+n) H2 (g)

CH4 (g) + H2O (g) + Heat -----> CO (g) + 2 H2 (g)

CO (g) + H2O (g) ----------------> CO2 (g) + H2 (g) + Heat

The first reaction is the reforming reaction; whereas, the second reaction is the shift reaction. Both reactions produce hydrogen, each being limited by chemical equilibrium. The net reaction is endothermic, with the heat supplied by combustion in the radiant zone of the furnace. The reforming reaction takes place under carefully controlled external firing conditions. The combustion gases leaving the reformer are used to superheat the mixture of feed gas and steam then fed into the waste heat boiler.

The reformed gas exiting the catalyst tubes will consist of H2, CO, CO2, CH4, H2O and inert (if present in the feedstock). The percentage composition will approach equilibrium at the design outlet conditions of approx. 1550°F (843oC).

1.3 CARBON MONOXIDE SHIFT CONVERSION

The process gas stream exiting the Reformer is quenched in the Desuperheater and conditioned to approx. 700°F (371oC) for the second reaction in the shift converter. The temperature is automatically controlled varying condensate flow to the desuperheater. Heat from these gases leaving the exothermic reaction of the shift converter is used to preheat feed gas. Shift conversion produces additional hydrogen by the reaction.

CO (g) + H2O (g) --------------> CO2 (g) + H2 (g) + Heat

The reaction is limited by equilibrium and the equilibrium is favored by low temperature.

The High Temperature Shift Converter contains an iron-chromium catalyst, which converts approximately 65% percent of the incoming carbon monoxide by the shift reaction. The temperature of the gas leaving the High Temperature Shift Converter is approximately 790°F (421oC).

1.4 GAS COOLING

Final cooling of the gas to 100°F (38oC) is accomplished by heat exchange with cooling water in the Process Cooler.

The cool process gas flows to the Process Knock-Out Drum and then to the Hydrogen Purification Unit.

1.5 HYDROGEN PURIFICATION UNIT (HPU) BY

PRESSURE SWING ADSORPTION

1.5.1 PROCESS DESCRIPTION

The HPU Unit is designed and employs a pressure swing adsorption process (PSA) to purify the feed streams rich in hydrogen coming from various processing units and will produce a high purity hydrogen product stream up to 99.95%. The process uses 4 or 6 combined adsorbent beds to provide a continuous flow of pure hydrogen product. The absorbers operate in cascade on an alternating cycle of adsorption and regeneration. One of the four adsorber vessels is always in the adsorption step, while the other three are in various stages of regeneration.

The HPU operates in a continuous mode and is automatically controlled with a local or remote PLC. All control valves are actuated by an electric/pneumatic control system. All controls are built in the operator interface to regulate times, pressures and flows. The capacity of the unit can be regulated automatically from 100% of design to a minimum of 30 % with the possibility of approaching to zero by the master control rate built in the PLC. At the lower capacities, the hydrogen recovery will decrease unless the cycle time is increased. The cycle time is remotely regulated automatically. Alternatively the HPU can use 6 adsorber vessels (V-501 A-F), including a waste gas surge tank. The alternate HPU Unit is described as Q-PSA and uses 2 multiport valves. The multiport valves, ranging from 6” to 24” in

diameter, are made of advanced composite materials enabling them to rotate and seal with minimal friction. This reduces wear and allows the valves to operate at several cycles per minute without degrading performance. Virtually no maintenance is required.

This is a newly developed technology in Pressure Swing Adsorption which provides an effective and energy efficient gas separation process. While in a conventional HPU, a valve skid coordinates the flow of gas through a number of columns filled with adsorbent which trap certain gaseous impurities at high pressure while allowing pure hydrogen pass by and working in a complex sequence as indicated above, the Q-PSA Unit uses only 2 multiport valves which replace the series of 24 separate valves on the top and bottom of each adsorbent bed, eliminating the valve trains of conventional HPU.

1.6 OFF-GAS RECOVERY AS FUEL

The off gas from regenerating the HPU absorbers flows to the HPU Vent Tank from which it is sent on flow control to the reformer burner to provide a significant portion of the fuel requirements.

1.7 STEAM GENERATION

Steam generation using the heat in the reformer flue gas and the process gas satisfies the process steam requirements.

Instrumentation is provided to automatically adjust the amount of steam generated by auxiliary firing as steam demands varies.

The steam system generates 200 psig (13.79 bar) saturated steam. This system consists of a Waste Heat Steam Generation System located in the reformer convection section.

2.0 HYDROGEN PLANT MAIN EQUIPMENT

DESCRIPTION

2.1 REFORMER FEATURES

The Reformer is a cylindrical, up-fired, up-feed flow design. The shell will be internally insulated with high temperature blanket insulation. Ambient air is prevented from entering the furnace with insulating collars around each tube top and bottom.

A platform will be provided at the top of the Reformer for catalyst tube loading and an intermediate step-off platform for thermocouple access. A caged ladder will be provided f or access to the platforms.

Catalyst tubes are centrifugally cast. The tubes will be supported from the top and allowed to expand downward. Each tube will have a flange on the top and bottom for quick and easy change of the catalyst without requiring the removal of the catalyst tube.

Each tube inlet and outlet will be connected to a trombone loop. The loops will be connected at the other end to an inlet and outlet header.

Air tight, bottom access peep doors will be provided in the Reformer for viewing the catalyst tubes. The quantity provided will depend on the number of tubes. A side entrance access door with peep door will be provided on the lower section of the Reformer.

A burner(s) will be provided as the heat source for the Reformer. The burner will be designed to burn the HPU waste gas plus a customer supplied make-up fuel. The burner will be provided with an electric ignition for the pilot and a safety monitoring system.

2.2 DESULFURIZER

The Desulfurizer is a vertical pressure vessel equipped with one loading nozzle and one cleanout nozzle. The cleanout nozzle will be fitted with a catalyst hold back plate. A bucket screen is attached to the outlet to prevent catalyst from entering the piping systems. The bottom head is filled with ceramic balls to provide even gas distribution through the catalyst bed. The vessel will be insulated with calcium silicate and the loading and cleanout nozzles will be insulated with blanket covers. The vessel will be supported by a skirt with an inspection port and three vents.

2.3 HIGH TEMPERATURE SHIFT CONVERTER

The HTS Converter is a vertical pressure vessel equipped with one loading nozzle and one cleanout nozzle. The cleanout nozzle will be fitted with a catalyst hold back plate. A bucket screen is attached to the outlet to prevent catalyst from entering the piping systems. The bottom head is filled with ceramic balls to provide even gas distribution through the catalyst bed. Ceramic balls are placed above the catalyst bed to insure the integrity of the catalyst during startup and shutdown. The vessel will be insulated with calcium silicate and the loading and cleanout nozzles will be insulated with blanket covers. The vessel will be supported by a skirt with an inspection port and three vents.

2.4 HYDROGEN PURIFICATION UNITS

The HPU Adsorber is a vertical pressure vessel equipped with one loading nozzle/manway. Bucket screens are attached at both the inlet and outlet to prevent adsorbent from entering the piping system. The bottom head is filled with ceramic balls to provide even gas distribution

through the adsorbent bed. The vessel is supported by a skirt

with an inspection port and three vents. Cyclic analysis is performed to determine the fatigue life of the vessel. The vessel is post-weld heat treated due to process conditions.

2.5 WASTE HEAT BOILER

The Waste Heat Boiler is a fire tube type boiler. The plenums will be internally insulated with eight pound density, ceramic fiber blanket. The boiler shell is externally insulated with calcium silicate. Manways will be provided. The vessel will be post-weld heat treated. The tube sheets will have a J-bevel preparation and access to the tubes will be provided by incorporating flange end closures.

2.6 VESSELS AND HEAT EXCHANGERS

Vessel and heat exchanger design and fabrication will be in accordance with Section VIII, Division I, of the latest ASME Code for Unfired Pressure Vessels. Spot radiograph will be provided for all vessels as a minimum.

2.7 PIPING AND VALVES

All piping systems will be designed and fabricated in accordance with ANSI B31.3 and other applicable ANSI, ASME and PFI codes and standards. The equipment spacing will be as close as is practicable to allow accessibility and yet minimize hydraulic and heat losses.

2.8 INSTRUMENTATION/CONTROL SYSTEM

The control system shall operate from a programmable logic controller (PLC), located either remotely or skid-mounted. From this point, the plant capacity can be changed from 50% capacity to 100% capacity simply by adjusting one controller. Local control loops will be pneumatic; remote instrumentation will be electronic and be completely controllable from Control Room or local control panel mounted on skid.

Local indicating instruments, pressure gases, temperature indicators, and level gages will be supplied to permit the operating plant to be adequately monitored.

Plant can be designed to control and monitor the operation remotely from any part of the world via internet.

Relief valves will be supplied to meet the requirements of ASME Section I and VIII and API RP500.

A flame safeguard system will be supplied with pre-wired field terminal box to monitor the Reformer flame and to shutdown the fuel system in the event certain parameters deviate from the desired control points. A similar system will be employed for the auxiliary burner. As an option, a qualitative product analyzer could be supplied to continuously monitor product impurities (Range 0-1% CO).

2.9 ELECTRICAL SYSTEM

The electrical equipment shall be designed for hazardous area classification, Class I, Group B, Division II. Electrical equipment in the Reformer area will be classified as non-hazardous, weatherproof.

Motor start/stop stations will be provided and wired to the motor junction boxes. Installation of power wiring from the MCC to motors will be by Client. MCC will be supplied by Client.

All electric motors greater than 3/4 HP shall be 480/220V/3 phase/60 cycle Hertz. Smaller motors and instruments shall be 110V/1 phase 60/Hertz. All motors shall be TEFC. Motor Control Center furnished by Owner.

All 3 Phase electrical motors will be furnished with stop-start pushbuttons on the skid unit.

Control wiring will be 110 or 24VAC.

Wiring shall be done to latest issue of National Electric Code and IEC for transformers when required.

2,10 CATALYST AND ADSORBENTS

The catalyst and adsorbents typically have an operating life as follows:

Catalyst Expected Fife

Reformer 5

Desulfurizer 2

HTS Converter 2

Adsorbents

Adsorbent H-1 10

Adsorbent H-2 10

3.0 HYDROGEN PLANT FEATURES

3.1 DESIGN FEATURES OF THE HYDROGEN GENERATING PLANT.

? Modular design for easy transportation and installation.

? All pipe racks pre-assembled in the shop.

? All elevated equipment is skid mounted.

? Fully automatic operation designed for semi-unattended operation.

? Automatic turndown accomplished through the use of a master production rate controller.

? All heat exchanger bundles fully accessible for maintenance.

? All control valves located at grade or on platform for accessibility.

? Quiet operation. From experience, during normal operation, the maximum noise level will not exceed

88 dB when measured one meter from the device.

? High flexibility in accommodating feed gases of varying composition.

? High operating reliability with minimal unplanned downtime.

? Quick and easy removal and replacement of Reformer catalyst without removing the catalyst tube

via platform access and top and bottom tube flanges.

? All vents routed to a common header and vented above all operating platforms.

? Fail safe emergency shutdown system to guard against process upsets caused by loss of utilities. 3.1 GENERAL SCOPE OF SUPPLY

Contractor’s scope of responsibility for a project, within battery limits, includes the following:

? Process Design

? Detail Design

? Procurement of Equipment and Materials

? Fabrication and assembly of modules

? Supervision Field Assembly and Installation

? Commissioning and Start Up

? Training

Items to be completed by Purchaser includes:

? Shipment of modules to the job site.

? Import of Plant Equipment, Site Preparation.

? Civil works, (including foundations).

? Piping and wiring for utilities to Hydrogen Plant modules terminal points.

? Product piping from modules terminal point

? Plant lighting, fire protection

? Permits, taxes and any other fees required for plant installation and operation.

3.2 PERFORMANCE SPECIFICATIONS

Performance specifications for a typical hydrogen generation plan with a capacity of 150 Nm3H.

3.2..1 QUALITY AND QUANTITY OF HYDROGEN PRODUCT

New Plant

Quantity, Nominal Plant Capacity:

Nm3H, max. 150

SCFH, max. 5,598 Hydrogen Purity,

(Mole % Min.) 99.95

Impurities:

- CH4, < 10.0 (ppmv)

- CO, < 10.0 (ppmv)

- CO2, < 10.0 (ppmv)

- H20, 1.0 ppmv or less

- O2< 1 (ppmv)

- N2, Balance

Pressure 115 psig 7.93 bar Temperature 1145oF 46oC

Note: SCFH means “Standard Cubic Feet per Hour”

wherein the standard conditions of Measurement

are 60°F and 14.695 psia. Nm3H means “Normal

Cubic Meter per Hour” measured at 0°C and

14.695 psia.

SCF (60°F at One Atmosphere)

1 NCM = 37.3

2 SCF

1 bar = 14.5 psi

3.2.2 HYDROCARBON GAS FEED COMPOSITION

Component Mol. Percent Methane CH490.3 Ethane C2H6 6.6 Propane (+) C3H8 3.1 Total 100.0 H2S Content =<10.0 ppmv Pressure: 200 psig 13.8 barg Temperature: 77oF 25oC

3.2.3 UTILITY SPECIFICATIONS

The following utilities are required at the area battery limits at the stated conditions:

Boiler Feed Water Make Up

Pressure: 30 psig 2.06 barg Temperature: 77oF 25oC Demineralized by Owner: Chloride less than 4 ppmv

Cooling Water:

Pressure: min. 50 psig 3.45 barg Temperature, ° F. max 77°F w/18°F Max. Temp. rise

25°C w/10°C Max. Temp. rise Electricity: 220/110 volts, 3 phase 60 Hz.

Nitrogen: For Testing and Purging

(Hydrocarbon free, less than 5 ppm Oxygen)

Pressure 109 psig (dry) 7.5 bar (dry) Temperature AMB. AMB. Instrument Air: Pressure, min. 125 psig 8.6 bar Dew Point -40°F -40°C Ambient Air (assumed): Relative humidity, % 30 30 Normal Temperature 86oF

30oC Barometer Pressure 14.7 psia 1.01 bar a

3.2.4 UTILITIES CONSUMPTION @ 150 Nm3H (5,598 SCFH)

HYDROGEN PRODUCTION (PRELIMINARY)

The above utilities are contingent upon providing sufficient supplies for the operation of the plant as well as adequate feedstock and utilities having characteristics stated in the Design Basis.

4.0 CODES & STANDARDS

Plant will be designed and fabricated in accordance with following national and industry codes and standards where applicable:

American Institute of Steel Construction, Inc. - AISC American Iron and Steel Institute - AISI American National Standards Institute - ANSI American Petroleum Institute - API American Society of Mechanical Engineers - ASME American Society for Testing and Materials - ASTM Association of Iron and Steel Engineers, Inc. - AISE Institute of Electrical and Electronics Engineers, Inc.

- IEEE Instrument Society of America - ISA National Board - NB National Electrical Manufacturers Association - NEMA

National Fire Protection Association - NFPA Tubular Exchanger Manufacturers Association

- TEMA Uniform Building Code

- UBC International Electro Technical Commission

- IEC

All ladders, platforms, coupling guards, belt guards shall be in accordance with OSHA standards.

5.0 HYDROGEN PRODUCTION ECONOMICS

Hydrogen production via Reforming of hydrocarbons with steam or water vapor, is more economical than other forms of generation like electrolysis. About 90 % of the current hydrogen generation in the food industry is generated by reforming either natural gas or LPG.

Traditionally the hydrogenation industry in Continental America uses their own hydrogen generation plants in the range of 100 to 2,680 Nm3H. Few generate hydrogen via electrolyser or purchase their hydrogen from gas vendors. All this is driven by the constant increase of energy cost or delivery of hydrogen via high pressure tanks by local suppliers.

The minimum economic plant capacity for generation via reforming is in the range of 50 to 100 Nm3H. These size plants have the same features and characteristics that anyone of much larger capacity and they are as efficient as the bigger plants.

The following charts indicate a comparative cost of production between Reforming, electrolyses and purchase by high pressure tanks.

For additional information contact the author at H2Plant@https://www.wendangku.net/doc/6b18396587.html, , Ph: (956) 546-8297; Fax: (956) 544-7469

Standard Hydrogen Plant

Plant Design Capacity: 150-300 Nm3H Preliminary

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