Module No.

13 : Utilities

Unit No. 5- Hydrogen generation

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UNITS IN THIS COURSE

UNIT 1 UNIT 2 UNIT 3 UNIT 4 UNIT 5 DESALINATION WATER TREATMENT STEAM GENERATION BOILERS NITROGEN GENERATION HYDROGEN GENERATION

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

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TABLE OF CONTENTS
Para 5.0 5.1 5.2 OBJECTIVE USES OF HYDROGEN GAS IN THE REFINERY HOW THE HYDROGEN GAS IS PRODUCED 5.2.1 5.2 2 5.2.3 5.2.4 REFORMER FURNACE REFORMER CHEMICAL REACTIONS SHIFT CONVERTOR REACTOR PRESSURE SWING ABSORPTORS (PSA'S) 5.2.4.1 PSA REGENERATION Page 3 4 4 4 6 6 7 7

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

5.0

OBJECTIVE

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As a plant operator, you should have a general knowledge and understanding of how your Company operates their hydrogen generation equipment. This unit will explain the following things: Why oil processing plants (refineries) need hydrogen gas How the hydrogen gas is produced.

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

5.1

USES OF HYDROGEN GAS IN THE REFINERY

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Pure hydrogen gas is needed in the following processes. The hydro-cracker The reformer The hydro-desulphuriser (hydro-kimmer desulphuriser)

How these processes work will be explained in other modules. 5.2 HOW THE HYDROGEN GAS IS PRODUCED The process changes natural gas into hydrogen and carbon dioxide gas. This is done by mixing the natural gas with superheated steam at very high temperature in the presence of a catalyst. The natural gas that feeds the process (the feedstock), contains methane, (CH 4), ethane, (C2H6) and some propane, (C3H8). The feedstock also contains Impurities that have to be removed. These impurities are mercaptans (RSH), carbon dioxide (CO 2), and hydrogen sulphide (H2S). The feedstock is pre-treated to remove these impurities. The pre-treatment is done by passing the feedstock through a hydrogenator reactor and then through desulphuriser adsorptors. Recall that the hydrogen unit operates at high temperature. The feedstock is preheated by a preheat heat exchanger. If this heat exchanger is out of service we can pass the feedstock through a gas fired heater. This heater is normally on standby. The main part of the process takes place in the reformer furnace. 5.2.1 REFORMER FURNACE Extra heat energy is given to the incoming superheated steam.

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

This is done by passing the steam delivery tubes through the hot exhaust gases in Page 9/8

the reformer furnace. The very hot, super-heated steam is then mixed with the clean hot feedstock gas. The mixture of super heated steam and feedstock gas then passes through the tube bundles inside the reformer furnace. The tube bundles contain a solid catalyst. The catalyst used is a nickel alumina based catalyst. The feedstock gas is reformed in the furnace tube bundles in an endothermic chemical reaction. Recall that enclothermic means that the reaction takes in heat energy in order to happen. The reformed gas contains the following products. Hydrogen (H2) Carbon monoxide (CO) Carbon dioxide (CO2) Methane (CH4) Steam (H2O)

The chemical reactions that produce these products are given below. You will see that there are two reactions. The second reaction converts the carbon monoxide produced in the first reaction to carbon dioxide. Note -that some of the carbon monoxide is not converted to carbon dioxide. That is why we have carbon monoxide in the produced gas exiting the reformer furnace. Some of the methane also passes through the reformer unchanged.

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

5.2.2

REFORMER CHEMICAL REACTIONS

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1 st Reaction Methane: CH4 CO C2H6 2CO C3H8 3CO + + H2O H2O

2nd Reaction 3H2 H2 4H2 2H2 7H2 3H2 + + + + + + CO } CO2} 2CO} 2CO2} 3CO} 3CO2}

Final Product 4H2 +CO2

Ethane:

+ H2O + 2H2O + + 3H2O 3H2O

6H2 + 2CO2

Propane:

10H2 + 3CO2

This hot raw hydrogen product is then passed through a heat exchanger. There, some of its heat energy is used to generate steam. This cools the raw hydrogen product. The cooled hydrogen product is then passed through a shift convertor reactor vessel. 5.2.3 SHIFT CONVERTOR REACTOR In the shift convertor any carbon monoxide present in the hydrogen product reacts with the steam to give more hydrogen and carbon dioxide. CO + H2O --> H2 + CO2 We now have a raw hydrogen product containing a lot of carbon dioxide gas. Recall the hydrogen product also contains some methane, some carbon monoxide and, of course, some water (steam). These product impurities must be removed. This is done in special vessels called pressure swing adsorptors. (PSA's) Before passing through the pressure swing adsorptors the raw hydrogen product is cooled in a cooler.

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

5.2.4

PRESSURE SWING ABSORPTORS (PSA'S)

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The PSA's remove any CO, CO2, CH4, and water. The PSA's contain molecular sieves. Pure hydrogen product leaving the PSA's is 99.9% pure. 5.2.4.1.PSA REGENERATION How the PSA's are regenerated is clever, but simple. Recall that fluids always flow from high pressure to low pressure. The pressure is reduced in the PSA which needs to be regenerated. This is done by closing the inlet valve and the product outlet valve. The purge valve is then opened. When the pressure inside the PSA is lowered to a set point the product outlet valve is reopened. Pure hydrogen product then backflows through the PSA and out of the purge valve. This purge gas removes the adsorpted impurities. It is then used as fuel gas for the reformer furnaces. When the regeneration is complete the purge valve is closed. Pure product hydrogen continues to flow into the PSA until the pressure in the PSA is the same as the pressure in the product header. The inlet valve is then opened and the PSA is back on stream. This whole process is controlled by a computer programme.

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Module No. 13 : Utilities

Unit No. 5- Hydrogen generation

Hydrogen Generation Unit - Simplified Flow Diagram Page 15/8

Figure 5.1

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