Hydrogen generation for modern refineries

Luigi Bressan, Guido Collodi and Fabio Ruggeri Foster Wheeler Italiana SpA

ith increasing demand for diesel, more stringent product specifications for cleaner fuels, reduced fuel oil demand and the economic advantages in processing heavier sourer crudes, the demand for hydrogen in refineries continues to grow. As a result, a modern 10 mmtpa refinery will often require 150 000 Nm3/hr or more of hydrogen. This demand can be met by applying a systematic, cost-effective approach to hydrogen management, including the optimisation and revamp of existing hydrogen generation facilities. The paper will focus on the design of a modern hydrogen production unit based on steam reforming of hydrocarbons using a Foster Wheeler Terrace-Wall furnace. It will look at some of the key features of this design that deliver benefits in operation and maintenance, and the high availability that is essential in hydrogen production.

which converts feedstock and steam to syngas at high temperature and moderate pressure The third section is the syngas heat recovery and incorporates CO shift reactor/s to increase the hydrogen yield The final section is raw hydrogen purification, in which modern plants employ a pressure swing adsorption (PSA) unit to achieve the final product purity In addition to the core process sections, compression is often needed to raise the feedstock and product hydrogen pressures. SMR is a mature technology and is now less likely to yield any large step-changes in economic benefit from technological developments. Incremental economic improvements by means of a continuous improvement programme are the order of the day.

Chemistry
The reforming reaction between steam and hydrocarbons is highly endothermic and is carried out using specially formulated nickel catalyst contained in vertical tubes situated in the radiant furnace of the reformer. The simplified chemical reactions are:
For saturated hydrocarbons CnH2n+2 + nH2O = nCO + (2n+1)H2 For methane CH4 + H2O = CO + 3H2 delta H = + 206 kJ/mol

Steam reforming principles

Hydrogen is increasingly being considered as a utility gas within the refining and petrochemical industry. From an end users perspective, investment in hydrogen plant capacity is often evaluated using the lifecycle cost of hydrogen, expressed, for example, as Euros per Nm3. This is because the plant with the lowest capital cost may not always produce the cheapest hydrogen, given the feedstock and utility costs commonly experienced today. For many years, steam methane reforming (SMR) plants have continued to be the leading technology for generation of hydrogen in refining and petrochemical complexes. These plants consist of four basic sections: The first is feedstock treatment where sulphur and other contaminants are removed The second is the steam methane reformer,

In the adiabatic CO shift reactor vessel, the moderately exothermic water gas shift reaction converts carbon monoxide and steam to carbon dioxide and hydrogen:
CO + H2O = CO2 + H2 delta H = -41 kJ/mol

The PSA purification unit removes by adsorption

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Figure 1 Hydrogen production plant process flow scheme

from the hydrogen the resulting CO, CO2 and CH4 gases. The four process sections can also be seen in Figure 1 of a typical SMR hydrogen plant, in which the reformer stands at the centre and the PSA is on the right.

Today, in most cases, feedstock and fuel and steam have the same value on a calorific basis and, as consequence, the optimum is achieved with the minimisation of the following mathematical formula:
( Feedstock(Gcal/h) + Fuel(Gcal/h) - Steam(Gcal/h) ) / H2 flow rate (Net thermal efficiency)

Hydrogen plant in a refinery

Refineries can use different feedstocks to produce hydrogen, such as natural gas, refinery gas, LPG, light naphtha, heavy naphtha and even straightrun naphtha, depending on their internal value and availability, to assure the availability of the most economical feedstock to the hydrogen plant. The characteristics of the feedstock will define the processing capability of the plant. However, the correct selection of the hydrogen plant design and operating parameters depends on the economic values attributed to the feedstock, the fuel and the steam produced, these being the key process streams influencing the economics of the plant.

where steam is the net export flow rate of steam from the plant.

Key process elements

Hydrodesulphurisation section

The feedstock is first hydrotreated and the resulting H2S is captured in a zinc oxide bed. There are different desulphurisation schemes available, but the most commonly used is the lead-lag arrangement eventually followed by a deep desulphurisation polishing bed. The reaction temperatures are obtained by thermal exchange.

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Pre-reforming section

The pre-reforming section is generally installed to eliminate long-chain hydrocarbons in heavier feedstocks before entering the reforming section; this allows the use of reduced steam-to-carbon ratios. When natural gas is used as feedstock, the use of a re-reforming section lowers the reforming duty, thus reducing the cost of the steam reformer, which is the most expensive part of the plant; for this reason, it is recommended that large-sized plants should have a pre-reforming section.
Reforming section

The reforming section is the key section of the plant; Foster Wheeler uses its proprietary Terrace Wall technology. Steam reformer outlet temperatures up to 920C can be used with heat fluxes above 100 000 Kcal/(h*sqm). The process effluent from radiant cell is sent to the process gas boiler, through the outlet manifold, outlet cone and transition piece. The hot gases leaving the radiant section are cooled down in the convection section located on the radiant top, preheating the process stream, the prereformer feed stream, if any, the feed gas to desulphurisation unit and producing superheated steam. The required heat is supplied with ultra-lowNOX burners (forced or natural draft). Burners are placed at two different levels in the combustion chamber and they are equipped with a double set of firing tips, one for refinery fuel gas and one for vent gas from PSA unit. The steam produced in the convection section and in the process gas boiler is separated from water in the steam drum, placed above the convection section. The process gas boiler is natural circulation type and it is placed at grade level in the middle of the radiant cell. Such an arrangement allows a transfer line to be avoided.
Syngas cooling and shift reaction section

Isothermal shift. The adoption of the second option as an alternative to the first option is a matter of economics; both alternatives need a steam-to-carbon ratio above 2.7 and this may influence the economics when export steam has a high economic value. The process steam consumption can be reduced when both the medium temperature and the isothermal shift are adopted (unless steam is needed in the pre-reforming section). The medium-temperature shift may generate excessive amounts of methanol in the syngas stream, with possible contamination problems unless design precautions are taken. When natural gas only is considered as feedstock, it is possible to adopt steam-to-carbon ratios below 2.0.

PSA section

Hydrogen purification is obtained using the wellknown PSA technology. The process parameters need to be carefully defined in order to optimise capital cost. An unnecessarily stringent specification in the hydrogen purity may cause undesired and unnecessary capital cost; an example is the residual concentration of nitrogen that should not be less than 100 ppm. The proposed scheme is outlined in Figure 1. With the indicated scheme, a net thermal efficiency of less than 3.0 Gcal/Nm3 of produced hydrogen can be easily achieved.

Foster Wheeler Terrace-Wall steam reformer

The patented Terrace-Wall steam reformer heater is a side-fired heater with burners located along lateral walls, with flames vertically arranged. The catalyst tube section is composed of a single row of vertical tubes, heated from both sides and aligned inside the radiant cell. The catalyst tubes are flanged at the top in order to allow the loading and unloading of the catalyst. The reformer heater features a radiant section consisting of a firebox containing a single row of catalyst tubes, with two terraces on both sides of the tubes on which the burners are installed.
Key advantages

The syngas cooling section is normally optimised using pinch technology aimed at finding the optimum cooling scheme. For the shift reaction section, there are four options available: High-temperature shift High-temperature shift followed by a lowtemperature shift Medium-temperature shift

The following are the main advantages of the Terrace-Wall design: A single train unit can produce up to about 200 000 Nm3/h of hydrogen

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Modular radiant section capability, reducing site construction time and cost Can operate in natural draft mode Steam reformer outlet temperatures up to 920C can be used with heat fluxes above 100 000 Kcal/(h*sqm). Very compact design, reducing the plot area requirement Minimum number of low-NOx burners Operating cost saving (reduced number of rotating machines) Maintenance cost saving (very simple design) Investment cost saving. Foster Wheeler Terrace-Wall reformers have been in operation for many years with a very wide range of feedstocks and have been used for hydrogen, methanol and ammonia production. This technology offers several advantages over competing technologies; namely: High flexibility to handle a full range of feedstock from natural gas to heavy naphtha Uniform heat flux distribution, giving a long reformer tube life Sloped walls with two firing levels, enabling control of flux density along the catalyst tube High reliability Positive reformer furnace firing control Low maintenance requirement. The specific advantages of sloping walls include avoiding tube hot spots and prolonging tube life: The inclined Terrace-Walls are uniformly heated vertically by the rising flow of hot gases, with each terrace capable of being independently heated to provide the particular heat flux desired in its zone. The operator can match the vertical heat flux to the process heat demand within the catalyst tube. Controlled delivery of heat to the reformer catalyst tubes helps control hotspots, which can reduce the design life of the tubes The incline of the wall also localises the effectiveness of the terrace to that portion of the heat-absorbing surface directly opposed to it. Actual experience has shown that the TerraceWall design accomplishes this to a far great extent than any flat wall construction, and is distinctly better than in down-fired designs Flame impingement on catalyst tubes is practically impossible in the Terrace-Wall design.

Continuous improvement and development

Recent developments to further enhance the design and performance of the Terrace-Wall reformer include: Modified geometry of the radiant section to tailor flux profile and improve thermal efficiency without increasing catalyst tube temperature Outlet pigtails arranged vertically, providing better access for an easier welding and nipping, which dispenses with the need for a cold bottom flange for catalyst removal. Vacuum-type catalyst removal systems allow removal of catalyst via the tube inlet flange Reduced number of burners by about 30% due to increased capacity with the new burners using staged fuel and staged air combustion techniques for lower NOx emissions.

Conclusions
Todays refineries face the tremendous challenge of meeting an increasing demand for cleaner transportation fuels, as specifications continue to tighten around the world and markets decline for high-sulphur fuel oil. Innovative ideas and solutions to reduce refinery costs must always be considered, including: Identification and optimisation of the hydrogen distribution network Use of hydrogen recovery technologies to maximise availability and minimise capital investment Multiple feedstock, utility and steam options Economic evaluation of solutions Optimisation of new plant capacity. Significant experience and expertise in optimising and revamping existing hydrogen systems can help our customers in finding the lowest cost route to meeting their hydrogen needs. If a new hydrogen plant is required, it is important that it is right sized in line with the clients business objectives and with current and potentially future needs.

LinkS
More articles from: Foster Wheeler USA More articles from the following category: Hydrogen Management

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