BIOGAS MEMBRANE REFORMER FOR DECENTRALIZED …...required represented on a schematic plant layout....

BIONICO

BIOGAS MEMBRANE REFORMER FOR DECENTRALIZED HYDROGEN PRODUCTION

FCH JU GRANT AGREEMENT NUMBER: 671459

Start date of project: 01/09/2015 Duration: 3 years

WP2 – Industrial Specifications

D2.4 Industrial specifications

Topic: FCH-02.2-2014 - Decentralized hydrogen production from clean CO2-containing biogas Type of Action: FCH2-RIA Research and Innovation action Call identifier: H2020-JTI-FCH-2014-1

Due date of deliverable: 2016-02-29

Actual submission date: 2016-04-13

Reference period:

Document name: BIONICO-WP2-D24-DLR-AH-20160413-v04.docx Prepared by (*): AH

Version DATE Changes CHECKED APPROVED

V00 2016-02-29 First release AH NIL

V01 2016-03-18 Review on the system layout POLIMI MB

V02 2016-03-29 Corrections on the system layout AH RPM

V04 2016-04-07 Minor changes to the content POLIMI GDM

Dissemination Level

PU Public X

PP Restricted to other programme participants (including the Commission Services)

RE Restricted to a group specified by the consortium (including the Commission Services)

CO Confidential, only for members of the consortium (including the Commission Services)

CON Confidential, only for members of the Consortium

This project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 671459. This Joint Undertaking receives support from the European Union’s Horizon 2020 research and innovation programme and

Hydrogen Europe and Hydrogen Europe Research. _____________________________________________________________________ (*) indicate the acronym of the partner that prepared the document

BIONICO Industrial specifications

Proj. Ref.: BIONICO - 671459 Doc. Ref.: WP2-D24-DLR-AH-20160413_v04 Date: 2016/04/13 Page Nº: 2 of 33

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PUBLISHABLE SUMMARY Potential market applications for membrane reactor technology has been evaluated and described in terms of possible biogas producers and possible final consumers of the hydrogen produced, considering a hydrogen production target of 100 kg/day. The potential markets identified consider different industrial applications like glass production, metal processing, electronic industry, food industry and hydrogen fuelling stations. Among these applications, a small hydrogen fuelling station (80kg/day) has been selected as potential application of Bionico project. A preliminary configuration of the system to produce hydrogen from biogas with catalytic membrane reactor technology has been defined including plant specifications, general considerations for the design (location, onsite conditions, raw material specifications, noise limitations) and a preliminary process design. The process design includes general considerations (location, onsite conditions, raw material specifications, noise limitations) and a description of the process to produce hydrogen from biogas considering the balance of plant required represented on a schematic plant layout. The process proposed does not require the upgrading of biogas to biomethane, performing the direct conversion of biogas to hydrogen. Nevertheless, a pre-cleaning stage is required to remove hydrogen sulphide and other components of the biogas that could cause catalyst and membranes poisoning reducing the process lifetime



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Content

PUBLISHABLE SUMMARY .................................................................................................................. 2

1. OBJECTIVE AND SCOPE ............................................................................................................. 6

2. PLANT SPECIFICATIONS ............................................................................................................ 6

3. PROCESS DESINGS BASIS ......................................................................................................... 6

3.1. General considerations ............................................................................................................... 7

3.1.1. Plant Location .................................................................................................................. 7

3.1.2. Onsite environmental conditions....................................................................................... 7

3.1.3. Raw material specifications .............................................................................................. 8

3.1.4. Noise limitations ............................................................................................................... 10

3.2. Biogas pre-cleaning ..................................................................................................................... 10

3.3. Biogas upgrading ......................................................................................................................... 12

3.4. Biogas Reforming ........................................................................................................................ 12

3.4.1. Steam reforming process (SR) ......................................................................................... 12

3.4.2. Autothermal reforming process (ATR) .............................................................................. 13

3.5. Process Flow Diagram ................................................................................................................. 14

3.6. Plan layout .................................................................................................................................... 15

4. POTENTIAL MARKET APPLICATIONS ....................................................................................... 16

4.1. Analysis of potential market applications for biogas producers .............................................. 16

4.1.1. Current situation ............................................................................................................... 17

4.1.2. Key industry players ......................................................................................................... 19

4.2. Analysis of potential market applications for hydrogen consumers........................................ 21

4.2.1. Market research by industries .......................................................................................... 23

4.2.2. Current situation ............................................................................................................... 24

4.2.3. Processes using hydrogen ............................................................................................... 29

4.3. Selection of the potential applications in terms of biogas resource and hydrogen demand . 31

5. REFERENCE DOCUMENTS ......................................................................................................... 31



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Figures

Figure 1 Typical scheme of a FBMR. [5] ................................................................................................... 7 Figure 2 Chamusca´s landfill (left) and Landfill gas valorization plant (right). Font ENC. .......................... 7 Figure 3 Bionico preliminary PFD SR reactor plant. ................................................................................ 14 Figure 4 Bionico preliminary PFD ATR reactor plant............................................................................... 15 Figure 5 Bionico prototype layout. .......................................................................................................... 15 Figure 6 Preliminary isometric view of Bionico project prototype............................................................. 16 Figure 7 Overview of biogas utilization. .................................................................................................. 17 Figure 8. Evolution of biogas/landfill gas installed capacity [22]. ............................................................. 17 Figure 9 Evolution of biogas/landfill gas installed capacity by continent [22]. .......................................... 18 Figure 10 Biogas upgrading technology shares in EU plants [24]. .......................................................... 18 Figure 11 Biogas upgrading capacity shares in EU plants [24]. .............................................................. 19 Figure 12 Expected trend of Biogas/Biomethane potential [26]. .............................................................. 19 Figure 13 Evolution of number of biogas upgrading plants by technology [27]. ....................................... 20 Figure 14 Distribution raw material for hydrogen production [28]. ........................................................... 22 Figure 15 Cost comparison of hydrogen production by different production technologies [29]. ............... 22 Figure 16 Refineries and steam cracker in EU [31]. ................................................................................ 25 Figure 17 Global ammonia production (in tons) [32]. .............................................................................. 25 Figure 18 Global ammonia consumption [33].......................................................................................... 26 Figure 19 World electronics production evolution 2012-2020 (Million USD) [36] .................................... 28 Figure 20. Coverage transport modes and autonomy of the main alternative fuels ................................. 29



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Tables

Table 1 Onsite conditions. Source ENC.................................................................................................... 8 Table 2 Biogas composition ENC Landfill (Chamusca). Source ENC. ...................................................... 8 Table 3 Air composition ENC Landfill (Chamusca). Source ENC. ............................................................. 9 Table 4 Water composition ENC Landfill (Chamusca). Source ENC. ........................................................ 9 Table 5 List of manufacturers of upgrading units by technology [27] ....................................................... 20 Table 6 World hydrogen demand from 2008 to 2018 [30] ....................................................................... 23 Table 7 World flat glass demand [34]. .................................................................................................... 26 Table 8 Steel World Production [35]. ...................................................................................................... 27 Table 9 Subsector global production [35]. ............................................................................................... 27 Table 10 Standard hydrogen production capacities of the hydrogen refueling. ....................................... 29



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1. OBJECTIVE AND SCOPE The objective of this document is to define a preliminary system to produce hydrogen from biogas with the catalytic membrane reactor technology, considering a hydrogen production target of 100 kg/day. In addition, it will be described the technologies and defined the plant specifications in other to choose the best technology for this application in terms of performance and costs. Finally, potential market applications for this technology will be analyzed and described in terms of possible biogas producers and final consumers of the hydrogen produced.

2. PLANT SPECIFICATIONS The Bionico project will develop, build and demonstrate an innovative biogas upgrading system to produce hydrogen at a real biogas plant (landfill) with a novel reactor concept, integrating hydrogen production and separation in a single vessel. In particular, by integrating the separation of hydrogen in situ during the reforming reaction, the methane in the biogas will be converted to hydrogen at a much lower temperature compared with a conventional reforming system. The adoption of a membrane reactor (MR) can improve the conversion efficiency due to combining the biogas conversion to hydrogen and its separation in one single reactor. The hydrogen production capacity will be of 100 kg/day what results in more than 100 membranes integrated in the membrane reactor. By using the novel intensified reactor, an increase of the overall efficiency and strong decrease of volumes and auxiliary heat management units. Therefore, construction and demonstration should be subjected to the following specifications [2].

Hydrogen production capacity will be of approximately 100 kg/day.

High Hydrogen purity (higher than 3.0) (to be confirmed).

Overall system efficiency up to 72%.

3. PROCESS DESINGS BASIS The system in the Bionico project aims to use selective removal of hydrogen in the reforming of biogas to produce pure hydrogen and achieve an overall efficiency up to 72%. This requires integration of both purification and catalysis in the same reactor. In particular, the utilization of hydrogen perm-selective membranes allowed for the realization of better performance than conventional reactors (CRs) at milder conditions, collecting also a highly pure hydrogen stream. In addition, supplementary improvements can be realized by combining fluidization technology with membrane separation. Indeed, membrane technology seems to be the most promising candidate for substituting the conventional reforming systems [3]. The integration of both catalysis and membrane is possible in different types of membrane reactors. On this route, two different reforming reactor configurations are considered for the Bionico project are the packed bed (PBMR) and the fluidized bed membrane reactors (FBMR). The packed bed reactor is the first and most studied because of its simplicity in design and scale up. The packed bed membrane reactor confines the catalyst in a fixed bed in contact with the membrane. The most used is the tubular packed bed where the catalysis is either placed inside the membrane tube or surrounding the membrane both configurations. The biogas is converted over the catalyst bed. The produced hydrogen is transported from the bulk of the catalyst to the membrane wall where it is removed. In the early research on this kind of reactors, due to the low flux membranes used, the bed-to-wall mass transfer was not limiting. However, with the increase in hydrogen flux through the membrane it became a limiting factor for the permeation of hydrogen. In case of the fluidized bed membrane reactor, the membranes are immersed in bed of catalytic particles (as shown in Figure 1). The catalytic particles are brought to fluid like conditions where the superficial gas flow counter balances the frictional forces of the catalytic parties. A bubbling behaviour of the bed is achieved with a high enough gas velocity. The fluidization of the catalyst makes also possible to overcome problems with temperature control (formation of hotspots or too low temperature), to operate with smaller particles while still maintaining very low pressure drops and to overcome any concentration polarization issue associated with more conventional fixed bed membrane reactors.



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Figure 1 Typical scheme of a FBMR. [5]

Though the packed bed reactor is the first and most studied because of its simplicity in design and scale up, for the prototype, that will be developed, the fluidized bed configuration is selected to exploit the full potential of the selective removal of hydrogen.

3.1. General considerations The hydrogen production will be conducted in a novel reforming reactor that needs to be feed with cleaned biogas (low concentration of contaminants), water steam, air (in case of autothermal reactor) and sweep gas for the hydrogen draw; thus, a balance of plant is required to adequate the biogas produced in the landfill, water supply and air onsite to the requirements of the process.

3.1.1. Plant Location Bionico project will be integrated at a real biogas plant with biogas coming from a landfill. The biogas plant, already under operation, is located in Chamusca, Santarém (Portugal) and belongs to one of the partners of the consortium, ENC Power.

Figure 2 Chamusca´s landfill (left) and Landfill gas valorization plant (right). Font ENC.

3.1.2. Onsite environmental conditions Environmental conditions to be considered for the design are included in Table 1.



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Table 1 Onsite conditions. Source ENC.

Temperature (min / max) 6,6 / 31,5 ºC

Average Barometric pressure (mbar)

1,013 bara

Altitude above sea level 200 m

Relative humidity (min / max) 62% / 80%

Maximum wind speed 20 km/h

Average wind speed 5 km/h

3.1.3. Raw material specifications The specification of the raw material composition and main characteristics is a key aspect for the definition of the process; balance of plant components and to ensure the correct operation of all installations on the plant. This information has been extended by ENC Power and is attached below. Biogas The landfill biogas pressure available at the moment is 80 mbarg and the temperature is around 45ºC. Biogas composition is reported in

Table 2.

Table 2 Biogas composition ENC Landfill (Chamusca). Source ENC.

Characteristic Units Lower value Higher value Average

LHV MJ/Nm3 17,5 19,5 18,5

MJ/kg 90,5 109 99,75

CH4 % vol 42 49 46

CO2 % vol 33 37 35

N2 % vol 14 19 17

O2 % vol 1,5 4 3

CO ppm 5 8 6,5

H2 ppm 154 186 170

H2S (before cleaning) ppm 33 50 41,5

NH3 ppm -- -- --

Higher HC ppm -- -- --

Total Chlorine mg/Nm3 14 28 21

H2O -- Relative humidity

100% @ 25ºC -- --

Siloxanes mg/Nm3 1 8 4,5

Halides -- -- -- --

Ambient air Air on industrial sites usually presents some contaminants that could result harmful for the system (particles, metals, sulfur compounds, halogens, siloxanes, etc.). Air composition onsite has been provided for ENC Power and it is reported on Table 3 below, this composition does not include the contribution of any diffuse emissions.



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Table 3 Air composition ENC Landfill (Chamusca). Source ENC.

Contaminant Units Value

PM 2,5 µg/m3 34

PM 10 µg/m3 67,7

NO2 µg/m3 28

SO2 µg/m3 22,6

O3 µg/m3 163,7

Water supply The water supply onsite is made directly by the local water company at a pressure over 2 – 3 bara. The composition

is reported on Table 4. According to this composition and depending on catalyst, membranes and

evaporation system limitations a water treatment system will be defined. The selected system should include a treated water storage tank to allow the operation of the prototype in case the water cut-offs.

Table 4 Water composition ENC Landfill (Chamusca). Source ENC.

Component Units Value

Basic and saline parameters

Residual disinfectant (Cl2) mg/L 1,4

pH mg/L 6,5 – 7,3

Conductivity uS/cm 0,209

Oxygen (O2) mg/L 2

Ammonium (NH4) mg/L 0,05

Nitrites (NO2) mg/L 0,02

Nitrate (NO3) mg/L 2,7

Bromate (BrO3) mg/L 0,005

Cyanide (CN) mg/L 0,01

Chloride (Cl) mg/L 25

Fluoride (F) mg/L 0,39

Sulfates (SO4) mg/L 5

Calcium (Ca) mg/L 3,3

Magnesium (Mg) mg/L 3,4

Sodium (Na) mg/L 30

Total Hardness (CaCO3) mg/L 22

Metals

Iron (Fe) ug/L 10

Aluminium (Al) ug/L 23

Manganese (Mn) ug/L 10

Boron (B) ug/L 0,5

Copper (Cu) ug/L 10



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Component Units Value

Cadmium (Cd) ug/L 1

Chrome (Cr) ug/L 5

Nickel (Ni) ug/L 5

Lead (Pb) ug/L 3

Antimony (Sb) ug/L 1

Arsenic (As) ug/L 8

Selenium (Se) ug/L 1

Mercury (Hg) ug/L 0,3

Volatile organic compounds (VOC)

1,2 - Dichloroethane ug/L 0,5

Chloroform ug/L 3

Dibromochloromethane ug/L 3

Trihalomethane ug/L 6

Bromodichloromethane ug/L 3

Bromoform ug/L 3

Tetrachloroethene and Trichloroethene

ug/L 3

Polycyclic aromatic hydrocarbons

Benzo(a)pyrene ug/L 0,002

Benzo(b)fluoranthene ug/L 0,005

Benzo(k)fluoranthene ug/L 0,002

Benzo(ghi)perylene ug/L 0,004

indeno (1 2 3-cd) pyrene ug/L 0,004

Total PAH ug/L 0,005

Total pesticides ug/L 0,014

3.1.4. Noise limitations Currently part of the biogas produced in the landfill is being used in a combined heat and power unit. The noise level of the CHP unit is 117 dB @ 1 meter, therefore this will be taken for noise limitation’s reference for Bionico project´s prototype.

3.2. Biogas pre-cleaning Considering biogas composition reported on Table 2, and membranes and catalyst efficiency limitations in presence of contaminants, a pre-cleaning stage is required for the successful integration of Bionico´s prototype in the landfill; mostly due to the presence of hydrogen sulphide (H2S) that will cause the poisoning and loose of activity of the reforming catalyst and membrane permeance and selectivity, but also due to the presence of other components (water, chlorine, siloxanes and particulates) that could cause to a greater or lesser degree adverse effects on the process (corrosion, performance decline, etc.) Below are presented some approaches on the biogas pre-cleaning stage. Water removal Biogas leaving the landfill is saturated. If this water content is not eliminated, it will condense in gas pipelines and together with sulphur oxide may cause corrosion. By increasing the pressure or decreasing the temperature, water will condense and thereby can be removed from the biogas stream. Cooling can be achieved naturally by leading it



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through a pipe in the soil equipped with a condensate trap or with an electric cooler. During water removal, some other undesirable components as siloxanes, ammonia or halogen compounds will be reduced or eliminated as they are soluble in water. Therefore, with an efficient cooling and condensation system, it is possible to remove water and also to reduce other contaminants, improving the efficiency of the whole plant and reducing maintenance costs and plant downtime considerably. Ammonia removal Ammonia is produced during anaerobic digestion when proteins broke down, so the levels of ammonia on biogas will depend on the amount of proteins on the feedstock to the landfill. Although no content of ammonia has been reported on biogas composition provided by ENC Power, the most common removals methods are mentioned below. In small scale plants, ammonia is dissolved in the condensate water and it is removed when water is drained. In large industrial plants ammonia is often removed by a washing process with diluted nitric or sulphuric acid which means stainless steel installations and higher costs. Another option would consist on ammonia removal with activated carbon or CO2 removing units (adsorption and absorption). For Bionico project, considering the lack of ammonia reported and the scale of the prototype a specific ammonia removal system will not be required. Siloxanes removal Siloxanes are compounds containing a silicon-oxygen bond. They are used in products such as deodorants and shampoos, and therefore can be found in biogas from sewage sludge treatment plants and in landfill gas. When siloxanes are burned, silicon oxide, a white powder, is formed and can create a problem in high temperature equipment. Siloxanes can be removed by cooling the gas, adsorption on activated carbon, aluminium or silica gel and by absorption in mixtures of liquid hydrocarbons. In case of cooling the gas, the siloxanes will be removed with the drained water; the efficiency is determined by the temperature and pressure used. Particulates removal Although it has not been reported in biogas composition, particulates can be present in biogas and cause mechanical wear in rotating equipment. They could be easily separated by a variety of mechanical filters (stainless steel or ceramic filter pack, cyclone separators, etc.). Hydrogen sulphide removal Hydrogen sulphide is produced during microbiological reduction of sulphur compounds (sulphates, peptides, amino acids) and it is always present in biogas, normally at concentrations between 80 – 4000 ppm [14] depending on the feedstock. The values reported in biogas composition are below these concentrations, with a maximum concentration of hydrogen sulphide of 50 ppm. Hydrogen sulphide is corrosive to most equipment (pipelines, compressors, gas storage tanks, engines, etc.) and acts as strong poison for reforming catalysts. Furthermore, H2S combustion leads to sulphur dioxide emissions, which have harmful environmental effects. Due to the potential problems that H2S can cause, it is recommended to remove it early in the process of biogas pre-cleaning. Hydrogen sulphide limitations depend on catalyst and membranes requirements and have been set on 10 ppb. These values should be taken for reference for the design or selection of the hydrogen sulphide removal system for Bionico project. There are four main technologies to remove hydrogen sulphide from biogas: precipitation, adsorption with activated carbon, chemical absorption and biological treatment.

Chemical absorption: one of the oldest methods for hydrogen sulphide removal is based on sodium hydroxide

(NaOH) washing. Because of the high technical requirements to deal with the caustic solution, its application is hardly applied anymore except when very large gas volumes are treated or high concentrations of H2S are present. The main disadvantage of this technology is that large quantities of contaminated water are produced. Hydrogen sulphide can also be absorbed using iron oxide-coated (Fe(OH)3 or Fe2O3) support material. Regeneration is possible for a limited number of times (until the surface is covered with natural sulphur), after which the tower filling has to be renewed. The process operates with two columns; one is absorbing, while the other is re-oxidized.



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Precipitation: addition of Fe2+ ions or Fe3+ ions in the form of FeCl2, FeCl3 or FeSO4, to the digester precipitates almost all the insoluble iron sulphide, which is removed together with the digestate. Reductions of H2S concentrations in the biogas down to 200 – 100 ppm have been achieved [14]. Removal to lower concentrations required a large excess of iron ions. At this respect, this method can only be considered as a partial removal process and must be used together with other technology to go down 10 ppb [14].

Biological treatment: is based on the activity of specific microorganisms that decontaminate polluted air through a range of steps: absorption, adsorption, diffusion and biodegradation. The microorganisms that could oxidize the hydrogen sulphide are the Thiobacillus and Sulfolobus species. The degradation process requires oxygen so a small amount of air (or pure oxygen if levels of nitrogen should be minimized) is fed for the biological desulphurization to take place. The degradation could take place inside the digester or in a trickling filter downstream the digester. Both methods are widely applied, but for those applications that required very low levels of hydrogen sulphide (<50 ppm) an additional method or a second cleaning step after a biological treatment must be utilized. Moreover, they are not appropriate for some applications (e.g. vehicle fuel or grid injection) due to the remaining traces of oxygen.

Adsorption on activated carbon: hydrogen sulphide is adsorbed on the inner surfaces of engineered activated

carbon with defined pore sizes. The activated carbon is usually impregnated or doped with caustic materials like sodium or potassium hydroxide to increase the speed of reaction and the total load. In the presence of oxygen, hydrogen sulphide can be converted by caustic catalysis, to produce elemental sulphur and water. The optimal reaction pressures vary between 7 and 8 bars [15] and typical operating temperatures range from 50°C to 70°C and it is extremely efficient with resulting concentrations of less than 1 ppm. The sulphur produced is adsorbed by the activated carbon while remaining traces of hydrogen sulphide would react with the base and thus can be easily immobilized. When the activated carbon bed is saturated, it can be replaced for a fresh one, or regenerated by washing with water. Adsorption is one of the most competitive technologies for precision desulfurization because it is simple and effective (>99%). Major drawbacks include a continually produced waste stream of spent media and growing environmental concern over appropriate waste disposal methods. Besides cleaning sulphur from biogas, this process also enables removal of minor contaminants such as ammonia, chlorine or fluorine.

According to this, hydrogen sulphide can be removed either in the biogas production stage, from the crude biogas or in subsequent purification or cleaning stages required for the process. In the case of Bionico project, the hydrogen sulphide removal system should have no impact on landfill operation or other systems currently under operation onsite. 3.3. Biogas upgrading Most of biogas projects consider the upgrading of the biogas to biomethane and its conversion on a conventional reforming process including reforming, water gas shift reactors (high and low temperature) and pressure swing adsorption or membranes for hydrogen purification. Most widespread technologies for reforming and biogas upgrading were studied, highlighting that the upgrading stage increases enormously the cost of hydrogen production and presents a significant impact on the footprint required for the plant. Bionico project approach will eliminate the upgrading step, performing the conversion of cleaned biogas into hydrogen without removing the carbon dioxide present in biogas. Specific catalyst, membranes and reactor system should be design and developed to work with specific feedstock concentrations.

3.4. Biogas Reforming Biogas is a high-potential versatile raw material for reforming processes, which can be used as an alternative CH4 source. , the most relevant reforming process using biogas to reach the skills of the plant specifications are steam reforming and autothermal reforming process. Following there is a description of the main biogas reforming process.

3.4.1. Steam reforming process (SR) Steam reforming is the combination of methane with water (steam) in the presence of catalyst, producing carbon monoxide (CO) and hydrogen (H2) (Eq.3). Steam reforming is a consolidated process considered as the most common process in industry for hydrogen production [6]. In order to eliminate the CO produced and increase the



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hydrogen production, steam reforming is commonly associated with the water gas shift reaction (Eq.4); equation 5 shows the reaction of methane SR associated with the shift reaction (WGS). Due to the high content of carbon dioxide (CO2) in biogas, 35% on average was reported on raw biogas composition, dry reforming (DR) could take place if methane reacts with carbon dioxide to produce carbon monoxide and hydrogen (Eq. 6) [11]. Dry reforming, produces less hydrogen and needs a higher amount of heat than steam reforming. Furthermore, this technology presents great tendency to coke formation that could be harmful for the membranes and catalyst. Both reforming reactions, steam reforming and dry reforming, are highly endothermic and would require an external heat source supply.

𝐶𝐻4 + 𝐻2𝑂 ↔ 3𝐻2 + 𝐶𝑂 (∆𝐻298 = 206,0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 3)

𝐶𝑂 + 𝐻2𝑂 ↔ 𝐻2 + 𝐶𝑂2 (∆𝐻298 = −41,0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 4)

𝐶𝐻4 + 2𝐻2𝑂 ↔ 4𝐻2 + 𝐶𝑂2 (∆𝐻298 = 164,9 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 5)

𝐶𝐻4 + 𝐶𝑂2 ↔ 2𝐶𝑂 + 2𝐻2 (∆𝐻298 = 247,0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 6) The steam methane reforming is affected by several limitations, such us thermodynamic equilibrium constraints, mass and heat transfer limitation and coke formation. Traditionally steam methane reforming is performed on high heat transfer reactors, under harsh conditions: high temperature (800-950ºC), high pressure (up to 20 bar), and with an excess of steam to avoid carbon deposition (typical feed S/C1 molar ratios between 2 and 5). In order to avoid aforementioned limitations, membrane reactor technology could be implemented achieving better performance than conventional reactor at milder conditions, collecting also a highly pure hydrogen stream. The simulation and design of the reactor requires information on thermodynamics and kinetics. The reactions indicated above have to be studied in some depth to define the process, reaction mechanism and diffusion limitations.

3.4.2. Autothermal reforming process (ATR) As stated before, steam reforming associated with the shift reaction is a highly endothermic reaction that requires external heating supply. A reactor´s internal heating system is generally more efficient than external heating, and a reaction that releases energy in the catalyst bed can make the hydrogen production process energetically more economical. Partial oxidation (Eq.7) presents the advantage of being exothermic, but produces less hydrogen in comparison with steam reforming. Based on these observations, the autothermal reforming is a combination of steam reforming and partial oxidation. Partial oxidation reaction of methane occurs simultaneously with steam reforming, significantly reducing energy costs due to the balance of endothermic reactions (steam reforming or dry reforming) and the exothermic reactions (partial oxidation and water gas shift). The main advantages of ATR concern temperature control in the reactor, reducing the formation the hot-spots and avoiding the deactivation of the catalyst and controllable H2/CO or CO2 ratio regulated by oxygen and water (steam) feed rates.

𝐶𝐻4 + 𝐻2𝑂 ↔ 3𝐻2 + 𝐶𝑂 (∆𝐻298 = 206,0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 3)

𝐶𝑂 + 𝐻2𝑂 ↔ 𝐻2 + 𝐶𝑂2 (∆𝐻298 = −41,0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 4)

1 The carbon, which is considered in this definition, is the fraction of organic carbon that takes part in carbon-forming reactions. Here, a general definition of organic carbon is considered. In biogas, organic carbons are presented in CH4

and CO2. Because this parameter is considered for coking tendency and CO2 does not have any influence on carbon formation, CO2 is not considered as a carbon carrier. Therefore, CH4 is the only compound that is relevant for the S/C ratio [11].



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𝐶𝐻4 +1

2𝑂2 ↔ 𝐶𝑂 + 2𝐻2 (∆𝐻298 = −35,6 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 7)

The ATR reaction, in order to perform the mass and energy balance could be expressed as follows:

𝐶𝐻4 +1

2(𝑂2 + 3,76𝑁2) + 3𝐻2𝑂 ↔ 2𝐶𝑂2 + 1,88𝑁2 + 7𝐻2 (∆𝐻298 = 0 𝑘𝐽𝑚𝑜𝑙−1) (𝑒𝑞. 8)

ATR is considered suitable for producing hydrogen for small scale applications such as distributed or small stationary fuel cell power systems because of its high efficiency and the speed with which the reactor can be stopped and restarted [12]. Experimental studies performed with biogas from anaerobic digestion and Ni based monolithic catalyst show that the highest hydrogen concentrations and methane conversion were attained at oxygen to carbon (O2/C) ratios of 0,45 – 0,55 and steam to carbon ratios (S/C) of 1,5 – 2,5 at 750 ºC [12]. In the development of Bionico project it should be studied how the steam to carbon (S/C) and oxygen to carbon (O2/C) ratios affect the temperature profiles and reaction properties in the ATR reaction of actual biogas, considering the methane concentration in biogas could vary slightly depending on the wastes on the landfill.

3.5. Process Flow Diagram Following is a preliminary process flow diagram (PFD) of the plant for both processes using steam reforming (see Figure 3) and autothermal reforming (see Figure 4).

Figure 3 Bionico preliminary PFD SR reactor plant.



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Figure 4 Bionico preliminary PFD ATR reactor plant.

3.6. Plan layout As first approach it has been considered an available footprint of 100 m2 for the demonstration prototype. As the project moves forward, the process will be defined and equipment will be selected, analysing different physical configurations and defining the main dimensions of the system. Figure 7 and Figure 8 show the preliminary plant layout.

Figure 5 Bionico prototype layout.



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Figure 6 Preliminary isometric view of Bionico project prototype.

4. POTENTIAL MARKET APPLICATIONS 4.1. Analysis of potential market applications for biogas producers The existing biomass resources on our planet can give us an idea of the global potential of biogas production. This potential was estimated by different experts and scientists, on the base of various scenarios and assumptions. Regardless the results of these estimations, the overall conclusion was always, that only a very small part of this potential is utilized today, thus there is a real possibility to increase the actual production of biogas significantly. The European Biomass Association (AEBIOM) estimates that the European production of biomass based energy can be increased from the 72 million tonnes (Mtoe) in 2004 to 220 Mtoe in 2020. The largest potential lies in biomass originating from agriculture, where biogas is an important player. According to AEBIOM, up to 20 to 40 million hectares (Mha) of land can be used for energy production in the European Union alone, without affecting the European food supply. The production and utilization of biogas presents environmental and socioeconomic benefits, some of them are listed below:

Biogas is a renewable energy source, so the use of biogas reduces greenhouse gas emissions and

contributes to the mitigation of global warming.

Biogas could be produced worldwide increasing security of local energy supply and reducing dependency

on imported fossil fuels.

Biogas plants do not only supply energy, the digester substrate is a valuable soil fertilizer.

Biogas production involves waste reduction as waste material is used as substrate for anaerobic digestion.

Biogas is a flexible energy carrier suitable for many energy applications.

Biogas presents many energy utilizations depending on the local demand and the final application requirements (end user). Generally, biogas can be used for heat production by direct combustion; electricity production by fuel cells or

micro-turbines, CHP generation, vehicle fuel and hydrogen production (see Figure 7Errore. L'origine riferimento

non è stata trovata.Figure 7).



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Figure 7 Overview of biogas utilization.

Depending on the nature of the biogas source (landfill, animal waste, sewage treatment plants, industrial wastewater, anaerobic digestion) different biogas purification stages and processes are required (biogas upgrading); these processes are more or less complex according to the final application (e.g. cogeneration, heat production, etc.).

4.1.1. Current situation The biogas sector differs considerably in different parts of the world. The size of plants varies from small scale household units to major plants using such raw materials as household waste, industrial waste and manure. Biogas is used in other ways in large parts of the world, often for the production of electricity and heat or directly for cooking and lighting in small communities.

Figure 8. Evolution of biogas/landfill gas installed capacity [22].

Different countries have invested in different types of biogas systems depending on widely different environment and energy programmes. The UK and South Korea for example gain most of their biogas from landfill sites, whilst Switzerland and Sweden have built up systems for decomposition at sewage plants. Denmark uses manure to a large extent as this has been a means of dealing with the overproduction of manure there. Germany, the UK and Sweden are examples of countries where biogas production comes from collecting food waste. Development is



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primarily influenced by the authorities - Germany for example has developed a largely agriculturally based biogas production system through subsidising production. China and Germany are world leaders within farm-based biogas production. There are no less than 24,000 small farm plants in China, and almost 8,000 agricultural plants in Germany of various sizes. The German plants contribute ca. 10,500 GWh of heat and 25,000 GWh of electricity per annum, corresponding to 3% of the country's electricity consumption. France, Holland, Austria and Italy also produce large amounts of farm-based biogas [23].

Figure 9 Evolution of biogas/landfill gas installed capacity by continent [22].

For most energy applications the quality of biogas has to be improved by removing hydrogen sulphide, water, carbon dioxide or halogenated compounds depending on the final application requirements (biogas upgrading), biogas source and biogas production process. Although the upgrading of biogas increases enormously the cost of production, it has gained increased attention and new plants are continually being built.

Figure 10 Biogas upgrading technology shares in EU plants [24].



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Figure 11 Biogas upgrading capacity shares in EU plants [24].

4.1.2. Key industry players As already stated, after a fist purification step to remove sulphur, dust and moisture the main routes to use biogas are:

Heat generation

Electricity generation or CHP

Upgrading for biomethane production

Out of 13.5 Mtoe of Biogas produced in 2013, the majority was converted in CHP plants producing about 32.1 TWhel of electric energy and 4.6 TWh of heat sold to heating networks, a lower fraction was converted into electricity only (producing 20.5 TWhel) or sold heat only (producing 0.8 TWh). About 24.7 TWh of heat where finally directly used onsite. A small fraction of the Biogas was finally sent to upgrading plants to produce biomethane (2% in 2012), mainly for grid injection.

As shown in Figure 12 there is an increasing demand for upgraded biogas, fuelled by an ever growing concern for

the environment, climate change and air qualities especially in the urban environment.

Figure 12 Expected trend of Biogas/Biomethane potential [26].



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Bio-methane production can be used to provide a fuel and heat source to promote regional development, as it is more ecofriendly than the extraction on fossil fuels to the environment. Bio-methane production can be used alongside existing transport infrastructures (trains, boat and vehicles). After upgrading it can be injected into existing gas grid locations, vehicle fuels or a high energy fuel.

Figure 13 Evolution of number of biogas upgrading plants by technology [27].

A list of the main manufacturers of upgrading unites is reported in the Errore. L'origine riferimento non è stata trovata..

Table 5 List of manufacturers of upgrading units by technology [27]

Company Technology

Acrona-systems

PSA

Carbotech

Cirmac

ETW Energietechnik

Guild

Mahler

Strabag

Xebec

DMT

Econet

Water scrubbing Greenlane Biogas

Malmberg Water

RosRoca

BIS E.M.S. GmbH

Chemical scrubbing

Cirmac

Hera

MT-Biomethan

0

50

100

150

200

250

2006 2003 <2001

2001 2002 2004 2005 2007 2008 2009 2010 2011 2012

Year of commissioning

Cryogenic separation Membrane Organic physical scrubber Chemical scrubber PSA Water scrubber



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Company Technology

Purac Puregas

Strabag

HAASE Energietechnik Physical scrubbing

Schwelm Anlagentechnik

Air Liquide

Membrane

BebraBiogas

Biogast

Cirmac

DMT

Eisenmann

EnviTec Biogas

Gastechnik Himmel

Haffmans

Mainsite Technologies

Memfoact

MT-Biomethan

Acrion Technologies

Cryogenic

Air Liquide

Cryostar

FirmGreen

Gas treatment Services

Gasrec

Hamworthy

Prometheus Energy

Terracastus Technologies

4.2. Analysis of potential market applications for hydrogen consumers This market research represents the hydrogen generation market in terms of its applications. Hydrogen is the most common element and is used in chemical processing, petroleum recovery and refining, basic chemical industry, food industry (sorbitol), electronics, glass industry, metal production processes, aerospace, and fuel cells. The sectors which have the largest demand for hydrogen are petroleum refinery and basic chemical industry (ammonia production), while automotive fuel is an emerging sector, with a huge potential in future. Although hydrogen is being traditionally used as a key ingredient of the industry, the hydrogen economy is being driven to use hydrogen as fuel not as a chemical reagent. Thus, the following applications have joined to traditional use of hydrogen as an industrial gas: use of hydrogen as fuel for transport, distributed power generation using fuel cells, the use of hydrogen vector as energy storage system (including here "Power to Power" and "Power to Gas" systems, which will be described later on this document) and applications for special sectors such as aerospace, defense, etc. Industries such as food, the manufacture of glass or steel, chemical industry and petrochemicals, etc., traditional hydrogen consumers, are already being supplied by gas sector companies that could transport the hydrogen to the site or can be produced in situ. However, these industrial areas are showing a growing interest in the development of hydrogen technologies, because they offer opportunities to meet new needs that are being identified as requirements for higher purity hydrogen, or new regulatory requirements aim to the reduction of environmental impact.



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The distribution of the sources of hydrogen production are: 96% produced from fossil fuels, the most used natural gas by 48%, followed by liquid hydrocarbons by 30%, coal by 18%, and electrolysis and other sources of hydrogen byproducts 4%.

Figure 14 Distribution raw material for hydrogen production [28].

The hydrogen production cost depend on the technologies used, Figure 15 compares the hydrogen production costs by different technologies in different temporary scenarios considered by several government institutions and projects, such as the Department of Energy (DOE), the World Energy Technology Outlook report - WETO H2, the European Hydrogen Platform (HFP) and the International Energy Agency (IEA). The work covered by these agencies includes different time horizons but not all technologies are considered in all of them. However, despite these limitations, the values shown in the graph are fairly illustrative:

Figure 15 Cost comparison of hydrogen production by different production technologies [29].

The global market for hydrogen will have an annual growth of 3.5% through 2018. The fastest growth will be in the manufacture of chemicals and industrial hydrogen markets. In the Errore. L'origine riferimento non è stata trovata.

Natural Gas48%

Liquid Hydrocarbons

30%

Coal18%

Electrolysis4%



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is showed the global hydrogen demand in trillion cubic meters, the annual growth in 2008-2013 and the planned 2013-2018:

Table 6 World hydrogen demand from 2008 to 2018 [30]

Billones of m3 % Annual Growth

2008 2013 2018 2008-2013 2013-2018

Hydrogen demand 218.0 254.5 302.5 3.1 3.5

North America 69.8 75.4 81.1 1.6 1.5

Western Europe 52.4 51.4 52.3 -0.4 0.3

Asia/Pacific 57.8 85.0 116.0 8.0 6.4

Other regions 38.0 42.7 53.1 2.4 4.5

4.2.1. Market research by industries Following is a summary of market research by main industry sectors identified above.

Refinery industry

Refinery industry is based on the chemical process of petroleum to produce several fossil fuels able to be used in combustion engines such as: petrol, diesel, etc. Additionally, and as a natural part of the process, various products such as mineral oils and asphalt are obtained. There is a different between the industries defined as above with the petrochemical industry, which is the removal of any chemical substance from fossil fuels. These include purified fossil fuels such as methane, propane, butane, gasoline, kerosene, diesel, jet fuel, as well as pesticides, herbicides, fertilizers and other items such as plastics, asphalt or synthetic fibers.

Ammonia synthesis Industry

Synthesis of ammonia is the most important industrial process for isolation of nitrogen as well as further production of nitrogen compounds of vital importance (urea, nitric acid and fertilizers). The reaction between gaseous N2 and H2 is exothermic, carried out at high pressures and temperatures and occurs with large yields when iron catalysts are present.

Glass industry

Hydrogen is used in glass industry for manufacturing of flat or float glass. Float or flat glass business is the fundamental basis on which the production and manufacturing of other glass is structured. Main applications of hydrogen in the glass industry are:

- Reducing atmosphere in the manufacture of flat glass - Gas fuel for fusion and cutting quartz - Fuel in glass polishing

Steel industry

The steel industry value chain includes all the processes required to transform raw materials (mainly coal, iron ore, electricity and scrap) into finished steel products. Generally, the following infrastructures are required to produce steel:

- Coke ovens - Sinter and pellet plants - Blast furnaces - Steel furnaces - Rolling and finishing mills

Electronic industry



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Electronics sector industries include telecommunications, equipment, electronic components, industrial electronics and consumer electronics. Electronics companies produce electrical equipment, manufacture electrical components and retail these products to make them available for consumers. The most profitable sector within electronics, the semiconductor industry, has a value of around $248 billion globally. The products produced by this sector are used in a variety of consumer and industrial electronics products.

Methanol industry

Methanol is a basic chemical element used in the manufacture of hundreds of products that affect our daily lives, p.e.: paints, plastics, furniture, carpets, car parts and windshield washer fluid. Methanol is also an emerging source of energy for running cars, trucks, buses and even electricity turbines. Methanol, also known as methyl alcohol or wood alcohol, is the simplest of all alcohols. Its chemical formula is CH3OH. Methanol is a colorless, light, flammable liquid at ambient temperature containing less carbon and more hydrogen than any other liquid fuel. It is a stable biodegradable chemical substance that is produced and distributed daily worldwide, and it has many industrial and commercial applications. Methanol is produced naturally in nature, and decomposes rapidly in both aerobic and anaerobic conditions.

Transport industry

Hydrogen has been used on all types of transport existing such as rail, naval, aviation and road sector (buses, trucks, vehicles, motorcycles, etc.). In most terrestrial applications (cars, buses and rail), it has hydrogen as a means of propulsion (fed into a fuel cell, in turn, produces electricity to supply an electrical engine); however, it has also examined the use of hydrogen in auxiliary power systems (APU, its acronym in English) in trucks. Naval sector, it has been used as fuel for propulsion systems in small boats and as APU systems in larger boats, or even submarines. Finally, in the aviation sector, we find some versions of APUs for aircraft, as well as feasibility studies are already talking about the possibility of using hydrogen as a fuel in aircraft propulsion. Hydrogen production via electrolysis of water is a well-established technology. Currently, electrolysis is mostly limited to applications requiring high purity hydrogen. It is a very clean process as long as the necessary electricity for electrolysis comes from clean, renewable energy sources.

Other industrial hydrogen markets

Other processes that use hydrogen are:

- Contaminated water treatment - Coal treatment - Organic Synthesis - Inorganic synthesis - High temperature Flames - Hydrogen Plasma - Pharmaceutical industry - Food and beverage industry - Power generation (cooling sytem)

4.2.2. Current situation Following is a summary of the current situation by main industry sectors identified above.

Refinery industry

The refining sector of the EU ensures the reliable supply of raw petrochemical, representing more than € 240,000 million in annual sales and employs nearly 800,000 people materials. The refining is tightly integrated with petrochemicals, contributing to the European economy in its broadest sense.



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It is a symbiotic relationship, as the petrochemical sells products to the refinery, including hydrogen (used to desulfurize) and other materials used as fuel components. This interdependence is enhanced by logistical links. For example, many intermediate products, such as gases, are difficult to transport, the short-distance transport is the only economically viable solution. That is the reasons of many petrochemical complexes in the EU are located within or contiguous to refineries. Of the 58 complexes with "steam cracker" (breaking through refinery hydrocarbon vapor) in the EU, 41 are integrated with refineries located 2 km on average. This proximity facilitates many other synergies, such as connecting pipelines, marine terminals and common shared support services, including energy optimization.

Figure 16 Refineries and steam cracker in EU [31].

The refinery best suited to your market demand, delivering products with the required specifications and compliance with environmental restrictions in force in the EU, will necessarily be complex in its production system, rational use of energy, whose consumption is high and therefore, its specific emissions will be high.


Around 80% of the ammonia produced is used as nitrogen source to make fertilizer, while the remaining 20% is used in various industrial applications such as the production of plastics, fibres, explosives, hydrazine, amines, amides, nitriles and other organic nitrogen compounds which serve as intermediates in the manufacture of dyes and pharmaceuticals. The inorganic products manufactured from ammonia include nitric acid, urea and sodium cyanide. Ammonia is also used in protective measures for the environment, for example, to remove NOx from combustion gases. Liquid ammonia is an important solvent and also used as a refrigerant. World production of ammonia has growth in the last decades, reaching a peak of 137 million tons in 2012. The figure below shows the global production of ammonia in tons:

Figure 17 Global ammonia production (in tons) [32].

Refinery sites (110 total)

Steam Cracker sites (58 total)

Refinery with steam cracking integrated sites(48 total)



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The two main drivers of consumption of ammonia are used in agriculture and the development of applications for industry use. The following graph shows the overall consumption of ammonia:

Figure 18 Global ammonia consumption [33].

Glass industry

Hydrogen is used in glass industry for manufacturing of flat or float glass. Float or flat glass business is the fundamental basis on which the production and manufacturing of other glass is structured. Main applications of hydrogen in the glass industry are: The 90% of the glass used in the world is produced industrially in furnaces by the float process. Currently, world production of glass is around 800,000 tons of glass per week. A float plant, which operates non-stop for 11 to 15 years, produces around 6,000 kilometers of glass a year. It has been awarded the license for the float process more than 40 manufacturers in 30 countries. Production of flat glass is dominated by China, which currently produces about half of flat glass in the world. At the end of 2013 there were 432 active lines floating around the world, of which 243 were located in China. The Asia/Pacific is the largest regional market for flat glass and accounts for 54% of demand worldwide in 2013. The following chart global demand for flat glass is observed by region in 2013. The following table shows the percentage growth in global demand for flat glass in the period 2008-2013 and the forecast growth in the period 2013-2018.

Steel industry

The EU metals sector contributes to the 10% of total manufacturing value added and 7.5% of its production volume. The steel and basic metals represent the 5% of total manufacturing output. Germany is the largest producer of metallurgical products, followed by Italy, France, UK and Spain (EU-5). Global steel production reached 821.3 million tons (mmt), representing an increase of 3.1% over the first six months of 2013. The growth was driven mainly by the EU (3.8%) and Asia (2.9%). In North America continues the decline in turnover of companies in the sector (-6.4% over 12 months), while their debt levels rise sharply. Nonetheless, production in the US keeps on stable, despite the pressure from imports, which increased by 34% over the same period in 2013, particularly in the sector of tubes and pipes. China consolidated its position as world leader in steel production, with a market share higher than 50%.



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Table 7 World flat glass demand [34].

Table 8 Steel World Production [35].

Steel production in June 2014 in millions of tons

(mmt)

World Production 821.3

China 69.3

Japan 9.1

Germany 3.6

Italy 2.1

France 1.4

Spain 1.3

Turkey 3.1

Ucraine 2.6

USA 7.2

Brazil 2.7

Electronic industry

In 2012 the global production of electronic equipment was 3,432 billion USD. The most producer subsector is the semiconductor production (1.033 billion dollars). The following table shows the global electronics production industry subsector:

Table 9 Subsector global production [35].

ISIC CODE Rev.3

Subsector Production 2012 (MMD)

% TMCA (2012-2020)

% Part.

D 321 Semiconductor 1033 1 30,1

D 33 medical equipment, precision

instruments, measurement, control and optical

835 7,4 24,33



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ISIC CODE Rev.3

Subsector Production 2012 (MMD)

% TMCA (2012-2020)

% Part.

D 30 Computation and office 654 7 19,1

D322 Communications 484 8,9 14,1

D 323 Audio and video 425 9,8 12,4

Total 3,432 - 100%

World production has increased steadily in the electronics industry since 2012, and is expected to continue increasing until 2020; as shown in the following graph:

Figure 19 World electronics production evolution 2012-2020 (Million USD) [36]

The Asia-Pacific was the most production in 2012 and it has three of the top producers in the world: China, South Korea and Taiwan. North America, including Canada, USA and Mexico, was the second most productive region followed by the European Union.

Methanol industry

The methanol industry is extended worldwide. Its production takes place in Asia, North and South America, Europe, Africa and Middle East. There are over 90 methanol plants worldwide with a total production capacity of over 75 million tons (nearly 90,000 million liters). Every day more than 100,000 tons of methanol is used as a chemical feedstock or as fuel for transport (125 million liters). The global methanol industry generates 36,000 million USD of US each year and creates more than 100,000 jobs worldwide.

Transport industry

Hydrogen has been used on all types of transport existing such as rail, naval, aviation and road sector (buses, trucks, vehicles, motorcycles, etc.). In most terrestrial applications (cars, buses and rail), it has hydrogen as a means of propulsion (fed into a fuel cell, in turn, produces electricity to supply an electrical engine); however, it has also examined the use of hydrogen in auxiliary power systems (APU, its acronym in English) in trucks. At present, the most important market is the vehicles industry which uses the hydrogen as fuel for engine vehicles. In this sense, the projects have left the demonstration stage, entering the marketing. The adoption in 2014 of the European Directive on the promotion of the use of alternative fuels for transport (Directive 2014/94/EU of 22th October 2014)2, being the hydrogen one of them, forces member states to promote the fuels on a limited time frame, by setting and drive specific strategies for this purpose.

2 Note: Directive 2014/94 / EU of 22th October 2014. Article 5. Hydrogen supply for road transport Member States which decide to include hydrogen refueling points accessible to the public in their national policy frameworks shall ensure that,



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Figure 20. Coverage transport modes and autonomy of the main alternative fuels

At present, Asian auto companies are leaders in all the word. Hyundai launched the Hyundai ix35 in 2013. In addition, Toyota has launched Mirai vehicle, this one has excited public opinion. It has to take account that Toyota announced the abandonment of electric vehicles sales in favour of fuel cell vehicles, carry on some liberalization of its patents. For its part, Honda recently announced the cessation of its activities in natural gas vehicles, to focus with greater effort in fuel cell vehicle, which plans to market in 2016. European and American manufacturers, meanwhile, announced the mass marketing of its hydrogen vehicles between 2017 and 2020. Therefore, the automotive sector must available of the necessary infrastructure to face the hydrogen demand to fill out Fuel Cell Vehicles. The use of hydrogen in vehicles raises the possibility of locally producing fuel needed for transport. So, each country must be able to have their adequate production capacities, distribution and dispensing. In the next figures are showed the action plan for construction of hydrogen refuelling network expected in the next years in different countries. The standard hydrogen production capacities of the hydrogen refuelling are showed in the following table.

Table 10 Standard hydrogen production capacities of the hydrogen refueling.

Capacity (kg/day H2)

Market Dispensers number

(@ 700 bar) Daily vehicles that fill out

400 European 2 70 – 100

1.000 European 4 150 – 250

1.500 Americanan 6 225 – 400

2.500 European 10 450 – 600

4.2.3. Processes using hydrogen Following is a summary of processes using hydrogen by main industry sectors identified above.

Refinery industry

Oil refineries are the biggest consumers of hydrogen, representing almost 90% of world consumption in 2008. Historically, most of the hydrogen consumption was captive refinery produced during refining. However, the production of fuels with low sulphur and cleaning ovens require massive amounts of hydrogen for hydrotreating petroleum distillates, which is driving demand for supplies of free market or "merchant". The refinery hydrogenation processes are aimed to obtaining light fractions from heavy crude oil fractions, increasing

by 31 December 2025, an appropriate number of such points are available, to ensure the circulation of hydrogen-powered motor vehicles, including fuel cell vehicles, within networks determined by those Member States, including, where appropriate, cross-border links.



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hydrogen content and decreasing molecular weight. Simultaneously undesired elements can be removed as sulphur, nitrogen and metals. Hydrogen, has always been an important component refining process, however, in recent times, is becoming an essential component. The need to achieve a higher degree of conversion of heavy fractions with the use of lower quality crude oils and in particular the increased demands for environmental quality to be met by products which also require the hydrotreating and desulfurization of intermediate process streams, make hydrogen consumption in this type of process has increased substantially in recent years. The main processes that consume hydrogen in refinery are as follows:

- Hydrodesulfurization - Hydrogenation - Hydrocracking of heavy residues - Hydroconversion of heavy residues


A typical modern plant producing ammonia first converts natural gas or other hydrocarbon, hydrogen gas. The method for producing hydrogen from hydrocarbons is known as "steam reforming". Ammonia is obtained by catalytic reaction between nitrogen and hydrogen. Ammonia synthesis operates at absolute pressures ranging from 60 to 180 bar, depending on the design. Different engineering and construction companies offer specific designs for ammonia synthesis plants.

Glass industry

In the float glass industry, hydrogen is used in combination with nitrogen to create a reducing atmosphere in the molten tin bath and prevent oxidation of the metal that may cause impurities in the glass. Hydrogen atmosphere is usually used with 5-10% nitrogen completely covering the melt in the furnace which is above the float glass bath. Additionally, hydrogen is also used in the glass industry as a fuel gas in combination with oxygen, for melting and cutting of quartz. The advantages of hydrogen over other fuel gases is the purity of the flame, which is free of carbon and thus prevents the inclusion of impurities in the product and reducing the formation of quartz crystals. Hydrogen is also used as fuel in polishing applications requiring high sensitivity flame. Nowadays, these markets are supplied by major gas companies, including, within their divisions of industrial gases, equipment and systems specifically designed to meet these needs, provided through the supply of pure gases needed (H2, N2, O2, etc.), either pressurized or liquid form, depending on the consumption or the required purity. Hydrogen consumption and hydrogen purity in the glass industry is around 100 Nm3/ h of hydrogen consumption and a quality rating of 5.0, equivalent to a purity of 99.999%.

Steel industry

The steel industry value chain includes all the processes required to transform raw materials (mainly coal, iron ore, In the steel industry, iron ore can be reduced using coke or a gas containing hydrogen, carbon monoxide, or mixtures thereof. This reducing gas may be obtained by steam reforming or partial oxidation of fossil fuels. Furthermore, in the metal industry, hydrogen is mixed with inert gases required to obtain reducing atmospheres in different processes in the metallurgical industry, as is the case of heat treatment of the steel and welds. It is often used in annealing stainless steel alloys and magnetic steel alloys, weld and sintering of copper. Sometimes hydrogen is used obtained from dissociation of ammonia, which produces a mixture of 75% hydrogen and 25% nitrogen, mostly mononuclear part (N2 instead of N). The mixture is used to create protective atmospheres in applications such as welding or bright annealing. Hydrogen is also used in the following applications:

- Stress relief annealing



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- Hardening - Recrystallization and soft annealing of cold-formed material - Annealing to polishing

Electronic industry

In the electronics industry, in order to produce doped semiconductors are deposited trace amounts of elements (Si, As, Ge, etc.) on a silicon die in the form of hydrides, mixed with a stream of high purity hydrogen. Hydrogen is used as:

- Carrier gas of minor active elements (trace), such as arsine and phosphine, diffusion processes for producing layers of semiconductor in integrated circuits;

- Reaction gas with oxygen to generate steam in wet oxidation processes; - In the creation of atmospheres for growth of epithelial layers on silicon wafers; - Fuel for oxy-H2 torches to facilitate the deposition or strengthening of quartz rods, etc.

Methanol industry

Currently, all the methane produced worldwide is synthesized by a catalytic process from carbon monoxide and hydrogen. This reaction occurs at high temperatures and pressures and requires large and complicated industrial reactors. The syngas (CO+H2) can be obtained in different ways. Currently the most widely used process for obtaining synthesis gas are the partial combustion of natural gas in the presence of water vapor and the partial combustion of liquid hydrocarbon mixtures or coal in the presence of water. The most widely used industrial processes; using any of the three feeds (natural gas, mixture of liquid hydrocarbons or coal) are developed by Lurgi signatures Corp. Ltd. and Imperial Chemical Industries (ICI).

Transport industry

Fuel Cell Vehicles are similar to electric vehicles in that they use an electric motor to power the wheels. However, these vehicles use "fuel cells" onboard the vehicle to generate electricity. In a fuel cell, hydrogen (H2) from the fuel tank is combined with oxygen from the air to generate electricity. The hydrogen is provided from hydrogen storage tank. The hydrogen gas must be compressed at extremely high pressure at 350 to 700 bar to store enough fuel to obtain adequate driving range. The hydrogen is produced by electrolysis process in the hydrogen refuelling. In the water electrolysis process the hydrogen is produced by electrochemically splitting water molecules (H2O) into hydrogen (H2) and oxygen (O2). Nowadays, atmospheric electrolyze capacity can reach 500 Nm3/h and pressurized electrolyze capacity can reach a range of 1 – 120 Nm3/h are standard products.

4.3. Selection of the potential applications in terms of biogas resource and hydrogen demand Based on this market survey of industrial hydrogen it is concluded that the size of an hydrogen generation system as Bionico is suited for industrial applications such as glass production, metal processing, electronics industry and food industry, or small refuelling station upgrading biogas produced from a landfill site.

5. REFERENCE DOCUMENTS [1] Bionico deliverable D2.1 Industrial Specifications for a catalytic membrane reactor to produce hydrogen from

biogas.

[2] Grant Agreement number 671459 – Bionico – H2020-JTI-FCH-2014-1.

[3] A. Basile, S. Liguori, A. Iulianelli, “2 – Membrane reactors for methane steam reforming (MSR).” Membrane

Reactors for Energy Applications and Basic Chemical Production, p. 31-59, 2015.

[4] Wilhelm, D., Simbeck, D., Karp, a., & Dickenson, R. “Syngas production for gas-to liquids applications:

technologies, issues and outlook.” Fuel Process Technology, 71, p. 139-148. 2001.



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[5] Gallucci, F., Van Sintannaland M., J.A.M. Kuipers, “Theoretical comparison of packed bed and fluidized bed

membrane reactors for methane reforming”. International journal of hydrogen energy 35, p. 7142–7150. 2010.

[6] Bartholomew, C. H., & Farrauto, R. J. “In Fundamentals of industrial catalytic processes”. Hoboken, New Jersey,

USA: John Willey and Sons (Chapter 6). 2006.

[7]. Xu, J. and Froment, G. F., AIChE J, 35(1): 88. 1989.

[8] Woods R.R., Cuzens J.E., Saint-Just J., “Autothermal reforming of natural gas: A key technology for fuel cells”

International gas research confenrence (IGRC) Amsterdam. 2001.

[9] Gallucci F., Van Sint Annaland M., Kuipers J.A.M., “Autothermal Steam Reforming of Methane in a novel Fluidized

Membrane Reactor. Part 1 Experimental Demonstration”. Topics in Catalysis; 51, p. 133–145. 2008.

[10] Gallucci F., Van Sint Annaland M., Kuipers J.A.M., “Autothermal Steam Reforming of Methane in a novel

Fluidized Membrane Reactor. Part 2 Comparison of reactors configurations”. Topics in Catalysis; 51, p. 146–157.

2008.

[11] Ashrafi M., Pröll T., Pfeifer C., Hofbauer H., “Experimental study of model biogas catalytic steam reforming: 1.

Thermodynamic Optimization”. Energy & Fuels; 22. p. 4182-4189. 2008.

[12] Araki S., Hino N., Mori T., Hikazudani S., “Autothermal reforming of biogas over a monolithic catalyst”. Journal

of natural gas chemistry; 19, p. 477-481. 2010.

[13] Araki S., Hino N., Mori T., Hikazudani S., “Durability of a Ni based monolithic catalyst in the autothermal reforming

of biogas”. International journal of hydrogen energy; 34, p. 4727-4734. 2009.

[14] Biogas upgrading Evaluation of methods for H2S removal, Laura Bailon Allegue, Jørgen Hinge, 2014

[15] Biogas upgrading and utilization, IEA Bioenergy, A. Wellinger, A. Lindberg, 2000

[16] Gatze Lettinga, Salih Rebac and Grietje Zeeman, Challenge of psychrophilic anaerobic wastewater treatment

[17] Deublein, D., Steinhauser, A., Biogas from Waste and Renewable Resources, Wiley-VCH, 2008;

[18] LFG energy project Development handbook

[19] Report Biogas and bio-syngas upgrading, Danish Technological Institute Laura Bailón Allegue and Jørgen Hinge

Kongsvang Allé 29 DK–8000 Aarhus C, December 2012

[20] Biogas production: current state and perspectives Peter Weiland

[21] Levelized cost of electricity renewable energy technologies study november 2013, Frounhofer

[22] Renewable energy capacity statistics, IRENA, 2015

[23] Biogas – From refuse to energy, IGU, 2015

[24] IEA Bioenergy. Energy Technology Network (http://www.iea-biogas.net/plant-list.html)

[25] Global Methane Emissions and Mitigation Opportunities, GMI, 2014

[26] Green gasg rid 2014

[27] Bauer, F. et al, Biogas upgrading – Review of commercial technologies, SCG, 2013

[28] Hydrogen by the Chemical Economics Handbook” publicado por SRI Consulting]

[29] www.worldenergyoutlook.org/

[30] The Freedonia Group, Inc.

[31] PFC Energy; http://www.fuellingeuropesfuture.eu/es

[32] USGS, (2013), Nitrogen Statistics and Information; http://tinyurl.com/llvfcq6

[33] Potashcorp, (2013), Overview of Potashcorp and its Industry; http://tinyurl.com/pahoul5

http://www.iea-biogas.net/plant-list.html

http://www.worldenergyoutlook.org/

http://www.fuellingeuropesfuture.eu/es



_________________________________________________________________________________________________________________ Public

[34] “World Flat Glass” report, by Freedonia Group en 2014.

[35] World Steel Association-Worldsteel, published by Metales&Metalurgia.com, 2014

[36] IHS Global Insight

http://www.metalesymetalurgia.com/?s=%22World+Steel+Association%22

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BIOGAS MEMBRANE REFORMER FOR DECENTRALIZED …...required represented on a schematic plant layout....

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