HYDROGEN FROM

BIOMASS

SR.NO PARTICULARS PAGE NO.

1 ABSTRACT 2

2 INTRODUCTION 4

3 BIOMASS AS A RENEWABLE SOURCE 6

4 PROCESS CONCEPT 9

5 PRODUCTION OF BIO-OIL 11

6 PRODUCTION OF HYDROGEN 14

7 RESULTS & DISCUSSION 17

8 ADVANTAGES OF PROCESS 20

9 CONCLUSION 22

10 BIBLIOGRAPHY 23

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A SEMINAR REPORT ON

HYDROGEN FROM BIOMASS

SUBMITTED BY GUIDED BY

PRASAD M. RANADE PROF. J.P.KAWRE

ABSTRACT

Many efforts have been made to produce an alternative to natural gas. One

leading idea is that of renewable hydrogen. Hydrogen is the prototype of the

environmentally cleanest fuel of interest for power generation using fuel cells. At

present, hydrogen is produced almost entirely from fossil fuels such as natural

gas, naphtha and inexpensive coal. However these processes are not environment

friendly as carbon emissions are always associated with them. Biomass as a

product of photosynthesis is a renewable source that can be used for sustainable

production of hydrogen. However, direct production of hydrogen from biomass by

gassification/water gas shift technology is unfavorable economically, except for

very low cost feed stocks and very large plants. The approach proposes an

alternative strategy with potentially better economics resulting from the combined

production of hydrogen with valuable co-products. The proposed strategy can be

applied to any lignocellulosic biomass either from agriculture or from forest

operations. Cont…

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The process involves the thermo-chemical conversion of biomass to

hydrogen by catalytic steam reforming of specific fractions derived from fast

pyrolysis and aqueous/steam process of biomass. Bio-oil (as a whole or it’s

selected fractions) can be converted to hydrogen via catalytic steam reforming

followed by a water gas shift conversion step. Fast pyrolysis, a technology near

commercial scale, could be carried out in a regional network of plants that would

supply bio-oil to a central reforming facility. The preferred option is to separate bio-

oil into a lignin-derived fraction, which could be used for producing phenolic resins

or fuel additives and a carbohydrate derived material that would be steam

reformed to produce hydrogen. The co-product strategy can also be applied to

residual fractions derived from pulping operations and from ethanol production.

Hydrogen can be generated from these fractions that are currently available in

most pulp mills and that will available in future.

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2 .Introduction
It is widely acknowledged that hydrogen is an attractive energy source to

replace conventional fossil fuels, both from the environmental and economic

standpoint. It is often cited as a potential source of unlimited clean power. When

hydrogen is used as a fuel it generates no pollutants, but produces water, which

can be recycled to make more hydrogen (Figure 1).

FIGURE 1. HYDROGEN ENERGY SYSTEM

Apart from its use as a clean energy resource, hydrogen can be used for

various other purposes in chemical process industries. It is used as a reactant in

hydrogenation process to produce lower molecular weight compounds. It can also

be used to saturate compounds, crack hydrocarbons or remove sulfur and

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nitrogen compounds. It is a good oxygen scavenger and can therefore be used to

remove traces of oxygen to prevent oxidative corrosion. In the manufacturing of

ammonia, methanol and synthesis gas, the use of hydrogen is well known. The

future widespread use of hydrogen is likely to be in the transportation sector,

where it will help reduce pollution. Vehicles can be powered with hydrogen fuel

cells, which are three times more efficient than a gasoline-powered engine. As of

today, all these areas of hydrogen utilization are equivalent to 3% of the energy

consumption, but it is expected to grow significantly in the years to come.

The commercially usable hydrogen currently being produced is extracted

mostly from natural gas. Nearly 90% of hydrogen is obtained by steam reformation

of naphtha or natural gas. Gasification of coal and electrolysis of water are the

other industrial methods for hydrogen-production. However, these processes are

highly energy-intensive and not always environment-friendly. More over, the fossil

fuel (mainly petroleum) reserves of the world are depleting at an alarming rate. So,

production of hydrogen by exploiting alternative sources seems imperative in this

perspective. Biomass is such an alternative.

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3. BIOMASS AS A RENEWABLE RESOURCE

Biomass is defined as a material that has participated in the growing cycle

in Agriculture waste, forest residue, urban wood waste, and trees and grasses

grown, as energy crops are materials commonly referred to as biomass. Because

biomass consumes as much CO2 in the growing cycle as is produced when it is

transformed into energy, the net CO2 contribution from biomass-derived fuels is

considerably less than from fossil-derived fuels. In addition, producing biomass on

a sustainable basis by growing energy crops will support agricultural sector, an

important part of our economy. Successful commercialization of this technology

will also reduce oil and gas imports of the country.

Biomass, as a product of photosynthesis, is the most versatile non-

petroleum renewable resource that can be utilized for sustainable production of

hydrogen (Table 1). Therefore, a cost-effective energy-production process could be

achieved in which agricultural wastes and various other biomasses are recycled to

produce hydrogen economically.

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SOURCE MAXIMUM OUTPUT COMMENT

Regenerative Source

Biomass 9 × 1012 W For total world land coverage.

For total world coverage.

Wind Power 6 × 10122 W Required heavy-duty storage
system.
Restricted to specific areas
Perhaps 109 W (mid-ocean ridges very long
G EOTHERMAL S OURCE term)

High Density Source

No more than 1K rise in

5
10 W or more environment temp. Problems
Nuclear Power of waste disposal & safety.

Pollution abatement is
9
10 W maximum essential for small & large-
Fossil Fuels allowable scale application.

Table 1. Earth-based world power sources and possible practical expectations

As an energy source, biomass has several important advantages.

Renewability is obviously a key feature. It also has unique versatility. The list of

plant species, by-products and waste materials that can potentially be used as

feedstock is almost endless (Table 2). Major resources in biomass include

agricultural crops and their waste by-products, lignocellulosic products such as

wood and wood waste, waste from food processing and aquatic plants and algae,

and effluents produced in the human habitat. Moderately dried wastes such as

wood residue, wood scrap and urban garbage can be burned directly as fuel.

Energy from water-containing biomass such as sewage sludge, agricultural and

livestock effluents as well as animal excreta is recovered mainly by microbial

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fermentation. Moisture, ash content and gross calorific values of different solid

biomass feedstock are given in Table 2.

BIOMASS MOISTURE (%) ASH (%) CV (MJ/Kg)

Bagasse 50.0 1.0-2.0 9.2
Bagasse pitch 40.0 2.0 7.5-8.4
Spent bagasse 40.0 10.0 12.5
Saw Dust 35.0 2.0 11.3
Rice husk 10.0-15.0 15.0-20.0 12.6-13.8
Rice straw 6.0 16.0 14.4
Deoiled rice bran 16.0 16.0 11.3
Coffee 11.0-14.0 2.0-5.0 15-17.5
Peanut shell 10.0 2.0-3.0 16.8
Coconut shell 10.0 1.0 18.8
Soya straw 7.0-8.0 5.0-6.0 15.5-15.9

TABLE 2. MOISTURE, ASH CONTENT & GROSS CALORIFIC VALUE OF DIFFERENT BIOMASS FEEDSTOCK

4. Process Concept

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Unfortunately, hydrogen content in biomass is only 6-6.5%, compared to

almost 25% in natural gas. For this reason, on a cost basis, producing hydrogen

by a direct conversion process such as the biomass gasification/water-gas shift

cannot compete with the well-developed technology for steam reforming of natural

gas. However, an integrated process, in which biomass is partly used to produce

more valuable materials or chemicals with only residual fractions utilized for

generation of hydrogen, can be an economically viable option. The proposed

method, which was described earlier , combines two stages: fast pyrolysis of

biomass to generate bio-oil and catalytic steam reforming of the bio-oil to hydrogen

and carbon dioxide. The original concept was that the pyrolysis oil could be

fractionated into two fractions based on water solubility. The water-soluble fraction

is to be used for hydrogen production and the water insoluble fraction could be

used in adhesive formulation . The bio-oil can be stored and shipped to a

centralized facility where it is converted to hydrogen via catalytic steam reforming

and shift conversion. Catalytic steam reforming of Bio-oil at 750-850ºC over a

nickel-based catalyst is a two-step process that includes the shift reaction:

Bio-oil + H2O CO + H2

CO + H2O CO2 + H2
The overall stoichiometry gives a maximum yield of 17.2-g H/100 g bio-oil

11.2 wt.% based on wood).

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Fig.2 Mass balance diagram of hydrogen production

The actual process involve two stages:

1) Production of bio-oil by fast pyrolysis

2) Production of Hydrogen by catalytic steam reforming

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5.PRODUCTION OF BIO-OIL BY FAST PYROLYSIS

Fast pyrolysis is a high temperature process in which biomass is rapidly heated in

the absence of oxygen. As a result it decomposes to generate mostly vapors and

aerosols and some charcoal. After cooling and condensation, a dark brown mobile

liquid is formed which has a heating value about half that of conventional fuel oil.

While it is related to the traditional pyrolysis processes for making charcoal, fast

pyrolysis is an advanced process, which is carefully controlled to give high yields of

liquid.

The essential features of a fast pyrolysis process are:

♦ Very high heating and heat transfer rates, which usually requires a finely

ground biomass feed.

♦ Carefully controlled pyrolysis reaction temperature of around 500oC in the

vapor phase, with short vapor residence times of typically less than 2

seconds.

♦ Rapid cooling of the pyrolysis vapors to give the bio-oil product.

The Process:
Pelletized peanut shells were pyrolyzed using the fast ablative pyrolysis

system (vortex reactor). The reactor wall temperature was maintained within the

range of 600-625°C, which has been proven to provide the highest bio-oil yield.

Nitrogen at a flow rate of 15 kg/h was used as the carrier gas for the biomass

particles in the pyrolysis reactor. The tests proceeded smoothly at the rate of

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10 kg/h. eventually, 200-300 kg of pyrolysis oil was generated from feedstock.

Peanut shell oil was collected in the scrubber of the pyrolysis system as a two-

phase liquid (water was used for scrubbing pyrolysis vapors), with the top

fraction containing 32.3% organics (6% are lignin-derived oligomers) and 67.7%

water. Water content of the liquids was determined by Karl-Fisher titration

method using a Metrohm 701 KF Titrino analyzer. Elemental composition,

including the carbon, hydrogen, and oxygen content of these liquids was analyzed

by a commercial laboratory. The aqueous solutions were then used in reforming

tests to produce hydrogen.

Figure 3. Production of bio-oil by fast pyrolysis

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PHYSICAL PROPERTIES TYPICAL VALUE

Moisture content 15–30%
pH 2.5
Specific gravity 1.20
Elemental analysis, dry basis C 56.4%
H 6.2%
O (by difference) 37.3%
N 0.1%
Ash 0.1%
HHV as produced (depends on moisture) 16–19 MJ/kg
Viscosity (at 40ºC and 25% water) 40–100 cp.
Solids (char) 0.5%
Distillation max. 50% as liquid degrades

Table 3 : Typical properties and characteristics of pyrolysis oil

Characteristics:
♦ Liquid fuel.

♦ Easy substitution for conventional fuels in many static appliance boilers,

engines, turbines.

♦ Does not mix with hydrocarbon fuels.

♦ Not as stable as fossil fuels.

♦ Heating value is about 40% that of fuel oil or diesel on a weight basis and

60% on volume basis.

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6. PRODUCTION OF HYDROGEN BY
CATALYTIC STEAM REFORMING
The experiments were carried out using a bench-scale fluidized-bed steam

reformer.

The schematic of the fluidized bed system is shown in Figure 4.

The two-inch-diameter Inconel reactor supplied with a porous metal distribution

plate was placed inside a three-zone electric furnace.

The reactor contained 150-200g of commercial nickel-based catalyst from UCI

(C11-NK) ground to the particle size of 300-500µm. The catalyst was fluidized

using superheated steam, which was also a reactant in the reforming process.

Steam was generated in a boiler and superheated to 750°C before entering the

reactor at a flow rate of 2-4 g/min.

Liquids were fed at a rate of 2-5 g/min using a diaphragm pump.

A specially designed oil injection nozzle supplied with a cooling jacket was used to

spray liquids into the catalyst bed.

The oil temperature in the injector was controlled by a coolant flow and

maintained below boiling point to prevent premature evaporation of volatiles

and consequent deposition of nonvolatiles. The condensate was collected in a

vessel whose weight was continuously monitored.

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The outlet gas flow rate was measured by a mass flow meter and by a dry test
meter.

The gas composition was analyzed every 5 minutes by an MTI gas chromatograph.

The analysis provided concentrations of hydrogen, carbon monoxide, carbon

dioxide, methane, ethylene, and nitrogen in the outlet gas stream as a function of

time.

The temperatures in the system as well as the flows were recorded and controlled

by the OPTO data acquisition and control system.

Figure 4. Hydrogen production from Biomass

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The measurements allowed determination of the total and elemental balances for

the reforming tests as well as the calculation of the yield of hydrogen generated

from the biomass-derived liquid feed.

The maximum (stoichiometric) yield of hydrogen was 2+m/2n-k/n moles per mole

of carbon in feed. Therefore, 63 g of hydrogen could be theoretically obtained from

1 L of peanut shell oil extract.

The steam reforming experiments in the fluidized bed reactor were carried out at

the temperature of 8000C and 8500C.

The steam to carbon ratio varied from 7 to 13, while the methane-equivalent gas

hourly space velocity GC1HSV was in the range of 1200-1500 h-1.

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7.RESULTS & DISCUSSION

Gas composition (on nitrogen free basis) obtained from the peanut shell pyrolysis

oil is shown in Figure 6.

Figure 6. Composition of the gas produced during steam reforming of peanut shell bio-oil
carbohydrate-derived fraction at 850°C and S/C=9

 During eight hours of the experiment, the gas composition was very stable and

only a small decrease in the concentration of hydrogen and an increase in

methane were observed.

 Methane concentration, though it grew to 3000-4000 ppm, still remained an

order of magnitude smaller than that of the three major gas components

and, therefore, is not shown in Figure 6.

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 More fluctuation was observed in the amount of gas produced and,

consequently, in the yield of hydrogen from the peanut bio-oil fraction, which is

presented in Figure 7.

Figure 7. Yield of hydrogen obtained during reforming of peanut shell bio-oil carbohydrate-
derived fraction at 850°C and S/C=9 [3].

 The hydrogen yield was still at the level of 80% of the stoichiometric potential

after eight hours on stream.

 Peanut shell liquid had a higher concentration of the organic compounds,

especially of lignin oligomers than the wood oil fractions. Large molecules of

lignin compounds are less reactive and probably required a longer contact time

with the catalyst than the smaller carbohydrate-derived fragments. They are

also more likely to form carbon deposits on the catalyst surface.

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 However, at 850°C, these deposits were removed and converted to hydrogen

and carbon oxides by steam processing (carbon to gas conversion of 92%).

 This resulted in hydrogen yields greater than 80% of the stoichiometric

potential during eight-hour catalyst time on stream.

 The yields of hydrogen would be 5-7% higher if the reforming was followed by

water-gas shift processing of carbon monoxide in the product gas.

 The global mass balance closure for the whole experiment was 94%, and 88-

91% of bio-oil carbon was converted to gases. Both the decrease in the

hydrogen production and the missing carbon in the mass balance suggest that

a small part of the carbon from bio-oil formed deposits on the catalyst surface.

Steam treatment of the used catalyst performed at 850°C resulted in the

release of hydrogen and CO2 in the amount corresponding to 4-5% of the

carbon fed (about half of the missing carbon). The other part of carbon

unaccounted for was probably entrained by product gases together with the

catalyst fines and collected in the cyclone and condensers.

 The steam treatment - by removing deposits from the surface also regenerated

the catalyst, which performed during the following test at the same level of

activity as the fresh catalyst.

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8.ADVANTAGES OF THE PROCESS

 The anticipated potential benefits or impact include:

 Use of biomass will support and further expand the agriculture-related sector.

 Application of the proposed technology will provide an economical and

environmentally acceptable means of disposing of the large quantity of peanut

shells .

 The demand for peanut shells as feedstock of the proposed technology will

improve the economic competitiveness of the peanut industry secures long-

term future.

 Widespread use of renewable hydrogen, the cleanest fuel for power

generation and for transportation applications, will reduce oil and gas

imports and will have significant environmental and health benefits for the

major cities .

 The proposed process will produce co-products in addition to hydrogen.

Alternative co-products that may be obtained from different bio-oil fractions

include phenol (for phenol-formaldehyde resins) and fuel oxygenates.

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 Similar to petroleum crude oil, biomass pyrolysis oil can be used for the

production of a multitude of fuel and chemical products, in addition to

hydrogen.

 The development of new agro-industrial infrastructure options that could result

in sustainable and equitable growth. The inclusion of small farms and the

attention to the appropriate scale of production technology will ensure the

ability to distribute the benefits of enhanced materials along the value chain

to the communities involved in generating the wealth.

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9.Conclusion

 Biomass can be a valuable resource for producing hydrogen if done as an

 integrated process that also generates higher value co-products.

 Fluidized bed reactor configuration proved to be efficient for reforming biomass-

derived liquids. It can be used for producing hydrogen by co-processing bio-

oils with natural gas or liquid hydrocarbons.

 The process needs to be optimized to determine conditions that allow for

maximum yields of hydrogen and minimum coke formation.

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BIBLIOGRAPHY

 I & EC Research, 36, 1507-1518.

 Production of Hydrogen from Biomass by Catalytic Steam Reforming of Fast

Pyrolysis Oil., Energy & Fuels, 12, 19-24.

 Web Sites:

 www.eere.energy.com

 www.eprida.com

 www.pyne.com

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