Upgrading of liquid fuel from the vacuum pyrolysis of biomass over the Mo-Ni/gamma-Al2O3 catalysts

High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo-10Ni/gamma-Al2O3 catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo-10Ni/gamma-Al2O3 catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC-MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. it is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil.

Scale study of direct synthesis of dimethyl ether from biomass synthesis gas

We investigated the synthesis of dimethyl ether (DME) from biomass synthesis gas using a kind of hybrid catalyst consisting of methanol and HZSM-5 zeolite in a fixed-bed reactor in a 100 ton/year pilot plant. The biomass synthesis gas was produced by oxygen-rich gasification of corn core in a two-stage fixed bed. The results showed that CO conversions reached 82.00% and 73.55%, the selectivities for DME were 73.95% and 69.73%, and the space-time yields were 124.28 kg m- 3 h- 1 and 203.80 kg m- 3 h- 1 when gas hourly space velocities were 650 h- 1 and 1200 h- 1, respectively. Deoxidation and tar removal from biomass synthesis gas was critical to the stable operation of the DME synthesis system. Using single-pass synthesis, the H2/CO ratio improved from 0.98-1.17 to 2.12-2.22. The yield of DME would be increased greatly if the exhaust was reused after removal of the CO2.

Effects of metal catalysts on CO2 gasification reactivity of biomass char

The effects of five metal catalysts (K, Na, Ca, Mg, and Fe) on CO2 gasification reactivity of fir char were studied using thermal gravimetric analysis. The degree of carbonization, crystal structure and morphology of char samples was characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The CO2 gasification reactivity of fir char was improved through the addition of metal catalysts, in the order K>Na>Ca>Fe>Mg. XRD analysis indicated that Na and Ca improved the formation of crystal structure, and that Mg enhanced the degree of carbon structure ordering. SEM analysis showed that spotted activation centers were distributed on the surface of char samples impregnated with catalysts. Moreover, a loose flake structure was observed on the surface of both K-char and Na-char. Finally, the kinetic parameters of CO2 gasification of char samples were calculated mathematically.

Operational characteristics of a 1.2-MW biomass gasification and power generation plant

In this study, we analyzed the operational characteristics of a 1.2-MW rice husk gasification and power generation plant located in Changxing, Zhejiang province, China. The influences of gasification temperature, equivalence ratio (ER), feeding rate and rice husk water content on the gasification characteristics in a fluidized bed gasifier were investigated. The axial temperature profile in the dense phase of the gasifier showed that inadequate fluidization occurred inside the bed, and that the temperature was closely related to changes in ER and feeding rate. The bed temperature increased linearly with increasing ER when the feeding rate was kept constant, while a higher feeding rate corresponded to a lower bed temperature at fixed ER. The gas heating value decreased with increasing temperature, while the feeding rate had little effect. When the gasification temperature was 700-800C, the gas heating value ranged from 5450-6400kJ/Nm3. The water content of the rice husk had an obvious influence on the operation of the gasifier: increases in water content up to 15% resulted in increasing ER and gas yield, while water contents above 15% caused aberrant temperature fluctuations. The problems in this plant are discussed in the light of operational experience of MW-scale biomass gasification and power generation plants.

Study on biomass circulation and gasification performance in a clapboard-type internal circulating fluidized bed gasifier

We investigated the solid particle flow characteristics and biomass gasification in a clapboard-type internal circulating fluidized bed reactor. The effect of fluidization velocity on particle circulation rate and pressure distribution in the bed showed that fluidization velocities in the high and low velocity zones were the main operational parameters controlling particle circulation. The maximum internal circulation rates in the low velocity zone came almost within the range of velocities in the high velocity zone, when uH/umf = 2.2-2.4 for rice husk and uH/umf = 3.5-4.5 for quartz sand. In the gasification experiment, the air equvalence ratio (ER) was the main controlling parameter. Rice husk gasification gas had a maximum heating value of around 5000 kJ/m3 when ER = 0.22-0.26, and sawdust gasification gas reached around 6000-6500 kJ/m3 when ER = 0.175-0.24. The gasification efficiency of rice husk reached a maximum of 77% at ER = 0.28, while the gasification efficiency of sawdust reached a maximum of 81% at ER = 0.25.

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O-2) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H-2+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 degrees C during 108 h lifetime test. However, no Coke deposition was detected for partial oxidation reforming process, which indicated that addition of O-2 can effectively prohibit the coke formation. O-2 Can also increase the CH4 conversion and H-2/CO ratio of the producer gas. The average conversion of CH4 in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H-2/CO ratio increased from 0.95 to 1.1 with the addition of O-2, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.

Design and Operation of A 5.5 MWe Biomass Integrated Gasification Combined Cycle Demonstration Plant

The design and operation of a 5.5 MWe biomass integrated gasification combined cycle (IGCC) demonstration plant, which is located in Xinghua, Jiangsu Province of China, are introduced. It is the largest complete biomass gasification power plant that uses rice husk and other agricultural wastes as fuel in Asia. It mainly consists of a 20 MWt atmospheric circulating fluidized-bed gasifier, a gas-purifying system, 10 sets of 450 kW(e) gas engines, a waste heat boiler, a 1.5 MWe steam turbine, a wastewater treatment system, etc. The demonstration plant has been operating since the end of 2005, and its overall efficiency reaches 26-28%. Its capital cost is less than 1200 USD/kW, and its running cost is about 0.079 USD/kWh based on the biomass price of 35.7 USD/ton. There is a 20% increment on capital cost and 35% decrease on the fuel consumption compared to that of a 1 MW system without a combined cycle. Because only part of the project has been performed, many of the tests still remain and, accordingly, must be reported at a later opportunity.

A study on the economic efficiency of hydrogen production from biomass residues in China

As part of Pilot Project of KIP of CAS, a feasibility study of hydrogen production system using biomass residues is conducted. This study is based on a process of oxygen-rich air gasification of biomass in a downdraft gasifier plus CO-shift. The capacity of this system is 6.4 t biomass/d. Applying this system, it is expected that an annual production of 480 billion N m(3) H-2 will be generated for domestic supply in China. The capital cost of the plant used in this study is 1328$/(N m(3)/h) H-2 out, and product supply cost is 0.15$/N m(3) H-2. The cost sensitivity analysis on this system tells that electricity and catalyst cost are the two most important factors to influence hydrogen production cost.

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen, However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/ N m(3) for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H-2/kg biomass. For biomass oxygen/steam gasification, the content of H-2 and CO reaches 63.27-72.56%, while the content Of H2 and CO gets to 52.19-63.31% for biomass air gasification. The ratio of H-2/CO for biomass oxygen/steam gasification reaches 0.70-0.90, which is lower than that of biomass air gasification, 1.06-1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.