Bioethanol Manufacturing from Lignocellulosic Biomass 1.

0 Problem Statement The process is to manufacture ethanol from lignocellulosic biomass by using advanced pretreatment and fermentation methods. The raw material used is the yellow poplar hardwood; perennial tree lived in moderate climate regions, cheap grow cost, and easy to be stored. 2.0 Problem Formulation The manufacturing process can be represented in the following block diagram:
Size reduction Dilute acid pretreatment

Enzyme production

Residual solids processing

Simultaneous saccharification and fermentation

Ethanol recovery

This process of ethanol manufacturing starts with reducing the size of the large materials and with addition of mechanical process of shredding of the material. Next, hydrolysis is promoted within the material by processing. Then the resulting slurried material is fermented to produce alcohol. Lastly, the alcohol is purified through filtration and distillation. For the conceptual design of the bioethanol plant, Aspen Plus will be used as the flow sheet simulator.

3.0 Problem Analysis

3.1 Chemical Components Definition Feedstock composition Component Cellulose Hemicellulose Lignin Acetate Moisture Total Xylan Arabinan Mannan Galactan 20 600 850 4 250 260 29 930 5020 51800 158 850 19.24 0.79 3.97 0.24 27.96 4.69 48.39 Flow rate (kg/h) 46 140 % dry basis 43.10

The components included in this process may be classified as vapor-liquid equilibrium components, and identifiable solids components. For the vapor-liquid equilibrium components, properties needed for the simulator are flash point, molecular weight, heat and free energy of formation, critical parameters, Antoine parameters, heat of vaporization, liquid molar volume, ideal gas capacity, and liquid heat capacity. Parameters required for the identifiable solid components include molecular weight, heat of formation, solid molar volume and solid heat capacity.

4.0 Problem Solution and Discussion 4.1 Biomass Pretreatment The pretreatment of lignucellulosic materials are to remove the lignin and hemicellulose, reducing cellulose crystallinity, and increasing the porosity of the materials. Among the methods used is mechanical treatment; chipping, grinding and milling, are used to reduce cellulose crystallinity. The size of the materials is 10-30mm after chipping, and 0.2-2mm after milling or grinding. There are several methods in the pretreatment such as steam explosion, ammonia fiber explosion (AFEX), acid hydrolysis, and alkaline hydrolysis. In this process, the acid hydrolysis is used as the pretreatment method: The milled wood chips are heated to about 100 C using low-pressure steam. Afterwards, steam and sulfuric acid are added to the mixture in a pretreatment reactor. The reactor temperature is 190C, while the pressure is 12.2 atm. The concentration of acid is 0.5%, while the concentration of solids in the outlet stream is 22%. The reactor outlet is flashed to 1 atm and 100C. This removes in the vapor stream (53 650 kg/h) about 25% of the water and 15% of the acetic acid. The next step is the separation of the solid and the liquid phases, which is modeled by a single-stage solid washer. The separation will leave the solid portion with about 40% insoluble solids. This means that not the entire amount of the toxic materials (acetic acid) will be found in the liquid stream. Washing with water can be done to remove more of this toxic material. In this process, the amount of water used is kg/h which is about 50% of the 5 initial amount of liquid: 211 x 10 kg/h. By this way, 65% of the acetic acid will be found in the liquid stream. From the liquid stream, about 88% of the acetic acid is removed in a continuous ionexchange unit, with the entire amount of sulfuric acid simultaneously. After that, the mixture is overlimed. The liquid pH is increased to 2 by sulfuric acid addition with amount of 90 kg/h. Then 68.5 kg/h of the lime is added to raise the pH to 10, and the mixture is heated with steam injection at 50C for 1 hour. Next the liquid pH is adjusted to

pH 4.5 and held for 4 hours. Thus, large gypsum crystals will be formed and can be separated by means of rotary drum filtration and hydrocyclone. The amount of gypsum produced is about 200 kg/h in which the solid content is 80%.

4.2 Saccharification and Fermentation The saccharification process requires cellulose enzymes, while for fermentation, the recombinant Z.mobilis grown in seed-fermentation train is used as ethanologen. The liquid is fermented for 7 days, to give total fermentation volume of about 60 000m3. Vapor products from the fermentation process is about 25 000 kg/h, mostly CO2, but also 300 kg/h of ethanol that is recovered by scrubbing with water. In addition to saccharification and fermentation, loss to other product occurs. About 7% of the sugars available for fermentation are considered lost to contamination. The fermentors are cooled by pump-around loops and external heat exchangers. The total energy required is 9.5 x 106kcal/h. 4.3 Ethanol Purification and Water Recovery Ethanol is recovered from the liquid by distillation and molecular-sieve absorption. First, solids component are separated. The liquid is mixed with the aqueous solution of ethanol recovered from the gas product of the fermentation process. The resulting mixture is about 3.23 x 105 kg/h with 8% ethanol weight. The liquid then fed to two distillation unit. The first unit delivers 1000 kg/h vapor distillate and 32 000 kg/h liquid distillate. The liquid distillate contains 77% ethanol and 20% water, with 3% furfural impurity. The recovery of ethanol is almost 100%. The bottom stream (2.9 x 105 kg/h) consists of water. The second unit delivers 26 730 kg/h distillate where the weight concentration of ethanol is 92.5%. The distillate is free of furfural. The bottoms are mixed with the bottoms of the first unit and sent to water purification.

5.0 Equation and Variables 5.1 Reaction in Pretreatment Reactor Reaction (Cellulose)n + n H2O (Cellulose)n + n H2O (Cellulose)n + 0.5n H2O (Mannan)n + n H2O (Mannan)n + m H2O (Mannan)n + n HMF (Galactan)n + n H2O (Galactan)n + m H2O (Xylan)n (Arabinan)n Acetate n Glucose m Glucose Oligomer 0.5n Cellobiose n Mannose n Mannose Oligomer 2n H2O n Glucose n Glucose oligomer Conversion 0.065 0.007 0.007 0.75 0.05 0.15 0.75 0.05 0.1 0.1 1

n Furfural + 2n H2O n Furfural + 2n H2O Acetic acid

5.2 Equation in Saccharification Reaction Reaction (Cellulose)n + m H2O (Cellulose)n + 0.5n H2O (Cellulose)n + n H2O m Glucose oligomer 0.5n Cellobiose n Glucose Conversion 0.068 0.012 0.8

Cellobiose + H2O

2 Glucose

1.0

5.3 Equation in Fermentation Reaction Reaction Glucose 2 Ethanol + 2 CO2 6 Z.mobilis+2.4H2O+0.3O2 2 Glycerol + O2 2 Succinic acid + O2 Conversion 0.92 0.027 0.002 0.008 0.022 0.013 0.85 0.029 0.029 0.009 0.024 0.014

Glucose + 1.2 NH3 Glucose + 2 H2O Glucose + 2 CO2 Glucose Glucose 3 Xylose

3 Acetic acid 2 Lactic acid 5 Ethanol + 5 CO2 5 Z.mobilis+2H2O+0.25)2 5 Glycerol + 2.5 O2 5 Succinic acid + 2.5 O2

Xylose + NH3

3 Xylose + 5 H2O 3 Xylose + 5 CO2 2 Xylose 3 Xylose

5 Acetic acid 5 Lactic acid

6.0 DOF Analysis Raw material 158 850 kg/h wood 102 030 kg/h dry matter Ethanol Production Energy produced Energy required 25 000 kg/h 293 x 106kcal/h 8 x 106kcal/h for steaming 80 x 106kcal/h for pretreatment 28 x 106first distillation column 19 x 106kcal/h second distillation column CO2 produced 23 760 kg/h from fermentation 94 675 kg/h from lignin burning Gypsum produced 158 kg/h