Patent Publication Number: US-10760022-B2

Title: Low carbon bio-oil and its manufacturing method

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This non-provisional application claims priority under 35 U.S.C. § 119 on Patent Application No. TW106136768 filed in Taiwan, Republic of China Oct. 25, 2017, the entire contents of which are hereby incorporated by reference in its entirety. 
     FIELD OF THE INVENTION 
     The present invention discloses a low carbon bio-oil, selected from the group consisting of a thermo-chemical oil product, a fatty acid containing bio-oil and a bio-alcohol. The invention also discloses a preparation method of preparing the low carbon bio-oil. 
     BACKGROUND OF THE INVENTION 
     Biofuel refers to a solid, liquid, or gas that is made of, or extracted from a biomass. Biomass can be converted into easy-to-use, energy-containing substances in three different transformations, including: thermal, chemical, and biochemical. Biofuel oil is an important renewable energy source. Currently, about 3 million tons of fuel oil is used in Taiwan. The heating value of biofuel oil is about half of that of fuel oil, and biomass pyrolysis oil market is about 300,000 tons of if we replaced 5% fuel oil. As the trend of traditional coal and oil use slows down due to the trend of carbon reduction, biofuels will play an important role in reducing carbon emissions in the future. However, thermochemical technologies can handle a large amount of biomass wastes and convert them into fuels. 
     In the prior art, Artur Pozarlik et al. conducted a study on the mixing of ethanol, biomass pyrolysis oil, diesel oil or butanol, pyrolysis oil and diesel oil. The mixture of ethanol and pyrolysis oil can be mixed about 10% with diesel, and the mixture of butanol and pyrolysis oil can be mixed about 50% with diesel. The results show that the mutual solubility of butanol is better than that of ethanol; US 20120167451 A1 indicate emulsifies the biomass pyrolysis oil into a dispersed phase through alcohols, water and surfactants to stabilize the biomass pyrolysis oil properties. However, the cost of the surface active agents is high and the heating value of water and alcohol is low, which makes the energy density of the fuel less ideal. US 20130327980 A1 states that the oil after mixed with the biomass pyrolysis oil, surfactant and the lipid can be used as fuel or as feedstock as follow-up process to produce oil. 
     However, the heating value of the bio-fuel from the conventional thermochemical technique is lower than other bio-fuel, and the bio-fuel from the traditional thermochemical technique is acidity. Therefore, the bio-fuel from the conventional thermochemical technique need to be modified by some adjustment to be applied on conventional heating equipment. Besides, the stability of the bio-fuel from the conventional thermochemical technology is poor than other bio-fuel, which makes it not able to transported under higher than room temperature. 
     However, by in aspect of chemical structure, the solubility of the fatty acids in bio-thermal chemical oil is higher than fuel oil, and the heating value of the fatty acid is twice as high as the bio-thermal chemical oil. It is expected that the heating value would be enhanced if the oils were mixed with some specific bio-fuel in specific ratio. Therefore, the present invention, combines the concept of blending solvent to stabilize the biomass thermal chemical oil, proposes the use of bio-alcohol and fatty acid-rich waste biomass oil to improve the bio-thermal chemical stability and heating value. Besides, the present invention intends to simplify the blending process, thereby reducing the fuel costs. 
     SUMMARY OF THE INVENTION 
     Accordingly, the present invention provides a low-carbon bio-oil selected from the group consisting of a biomass thermo-chemical oil, a fatty acid-rich bio-oil, and bio-alcohol, wherein a range of high heat combustion for the low-carbon bio-oil is 3000-7000 cal/g. 
     In one of the embodiments of the present invention, the weight percentage of the fatty acid-rich bio-oil of the low-carbon bio-oil is less than 20%. 
     In one of the embodiments of the present invention, the weight percentage of the bio-alcohol of the low-carbon bio-oil is 0.1-10%. 
     In one of the embodiments of the present invention, the biomass thermo-chemical oil is a biomass pyrolysis oil, a carbonized tar, or liquid product after carbonization, pyrolysis or gasification. 
     In one of the embodiments of the present invention, the fatty acid-rich bio-oil is a black high acid value oils, a white high acid value oil or a palm fatty acid distillate (PFAD). 
     In one of the embodiments of the present invention, the weight ratio of the biomass pyrolysis oil to the black high acid value oil is 1:1. 
     In one of the embodiments of the present invention, the weight ratio of the biomass pyrolysis oil to the white high acid value oil is 3:1. 
     In one of the embodiments of the present invention, the weight ratio of the carbonized tar to the black high acid value oil is 3:1. 
     In one of the embodiments of the present invention, the weight ratio of the carbonized tar to the white high acid value oil is 3:1. 
     In one of the embodiments of the present invention, the fatty acid-rich bio-oil is obtained from a waste oil after manufacture process. 
     In one of the embodiments of the present invention, the alcohol is ethanol, butanol or a higher alcohol. 
     In one of the embodiments of the present invention, the weight ratio of the biomass pyrolysis oil, the black high acid value oil and the bio-alcohol is 15:5:1. 
     The low-carbon bio-oil of claim  11 , wherein the weight ratio of the biomass pyrolysis oil, the white high acid value oil and the bio-alcohol is 15:5:2. 
     To solve the problem, the present invention provides a method for producing a low-carbon bio-oil of claim  1 , which comprises the steps of: (a) obtaining an oil mixture selected from the group consisting of a biomass thermo-chemical oil, a fatty acid-rich bio-oil, and bio-alcohol: (b) heating the oil mixture to 40-90° C.; and (c) settling the mixture at room temperature to obtain a low-carbon bio-oil. 
     Based on the above description, the present invention further tests different blending ratio of thermochemical oils, fatty acid-rich waste biomass pyrolysis oil and bio-alcohol. The present invention has the high heat value and high stability of low-carbon fuel oil, which can effectively improve the problem of low combustion calorific value and acidity of traditional bio thermochemical oils, and difficult to transport with high temperature etc. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The Sole FIGURE shows the method for producing a low-carbon bio-oil of the present invention. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     By way of illustration, the specific embodiments will be disclosed in detail below, however, the features of the invention are not limited to these embodiments. 
     The present invention provides a low-carbon bio-oil which is selected from the group consisting of biomass thermo-chemical oil, a fatty acid-rich bio-oil, and bio-alcohol, wherein the characteristics of the raw material used in the examples herein are as shown in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 characteristics of the raw material used in the examples 
               
            
           
           
               
               
               
               
               
            
               
                   
                 biomass 
                 black high 
                 white high 
                   
               
               
                   
                 pyrolysis 
                 acid value 
                 acid value 
                 carbonized 
               
               
                 item 
                 oil 
                 oil 
                 oil 
                 tar 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Weight percentage 
                 1.137 
                 0.9024 
                 0.9806 
                 1.19 
               
               
                 g/cm 3   
               
               
                 Ash content wt % 
                 0.1734 
                 0.0751 
                 0.6986 
                 0.113 
               
               
                 higher heating value 
                 3791 
                 9213 
                 7390 
                 4167 
               
               
                 (HHV) cal/g 
               
               
                 Viscosity 
                 5.98 
                 9.32 
                 150.4 
                 9.53 
               
               
                 50° C., cSt 
               
               
                 Flash point ° C. 
                 39 
                 99 
                 87 
                 145 
               
               
                   
               
            
           
         
       
     
     The present invention provides a method for producing a low-carbon bio-oil. Please refer to the Sole FIGURE, which comprises the steps of: mixing a biomass thermo-chemical oil, a fatty acid-rich bio-oil and bio-alcohol in a specific ratio in a pre-heating chamber, then heating the oil mixture to 40-90° C.; and transporting the oil mixture into the pre-heating chamber, keep the temperature same as the pre-heating chamber, then mixing the oil mixture for 2 hours: settling the oil mixture at room temperature to obtain a low-carbon bio-oil. 
     Example 1 
     15 kg biomass pyrolysis oil and 15 kg black high acid value oil is mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. The first analysis sample is shaken before sampling and is analyzed again due to the large difference. According to the data, 15 kg of biomass pyrolysis oil and 15 kg black high acid value oil are mixed and the phase separation is more serious (as shown in Table 2). 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Analysis result of example 1 
               
            
           
           
               
               
            
               
                   
                 item 
               
            
           
           
               
               
               
            
               
                   
                 1-1 
                 1-2 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Upper 
                 Middle 
                 Lower 
                 Upper 
                 Middle 
                 Lower 
               
               
                   
                 section 
                 section 
                 section 
                 section 
                 section 
                 section 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Weight percentage g/cm 3   
                 1.149 
                 0.9170 
                 1.162 
                 0.9182 
                 0.9182 
                 1.12 
               
               
                 Ash content wt % 
                 0.2206 
                 0.028 
                 0.4043 
                 0.0109 
                 0.293 
                 0.2822 
               
               
                 higher heating value 
                 3614 
                 9068 
                 2534 
                 8899 
                 8858 
                 Cannot 
               
               
                 (HHV) cal/g 
                   
                   
                   
                   
                   
                 be lit 
               
               
                 Viscosity 50° C., cSt 
                 6.91 
                 8.4 
                 7.05 
                 8.5 
                 8.47 
                 7.95 
               
               
                   
               
            
           
         
       
     
     Example 2 
     1125 g biomass pyrolysis oil and 375 g white high acid value oil is heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of weight percentage and ash content, the properties of upper section is close to white high acid value oil, and the properties of lower section is close to biomass pyrolysis oil. Higher heating value (HHV) shows large difference of different section. (as shown in Table 3). 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Analysis result of example 2 
               
            
           
           
               
               
            
               
                   
                 2 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Upper 
                 Middle 
                 Lower 
               
               
                   
                 item 
                 section 
                 section 
                 section 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Weight percentage 
                 0.939 
                 1.111 
                 1.125 
               
               
                   
                 g/cm 3   
               
               
                   
                 Ash content wt % 
                 0.0109 
                 0.1543 
                 0.2699 
               
               
                   
                 higher heating value 
                 3754 
                 3313 
                 3338 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 4.93 
                 4.8 
                 4.98 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 3 
     1125 g carbonized tar and 375 g white high acid value oil is heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of weight percentage and ash content, the properties of upper section are close to white high acid value oil, and the properties of lower section is close to biomass pyrolysis oil. Higher heating value (HHV) shows large difference of different section. (as shown in Table 4). 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Analysis result of example 3 
               
            
           
           
               
               
            
               
                   
                 3 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Upper 
                 Middle 
                 Lower 
               
               
                   
                 item 
                 section 
                 section 
                 section 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Weight percentage 
                 0.9745 
                 1.142 
                 1.161 
               
               
                   
                 g/cm 3   
               
               
                   
                 Ash content wt % 
                 0.4644 
                 0.4528 
                 0.2327 
               
               
                   
                 higher heating value 
                 3370 
                 3413 
                 3838 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 8.93 
                 7.05 
                 7.14 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 4 
     375 g carbonized tar and 125 g white high acid value oil is heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of data, the properties are close to original oil, which means the carbonized tar mixed well with white high acid value oil. (as shown in Table 5). 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Analysis result of example 4 
               
            
           
           
               
               
               
            
               
                   
                 Item 
                 4 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Weight percentage 
                 1.109 
               
               
                   
                 g/cm 3   
               
               
                   
                 Ash content wt % 
                 0.3341 
               
               
                   
                 higher heating value 
                 3838 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 7.51 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 5 
     375 g carbonized tar and 125 g black high acid value oil is heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of higher heating value (HHV), the properties are different from original oil, which means the carbonized tar cannot mixed well with black high acid value oil. (as shown in Table 6). 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Analysis result of example 5 
               
            
           
           
               
               
               
            
               
                   
                 Item 
                 5 
               
               
                   
                   
               
            
           
           
               
               
               
            
               
                   
                 Weight percentage 
                 1.142 
               
               
                   
                 g/cm 3   
               
               
                   
                 Ash content wt % 
                 0.4528 
               
               
                   
                 higher heating value 
                 8982 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 9.6 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 6 
     1125 g biomass pyrolysis oil, 375 g black high acid value oil and 75 g alcohol are heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of higher heating value (HHV), the alcohol can enhance the uniformity of overall oil. (as shown in Table 7). 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Analysis result of example 6 
               
            
           
           
               
               
            
               
                   
                 6 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Upper 
                 Middle 
                 Lower 
               
               
                   
                 item 
                 section 
                 section 
                 section 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Weight percentage 
                 0.9779 
                 1.049 
                 1.057 
               
               
                   
                 g/cm3 
               
               
                   
                 Ash content wt % 
                 0.1153 
                 0.085 
                 0.0898 
               
               
                   
                 higher heating value 
                 4050 
                 4084 
                 4288 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 6.8 
                 3.57 
                 3.48 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Example 7 
     1125 g biomass pyrolysis oil, 375 g black high acid value oil and 75 g alcohol are heated to 60° C., and then mixed and settling in room temperature, then take out as upper, middle and lower three sections. Then take out 500 g for each section to carry out specific gravity, ash content, higher heating value and viscosity analysis. From the test result of higher heating value (HHV), the alcohol can enhance the uniformity of overall oil. (as shown in Table 8). 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Analysis result of example 7 
               
            
           
           
               
               
            
               
                   
                 7 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Upper 
                 Middle 
                 Lower 
               
               
                   
                 item 
                 section 
                 section 
                 section 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                 Weight percentage 
                 0.9779 
                 1.077 
                 1.078 
               
               
                   
                 g/cm 3   
               
               
                   
                 Ash content wt % 
                 0.4417 
                 0.4241 
                 0.4230 
               
               
                   
                 higher heating value 
                 3930 
                 4049 
                 4115 
               
               
                   
                 (HHV) cal/g 
               
               
                   
                 Viscosity 
                 6.67 
                 4.2 
                 4.24 
               
               
                   
                 50° C., cSt 
               
               
                   
                   
               
            
           
         
       
     
     Although the present invention has been described in terms of specific exemplary embodiments and examples, it will be appreciated that the embodiments disclosed herein are for illustrative purposes only and various modifications and alterations might be made by those skilled in the art without departing from the spirit and scope of the invention as set forth in the following claims.