KR102539180B1 - Emulsion oil comprising catalytic pyrolysis bio oil and diesel and manufacturing method thereof - Google Patents

Abstract

In the present invention, bio-oil obtained by thermal decomposition of lignin at 600° C. was emulsified using the HZSM-5 catalyst. Stable emulsified oils were obtained by applying various emulsifier combinations such as Span 80, Tween 60, Span 80 and Atlox 4916, Atlox 4916 and Zephrym PD3315 under various HLB (5.8 to 7.3) conditions. In the present invention, light oil was added in addition to bio-oil, and emulsified oil was prepared using an ultrasonic emulsifier.

Description

Emulsion oil comprising catalytic pyrolysis bio oil and diesel oil mixture and manufacturing method thereof

The present invention relates to an emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and light oil and a method for preparing the same. Specifically, it relates to an emulsified oil obtained by mixing pyrolysis bio-oil and light oil by a ZSM-5 catalyst using an ultrasonic emulsifier and a method for producing the same.

Recently, the price of fuel raw materials is rising according to the increase in demand for energy and the decrease in fossil fuels. The supply of alternative resources is needed to meet growing energy demand and stabilize the market. One of the main solutions is to utilize renewable energy or to use renewable energy mixed with fossil fuel (see Non-Patent Document 1).

Biomass, which is a powerful energy resource, can be converted into liquid and gas by thermochemical conversion processes such as pyrolysis, gasification and liquefaction (see Non-Patent Documents 2 to 5). Pyrolysis can quickly convert biomass-based waste into bio-oil, which can also be used in various fields (see Non-Patent Documents 6 to 13).

Materials produced through thermal decomposition of biomass and their yields vary depending on the distribution of lignin, cellulose, and hemicellulose in biomass (see Non-Patent Document 14). During thermal decomposition, reactions such as diesel deoxygenation, aromatization, cracking, oligomerization, and cyclization using a catalyst are accompanied, and through this, high-quality bio-oil with a high content of aromatic and phenolic compounds can be produced (Non-Patent Document 15 see 22).

Non-Patent Document 16 investigated the quality change of pyrolysis bio-oil using KH-ZSM-5 zeolite having acidic properties. Oligomer conversion was improved by the catalyst, and deoxygenation and cracking were also increased. Non-Patent Document 15 also investigated the catalytic thermal decomposition of biomass using HZSM-5, where a significant increase in aromatic compounds was observed.

Bio-oil obtained by rapid pyrolysis cannot be immediately used as a fuel for engines due to its high viscosity, high water content (15-30% by weight), stickiness and low calorific value (16-19 MJ/kg) (Non-Patent Document 23, 24). Methods for reforming the bio-oil include catalytic hydrogenation, esterification, and emulsification (emulsification) (see Non-Patent Documents 25 to 27).

Among the above methods, emulsification is the most economical, simple, and effective reforming method. Typically, emulsification of bio-oil is emulsification of two or more immiscible (immiscible) liquids such as bio-oil and light oil using a surfactant. The surfactant can be selected according to the HLB value, and the surfactant can be used alone or in combination with several other emulsifiers (see Non-Patent Document 28).

General methods for producing emulsified oils in this way are already known. Emulsified oil produced through the conventional method still has many problems to use as a fuel for sensitive equipment such as engines because layer separation occurs over time or mixing is uneven.

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Upgrading Bio-oil through Emulsification with Biodiesel: Mixture Production. Energy & Fuels, 24, pp. 1358-1364. ('Non-Patent Document 26') Liu Y., Li Z., Leahy J.J. and Kwapinski W., 2015. Catalytically Upgrading Bio-oil via Esterification. Energy & Fuels, 29, pp. 3691-3698. ('Non-Patent Document 27') Lin B.-J., Chen W.-H., Budzianowski W.M., Hsieh C.-T.,and Lin P.-H., 2016. Emulsification analysis of bio-oil and diesel under various combinations of emulsifiers. Applied Energy, 178, pp. 746-757. ('Non-Patent Document 28')

An object of the present invention is to provide an effective method for changing bio-oil into emulsified oil through catalytic pyrolysis of biomass and a high-quality emulsified oil produced through the method.

In order to solve the above problems, the present invention comprises the steps of 1) obtaining bio-oil by catalytic pyrolysis of biomass; 2) mixing light oil and a surfactant with the bio-oil; 3) emulsifying the mixture of step 2) using an ultrasonic emulsifier; provides an emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and diesel oil and a method for producing the same.

The biomass has a lignin content of 50% by weight or more, the catalyst includes HZSM-5, the thermal decomposition proceeds at 600 ° C or more, and the surfactant includes span 80, Atox 4916, and Zephrym PD 3315 At least one or more may be selected from the group.

In the mixture including the bio-oil, light oil, and surfactant, the light oil may be 80% by weight or more, and the surfactant may be 2% to 5% by weight.

Meanwhile, in step 3), emulsification may be performed for 5 minutes or more using an ultrasonic emulsifier.

The present invention also provides an emulsified oil comprising the catalytic pyrolysis bio-oil and diesel mixture, an emulsified oil prepared by a method for preparing the same, and a fuel composition comprising the emulsified oil.

The present invention as described above provides an emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and light oil, and a method for preparing the same. Catalytic thermal decomposition according to the present invention takes a very short time, and the emulsified oil prepared by the method according to the present invention not only provides very uniform physical properties as a whole, but also shows stable characteristics that do not cause layer separation for a long time.

1 is a schematic schematic diagram of a bench-scale reactor according to the present invention.
2 is a schematic schematic diagram of an ultrasonic emulsifier according to the present invention.
3 shows the analysis results of the pyrolysis bio-oil according to the present invention.
Figure 4 is the result of various experimental examples tested to obtain a stable emulsified oil in the HLB range of 5.8 to 7.3.
Figure 5 is the result of observing the variation over time of the emulsified oil according to the present invention.

In this application, terms such as "comprise", "have" or "have" are intended to indicate that there is a feature, number, step, component, part, or combination thereof described in the specification, but one or more other It should be understood that it does not preclude the possibility of addition or existence of features, numbers, steps, operations, components, parts, or combinations thereof.

In addition, the same reference numerals are used for parts having similar functions and actions throughout the drawings. Throughout the specification, when a part is said to be connected to another part, this includes not only the case where it is directly connected but also the case where it is indirectly connected with another element interposed therebetween. In addition, including a certain component does not exclude other components unless otherwise stated, but means that other components may be further included.

Hereinafter, an effective method for changing bio-oil into emulsified oil through catalytic pyrolysis of biomass according to the present invention and a high-quality emulsified oil produced through the method will be described in detail with reference to the accompanying drawings.

The experimental procedure consisted of two steps. The first step is to create catalytic pyrolysis oil using lignin as the feedstock and nanoporous HZSM-5 as the catalyst. The second step is to prepare gas oil and catalytic pyrolysis bio-oil (hereinafter 'CPO') using a combination of emulsifiers based on the HLB value.

In the first step, CPO was produced at 600 °C in a bench-scale reactor using lignin as the feedstock and nanoporous HZSM-5 (SiO ₂ /Al ₂ O ₃ = 50, by weight) as the catalyst. The feedstock was used in powder form while the catalyst was used in pellet form. The catalyst/biomass (weight) ratio was maintained at 1/20. Bio-oil was collected in a condenser maintained at -12 °C. The material of the aqueous and organic phases was obtained through the condenser. An emulsified oil was prepared using only organic phase materials in the mixture. 1 is a schematic diagram of a bench scale reactor according to the present invention.

In the second step, CPO and light oil are emulsified using various emulsifiers. Stable emulsified oils were obtained by applying emulsifier combinations such as Span 80 and Tween 60, Span 80 and Atlox 4916, Atlox 4916 and Zephrym PD3315. The HLB value of Span 80 is 4.3, and the HLB values of Atlox 4916, Zephrym PD3315, and Tween 60 are 6.0, 12.0, and 14.0, respectively. Various emulsifier combinations were selected according to their HLB values. The HLB values ranged from 5.8 to 7.3 to obtain a stable emulsified oil. All experiments were conducted in a TU-1800Y ultrasonic emulsifier.

2 is a schematic schematic diagram of an ultrasonic emulsifier according to the present invention. The ultrasonic emulsifier according to the present invention includes an ultrasonic probe for pulse generation, a sensor for temperature measurement, a digital controller for overall control, and a soundproof box. Predetermined amounts of CPO (5 to 15 wt%), emulsifier (1 to 3 wt%) and light oil (83 to 93 wt%) were poured into a flask reactor into which an ultrasonic probe was inserted. All emulsifications were run using 40% power frequency for 10 minutes. 100 ml of the obtained emulsified oil was transferred to a cylinder and checked regularly for 10 days to observe stability.

The physical and chemical properties of the nanoporous catalyst (HZSM-5, pore diameter: 3.02149 nm) were analyzed using a Micrometrix 3Flex surface area and porosity analyzer, and the results are shown in Table 1.

Properties Value BET Surface Area 294.8 m2/g Pore volume 0.22 cm3/g Pore Diameter 3.02 nm SiO2/Al2O3 50

The measurement was performed according to the ASTM D3663 procedure and was based on isothermal adsorption of nitrogen. FIG. 3 shows the analysis results of the pyrolysis bio-oil according to the present invention. The pyrolysis bio-oil was analyzed using an Agilent 5977E GCMS. Analysis showed that benzene derivatives, phenols, acids and esters were the main constituents. Regarding MAH, only toluene was found to be present. PAHs, aldehydes and furans were observed in small amounts.

Figure 4 is the result of various experimental examples tested to obtain a stable emulsified oil in the HLB range of 5.8 to 7.3. Several emulsifier combinations were investigated with different concentrations of CPO, emulsifier and light oil. In Fig. 4, the conditions for (a) to (e) are as follows. (a) 1% by weight of Span 80 and Tween 60 of HLB 7.3; 10 wt% CPO; 89 wt% light oil, (b) 3 wt% Span 80, Tween 60, and PD3315 at HLB 7.3; 15% by weight of CPO; 82 wt% light oil, (c) 2 wt% Atlox 4916 and Span 80 at HLB 5.8, 15 wt% CPO, 83 wt% light oil, (d) 3 wt% Span 80 and Atlox 4916 at HLB 5.8, 15 wt% CPO, 82% by weight of diesel

Referring to FIG. 4, in the case of (a) to (d) of FIG. 3, phase separation was shown within 10 minutes. (e) 5% by weight of Atlox 4916 and Zephrym PD3315 of HLB 7.3, 15% by weight of CPO, and 80% by weight of diesel did not undergo phase separation for 8 hours.

Figure 5 is the result of observing the variation over time of the emulsified oil according to the present invention. Experiments have shown that the most stable emulsified oil is provided when the weight ratio of Span 80 and Atlox 4916 emulsifier, HLB 5.8 and CPO: emulsifier: light oil is 5:2:93. The emulsified oil was observed for 10 days, and as shown in FIG. 5, no change was observed for 10 days.

Moisture content, acid number, HHV and oxidation stability are important physical indicators of all fuels. Table 2 shows the properties for the most stable emulsified oil. The water content was 2.328% by weight, the acid value was 1.409 KOH/g, and the oxidation stability was 24 hours or more. The most stable emulsified oil according to the present invention has an HHV value of 44.21 MJ/kg, which is similar to commercial gas oil (45.65 MJ/kg). Thus, emulsified oil obtained from the emulsification of CPO and diesel can potentially be used as fuel for diesel engines.

Properties Value HHV (MJ/kg) 44.21 Total acid value (mg KOH/g) 1.409 Water content (wt%) 2.328 Oxidation stability More than 24 hours.

Claims (9)

1) obtaining bio-oil by catalytic pyrolysis of biomass;
2) mixing light oil and a surfactant with the bio-oil;
3) emulsifying the mixture of step 2) using an ultrasonic emulsifier;
In the method for producing an emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and light oil,
The biomass has a lignin content of 50% by weight or more,
The catalyst includes HZSM-5,
The surfactant is at least one selected from the group including span 80, Atox 4916, and Zephrym PD 3315,
The HLB of the surfactant is 5.8 to 7.3,
In the mixture including the bio-oil, light oil, and surfactant, the bio-oil is 5% to 15% by weight, the light oil is 80% to 93% by weight, and the surfactant is 2% to 5% by weight. Catalytic pyrolysis bio-oil Method for producing an emulsified oil comprising a gas oil mixture. delete delete According to claim 1,
The pyrolysis is a method for producing emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and diesel fuel that proceeds at 600 ° C or higher. delete delete According to claim 1,
Method for producing an emulsified oil comprising a mixture of catalytic pyrolysis bio-oil and diesel oil, which is emulsified for 5 minutes or more using an ultrasonic emulsifier in step 3). An emulsified oil prepared by a method for producing an emulsified oil comprising a mixture of the catalytic pyrolysis bio-oil according to any one of claims 1, 4, and 7 and diesel oil. A fuel composition comprising the emulsified oil according to claim 8.

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