WO2016060450A1

WO2016060450A1 - Method for preparing high-quality aviation biofuel by using non-cooking oil, and aviation biofuel prepared thereby

Info

Publication number: WO2016060450A1
Application number: PCT/KR2015/010800
Authority: WO
Inventors: 황경란; 이진석; 한정식; 이경환; 최일호
Original assignee: 한국에너지기술연구원
Priority date: 2014-10-14
Filing date: 2015-10-14
Publication date: 2016-04-21
Also published as: KR101607868B1

Abstract

The present invention relates to a method for preparing aviation biofuel by using non-cooking oil, comprising the steps of: (a) forming a reaction product containing a paraffin-based hydrocarbon and an aromatic compound through deoxygenation, isomerization and aromatization from a liquid non-cooking oil in the presence of a catalyst without adding hydrogen; and (b) extracting an aviation fuel fraction by distilling the reaction product. According to the present invention, high-quality 100% aviation biofuel of high energy density, containing an isoparaffin-based hydrocarbon and an aromatic compound can be directly and selectively prepared from a non-cooking oil, which is a starting material, by optimizing a catalyst and reaction conditions without adding hydrogen so as to induce deoxygenation, isomerization and aromatization through a single-step process, and thus the present invention is remarkably economical with respect to preparation cost reduction and process simplification.

Description

Manufacturing method of high quality bio aviation oil using non-edible fat and oil and bio aviation oil produced thereby

The present invention relates to a method for producing high quality 100% bio-air fuel from non-edible fats and oils and bio-air oil produced thereby.

Internationally, there is a growing interest in alternative energy, facing the problems of air pollution caused by the consumption of fossil energy and energy supply and demand due to the depletion of fossil energy. Since biomass is a carbon compound in which carbon dioxide, a global warming material, is fixed using solar energy, biomass is an energy storage material having a characteristic of carbon compound together with fossil fuel.

The term biomass described above is often used for vegetable sources such as corn, soybean, linseed, sugar cane and palm oil, but the term is generally used for all living organisms, or their metabolism, which is part of the carbon cycle. It can be extended to by-products.

At present, countries around the world are paying attention to the positive effects of biomass on global warming, and establishing and implementing biomass resource management policy as a concrete way to reduce carbon dioxide emissions. Active development and research.

The development and research of the resource-recycling technology for the recovery and utilization of energy from the existing biomass has been mainly conducted to replace the gasoline and diesel as transport oils, and the first generation produced by reacting with alcohol in the presence of a catalyst from various biomass. Biodiesel (Fatty Acid Methyl Ester, FAME) is a technology that has already been developed, but due to the oxygen contained in the FAME clogging the fuel filter in the vehicle application, corrosion of the internal control device of the distributed high-pressure pump or corrosion of the fuel injection nozzle It has been applied to the manufacture of vehicle fuel with a low mixing of 5 to 20% due to such low fuel properties.

Recently, in order to supplement the lower physical properties, a method of producing liquid fuel for transportation while removing oxygen from FAME or directly removing oxygen from various liquid biomass has been proposed.

Commercial and pilot processes for the production of such liquid fuel for transportation is a process that requires a large amount of hydrogen as a renewable jet process (RJP), neste oil (Neste oil), dynamic fuel (Dynamic Fuels) ) And the like.

1 is a process chart showing a process for manufacturing a conventional bio-air fuel, in order to produce bio-air fuel according to the prior art, hydrogen is required for the deoxygenation reaction, selective pyrolysis and isomerization reaction, and paraffin through this process. Synthetic Paraffinic Kerosene (SPK) having a series of hydrocarbons is prepared.

However, according to Kubicka (Collection of Xwechoslvak Chemical Communications, 73, 2008, 1015-1044), in order to manufacture a fuel such as synthetic paraffin kerosene having a paraffinic hydrocarbon as described above, converting non-edible fats and oils into fuels The amount of hydrogen used in order to report that more than 10 times the amount of hydrogen used in the existing commercial hydro-treater (hydro-treater) has a disadvantage of costly consumption.

Therefore, in order to apply the above process, it should be installed in connection with a refinery that can easily supply hydrogen. Since the use of such a large amount of hydrogen also affects the price of biofuels, efforts are continued to minimize the amount of hydrogen used.

As described above, US Patent Publication Nos. US 2004/0230085 and US 2014/0275670, which are conventional techniques for minimizing the amount of hydrogen used in a bio-air fuel production process, are basically (1) deoxygenation for bio-air fuel production. Reaction (2) Isomerization and selective pyrolysis require two steps (US 2004/0230085).

Figure 2 is a reaction schematic showing the three forms of deoxygenation reaction through hydrogenation in the conventional bio-air oil production process, the deoxygenation reaction according to the form of oxygen is removed as shown in Figure 2, Three methods exist, and in particular, the development of a catalyst for the decarboxylation reaction of removing intramolecular oxygen in the form of carbon dioxide, which has relatively low hydrogen consumption, has been mainly carried out (US 2014/0275670).

However, as shown in FIG. 1, two-step processes are required regardless of whether a large amount of hydrogen is used, and the biofuel produced is also used as bio aviation oil because it does not meet the bio aviation oil specification that requires high energy density because it corresponds to a hydrocarbon of paraffin series. To be possible, there was a problem in that an appropriate energy density had to be mixed at least 50 of aviation oils produced in an existing refinery to have aromatic compounds up to 25%.

Accordingly, US Patent Publication No. US 2014/0005448 discloses a 100% bio-air fuel by adding a step of separating a hydrocarbon having a short carbon number of a paraffinic hydrocarbon and modifying it into an aromatic in a paraffinic hydrocarbon produced after hydrogenation deoxygenation. In this case, a reactor for hydrocarbon reforming was operated under a reforming temperature of 300 to 520 ° C., a hydrogen pressure of 3 to 27 bar, and a hydrogen to carbon ratio of 0.5 to 10. The mixed bioair fuels contained 8 to 25% by weight of renewable aromatics. However, the above method requires an additional process such as a separation process and a reforming process, and is a process in which hydrogen is consumed in large quantities.

Accordingly, a study to simplify the multistage hydrogenation reaction into a one-step hydrogenation process has recently been reported as part of minimizing hydrogen use in the 100% aviation oil production process. According to Wang C (ChemSus Chem 5 (2012) 1974-1983, Catalysis Today, 234, 2014, 153-160), a single-process hydrogenation reaction of a triglyceride-containing fat was carried by supporting platinum (Pt) or nickel metal in zeolites. Biodiesel was prepared through. In the case of nickel-supported SAPO catalyst, the reaction was carried out at 370 ° C. under a hydrogen atmosphere of 300 ml / min, maintaining a pressure of 40 bar. As a result, 100% conversion and 100 alkane hydrocarbon selectivity were shown. 63% showed isomerization selectivity.

However, the above-mentioned method also has a problem in that hydrogen must be used and the petroleum-based aromatic compound must be mixed in the future because it does not contain an aromatic compound.

On the other hand, International Patent Publication No. WO 2014/049621, which is another example of the prior art for producing a bio-aviation oil requiring a high energy density as described above, produces an aviation oil containing an aromatic compound from a renewable feedstock The technical content of the process is disclosed.

In the above-mentioned patent publication WO 2014/049621, a process for producing paraffinic hydrocarbons and aromatic compounds through a single process hydrogenation reaction under existing refinery refining conditions.

At this time, using a sulfur-treated Ni-Mo, Ni-W catalyst, the reaction was carried out while supplying a reaction temperature of 300 to 500 ℃, hydrogen pressure of 20 to 150 bar, 100 to 5000 ml of hydrogen per 1 ml of the raw material, The conversion rate reached 92 to 99.9%. In addition, the aromatic fuel oil range accounted for 35 to 60% of the total aromatic hydrocarbon content of 1 to 18%.

However, the above-mentioned process also uses hydrogen, and when using a sulfided catalyst, sulfur has a high possibility of being present as impurities in the product.

As such, despite various technological developments, additional hydrocracking, hydroisomerization, and further mixing of aromatic compounds are required to directly and selectively produce paraffinic and aromatic hydrocarbons contained in 100% bio-air fuel. It is still necessary to develop a catalyst and a single process for a direct production process that is not needed, and thus, a study is needed.

The present invention has been made to solve the above problems, the object of the present invention is 100% having a high energy density as a raw material for non-edible fats and oils through a single-step process without supplying hydrogen It is to provide a method for producing bio aviation oil.

In order to achieve the above technical problem, the present invention provides a process for preparing paraffins through deoxygenation, isomerization and aromatization reactions from non-edible fats and liquids in the presence of a catalyst without adding hydrogen. Forming a reaction product comprising the system hydrocarbon and the aromatic compound; And (b) distilling the reaction product to extract the aviation oil.

In addition, the non-edible fat and oil proposes a method for producing bio-avid oil using non-edible fat, characterized in that the triglyceride (triglyceride) or free fatty acid (free fatty acid) as a main component.

In addition, the non-edible oil and fat is one selected from the group consisting of palm fatty acid distillate (PFAD), non-edible dark oil derived from edible oil, microalgae-derived oil, jatropha oil, camelina oil, waste oil, and animal fats and oils. It proposes a bio-air oil production method using a non-edible fat, characterized in that the above made.

In addition, the catalyst includes a support and a metal particle supported on the support, the support is a zeolite in which the volume fraction of the meso pores is larger than the volume fraction of the micropores, the metal particles are palladium (Pd), platinum (Pt) The present invention proposes a method for producing bio-avid oil using non-edible fats and oils, characterized in that it is made of at least one metal selected from the group consisting of nickel (Ni), gallium (Ga), copper (Cu), and zinc (Zn).

In addition, the step (a) proposes a bio-air oil production method using a non-edible fat, characterized in that carried out at a pressure of 10 to 50 bar and a temperature of 200 to 370 ℃ formed by an inert gas.

In another aspect of the present invention, the present invention is prepared by the method for preparing bio-air oil using the non-edible fats and oils, wherein the isoparaffinic hydrocarbon and the aromatic compound are 30 to 70% by weight. It proposes a bio aviation oil comprising a.

Existing multi-stage aviation oil production process that requires the addition of a plurality of hydrogenation processes that need to supply a large amount of hydrogen for deoxygenation and isomerization of raw materials, as well as the addition of a separate petroleum aromatic compound to satisfy the quality of the aviation oil after completion of the hydrogenation process In contrast, the method for producing high quality bio-air fuel using non-edible fats and oils according to the present invention is a starting material by inducing deoxygenation, isomerization and aromatization reactions through a single step process by optimizing catalyst and reaction conditions without adding hydrogen. High-density, high-quality, 100% bioair fuels, including normal paraffinic hydrocarbons, isoparaffinic hydrocarbons and aromatics, can be produced directly and selectively from non-edible fats and oils, which is very economical in terms of manufacturing cost reduction and process simplification.

1 is a process chart showing a conventional bio-air fuel production process.

Figure 2 is a reaction schematic showing three forms of deoxygenation reaction through hydrogenation in the conventional bio-air oil production process.

Figure 3 is a graph showing the oxygen removal rate in the raw material and the type and content of the components included in the bio-air oil prepared according to Example 2 of the present application.

Figure 4 is a graph showing the oxygen removal rate in the raw material and the type and content of the components included in the bio-air oil prepared according to Example 3 of the present application.

Hereinafter, the present invention will be described in detail.

Bio-air oil production method according to the present invention, (a) paraffinic hydrocarbons through the deoxygenation, isomerization and aromatization reaction from the liquid non-edible fat in the presence of a catalyst without the addition of hydrogen And forming a reaction product comprising the aromatic compound; And (b) distilling the reaction product to extract aviation oil.

The non-edible fats and oils supplied as a raw material to the reaction made in step (a) is composed of a hydrocarbon containing a carboxyl group as a non-edible biomass and is a mixture having no or more than one double bond in the hydrocarbon structure. , Preferably, triglyceride (triglyceride) or free fatty acid (free fatty acid) may be included as a main component, in this case, the carbon number of the fatty acid group or free fatty acid contained in the triglyceride is preferably 10 to 24, More preferably, it may be 16-20.

Specific examples of such non-edible fats and oils include palm fatty acid distillate (PFAD), non-edible dark oils derived from edible oils and fats, oils derived from microalgae, jatropha oil, camelina oil, waste oils, animal oils or mixtures thereof. However, it is not necessarily limited thereto.

Table 1 is a table showing the composition and characteristics of some substances belonging to the non-edible fats and oils used in the present invention.

Table 1

	Jatropha oil	Camelina Yu	PFAD	Soybean Oil Fatty Acids
Characteristic	TG-rich oil	TG-rich oil	FFA 99.5% TG 0.5%	FFA	62,5% TG 37.5%
C16: 0	12.2	5.1	41.9	10.5
C18: 0	7.3	2.7	4.6	1.4
C18: 1	42.2	15.2 (15.7)	41.2	22.5
C18: 2	37.3	17.9 (19.1)	10.3	53.6
C18: 3	-	34.6 (31.5)	0.1	7.7
C20: 1	-	15.1	-	-
Sum	99.0	90.6	98.1	98.4

Since the non-edible fats and fats are present in the form of gel or gel rather than liquid according to the content and season of free fatty acid, it is preferable to add the non-edible fat to the reactor in the state of maintaining at a temperature of from room temperature to 60 ° C. Do.

On the other hand, the catalyst used in the reaction in this step (a) is deoxygenated not only to remove oxygen present in the hydrocarbon molecular structure included in the non-edible fats and oils, but also to mediate isomerization and conversion to aromatic hydrocarbons. It is preferred to be a bifunctional catalyst composed of a metal having an active point and a support having an acid point.

As the support included in such a catalyst, a zeolite having a medium and strong Bronsted acid point, which is advantageous for cracking and isomerization, can be used, considering the carbon number range of the bio-air fuel fraction, among which 2 nm in diameter. It is preferable to use a zeolite having a large volume fraction of mesopores having a diameter of 2 to 50 nm as compared to the micropore volume fraction below, and furthermore, finer than a large pore zeolite or 10 zeolites having 10 or 12 oxygen atoms. It is more preferable to use zeolites having large pores and having 3D channels, which are advantageous for cracking reactions of hydrocarbons having long chains. For reference, the Si / Al ratio of the zeolite affects the distribution of the product after the reaction and is operated under optimum reaction conditions to obtain the desired distribution.

The metal active material to be supported on the support includes at least one metal selected from the group consisting of palladium (Pd), platinum (Pt), nickel (Ni), gallium (Ga), copper (Cu) and zinc (Zn). Particles consisting of can be used.

By using a catalyst having an intermediate acid point and a strong acid point configured as described above, it is possible to easily break the double bond and / or triple bond in triglyceride or free fatty acid included in non-edible fats and oils. In this case, when the catalyst is applied to the optimum reaction conditions to be described later, isomerization of triglyceride and free fatty acid proceeds at an appropriate ratio, and paraffinic hydrocarbons and aromatic compounds may be produced.

The deoxygenation, isomerization and aromatization reactions carried out in this step (a) are carried out in a reactor in which the non-edible fats and oils as raw materials are supplied to the reactor in the presence of the catalyst described above without hydrogen being supplied to the reaction. It is characterized by the anhydrous catalyst conversion process carried out.

At this time, the reaction of this step is preferably carried out at a temperature of 200 ℃ to 370 ℃, more preferably can be carried out at a temperature of 250 ℃ to 350 ℃. The type and content of the constituents of the reaction product obtained through this step are greatly influenced by the reaction temperature, operating at a relatively high temperature to increase the content of aromatic products, and relatively low temperature to increase the content of normal and isomerized hydrocarbons. You can drive at

And, it is preferable to adjust the initial reactor pressure to 10 bar to 50 bar by using an inert gas such as nitrogen, helium or argon so that the reaction can proceed while the raw material is maintained in the liquid phase at the reaction temperature.

In addition, the reaction time of the anhydrous catalytic decomposition process in this step may vary depending on the acidity of the catalyst used, but is preferably made in the range of 0.5 to 6 hours, more preferably by reacting for 1 to 3 hours Reaction products including paraffinic hydrocarbons and aromatic compounds can be prepared.

In addition, the step (a) may be configured to recover and reuse the used catalyst.

Next, the step (b) is a step of obtaining bio-air fuel by distilling the air product by distilling the reaction product obtained in the step (a) because it can use a known technique such as vacuum distillation (vaccum distillation) Will be omitted.

According to the method for producing high-quality bio-air fuel using non-edible fats and oils according to the present invention described above, a plurality of hydrogenation processes for supplying a large amount of hydrogen for deoxygenation and isomerization of raw materials are required, and after completion of the hydrogenation process, Unlike the existing multistage aviation oil production process, which requires the addition of a separate petroleum aromatic compound to satisfy the quality, the single-step process for deoxygenation, isomerization and aromatization reaction is performed by optimizing the catalyst and reaction conditions without adding hydrogen. It is possible to directly and selectively produce high-energy-dense, high-quality, 100% bioair fuels containing normal paraffinic hydrocarbons, isoparaffinic hydrocarbons and aromatics from the starting raw non-edible fats and oils through a step-step process. Extremely economical in terms of savings and process simplification The.

In addition, the bio-air oil prepared by the bio-air oil production method using the non-edible fat and oil is composed of 15 to 30% by weight of iso-paraffinic hydrocarbons and 30 to 70% by weight of aromatic compounds, It also contains normal paraffinic (n-paraffin) hydrocarbons, and has a high calorific value, good low temperature characteristics, and a hydrocarbon chain having 12 to 18 carbon atoms that does not contain impurities. have.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

However, the presented embodiments are merely illustrative for describing the present invention in more detail and are not intended to limit the scope of the invention.

In order to manufacture bio-air fuel according to the first embodiment, beta in which 5 g by weight of palladium is supported by 10 g of stearic acid or oleic acid, which are non-edible fats and oils, as an active material without solvent. Catalytic reaction was induced using a zeolite catalyst, and the catalytic reaction proceeded at a pressure of 15 bar under a nitrogen atmosphere.

Table 2 is a table showing the content and characteristics of the bio-air oil prepared according to the amount of catalyst, reaction temperature and reaction time used in the bio-air oil production process using the non-edible fat and oil according to the first embodiment.

TABLE 2

As shown in Table 2, when looking at the ratio of reactant to catalyst amount, the biofuel oil prepared according to Example 1 showed that the conversion rate of non-edible oil and fat was increased as the amount of catalyst supplied increased. The proportion of hydrocarbons between the corresponding C12 and C18 also increased. However, there was no significant difference between the reactants and the catalyst ratio of 1: 5 or less.

In addition, looking at the distribution of the product according to the reaction temperature, as the reaction temperature increases, the difference in conversion rate is not large, but the degree of cracking is increased, while the hydrocarbon ratio between C8 and C11 increases, whereas between C12 and C18 corresponding to aviation oil The hydrocarbon ratio was reduced.

In addition, as the reaction temperature increases, the proportion of aromatics between C12 and C18 increases significantly, while the proportion of normal paraffinic hydrocarbons decreases. As a result of checking the reaction time variables, there was no significant effect on the product distribution as much as the reaction temperature. The conversion between 1 and 3 hours was similar, and as the reaction time increased, the amount of normal paraffinic hydrocarbons decreased while the amount of aromatic compounds increased.

In order to manufacture the bio-air oil according to the second embodiment, 10 g of waste food oil (SBO), which is a non-edible fat and oil raw material, was zeolite (Pd (5) /), in which 5 wt% of palladium was supported by active material without solvent. Y) and 3 g of beta zeolite (Pd (5) / BEA) catalysts were used to induce the catalysis, which was carried out at 300 ° C. for 3 hours at 15 bar under nitrogen atmosphere.

As shown in FIG. 3, the bio-air fuel prepared from the waste cooking oil of Example 2 showed an oxygen removal rate (DO) of 95.5% or 76.1%, and normal paraffinic hydrocarbons at C12 to C18 corresponding to bio-air fuel fractions. , Isoparaffinic hydrocarbons and aromatic compounds accounted for 38-42% of the total product. In more detail, when bio-fuel oil was manufactured using a beta zeolite catalyst, the normal paraffinic hydrocarbon was 23.5%, the isoparaffinic hydrocarbon was 15.8%, and the aromatic compound was 60.7%.

In addition, in the case of the control group in which the decomposition reaction was performed without using a catalyst without adding hydrogen, the conversion was very low, and oxygen in the raw material was not removed at all.

In order to manufacture the bio-air fuel according to the third embodiment, 10 g of PFAD, a non-edible fat and oil raw material, was prepared using Y zeolite (Pd (5) / Y) and beta loaded with 5% by weight of palladium as an active material without solvent. Catalytic reaction was induced using 3 g of zeolite (Pd (5) / BEA) catalyst, and the catalytic reaction proceeded at 300 ° C. for 3 hours at a pressure of 15 bar under nitrogen atmosphere.

As shown in FIG. 4, the bio-air oil prepared by the PFAD of Example 3 showed 94.3% deoxygenation degree in the beta zeolite catalyst and 80% deoxygenation degree in the Y zeolite catalyst.

In addition, the normal paraffinic hydrocarbons, iso paraffinic hydrocarbons and aromatic compounds in the C12 to C18 corresponding to the bio aviation oil accounted for 35 to 40% of the total product.

In the case of manufacturing a bio-air fuel using a beta zeolite catalyst, the normal paraffinic hydrocarbon was 16.2%, the isoparaffinic hydrocarbon was 16.8%, and the aromatic compound was 69%.

In addition, when bio-fuel was manufactured using the Y zeolite catalyst, 45% of normal paraffinic hydrocarbons, 18.8% of isoparaffinic hydrocarbons, and 36.2% of aromatic compounds were composed.

Claims

(a) Deoxygenation, isomerization and aromatization reactions from a liquid, non-edible fat in the presence of a catalyst without the addition of hydrogen to form reaction products comprising paraffinic hydrocarbons and aromatic compounds Making a step; And

(B) distilling the reaction product to extract the aviation oil; bio-fuel oil manufacturing method using a non-edible oil and fat comprising a.
The method of claim 1,

The non-edible fats and oils manufacturing method using non-edible fats and oils, characterized in that the triglyceride (triglyceride) or free fatty acid (free fatty acid) as a main component.
The method of claim 2,

The non-edible fats and oils are non-edible, characterized in that at least one selected from the group consisting of palm fatty acid distillate (PFAD), dark oil, microalgae-derived oil, jatropha oil, camelina oil, waste fat, and animal fats and oils. Bio-air oil production method using fats and oils.
The method of claim 1,

The catalyst includes a support and a metal particle supported on the support, wherein the support is a zeolite having a volume fraction of mesopores larger than a volume fraction of micropores, and the metal particles are palladium (Pd), platinum (Pt), or nickel. (Ni), gallium (Ga), copper (Cu) and zinc (Zn) bio-fuel oil manufacturing method using a non-edible fat, characterized in that consisting of at least one metal selected from the group consisting of.
The method of claim 1,

Step (a) is a bio-air oil production method using a non-edible oil, characterized in that carried out at a pressure of 10 to 50 bar and a temperature of 200 to 370 ℃ formed by an inert gas.
Prepared by the method according to any one of claims 1 to 5, characterized in that it comprises 15 to 30% by weight of iso-paraffinic hydrocarbons and 30 to 70% by weight of aromatic compounds. Bio aviation oil.