KR20190006385A - Method of two-step reaction of producing deoxygenated fuels from oxygenated hydrocarbons - Google Patents

Abstract

Disclosed is a method for producing deoxygenated fuels from oxygenated hydrocarbons through a two-step reaction. The method comprises: a first stage reaction using a hydrogenation catalyst; and a second stage reaction using a hydrogenated deoxygenation catalyst, and thus there is an effect of improving the water-scavenging oxygen reactivity of oxygenated hydrocarbon compounds.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a method for producing a deoxygenated fuel from an oxygenated hydrocarbon by a two-

Disclosed herein is a process for producing a deoxygenated fuel from an oxygenated hydrocarbon in a two-stage reaction.

Organic waste such as wood, building waste, food waste, and biomass such as wood and herbaceous are attracting attention as future sustainable energy and chemical raw materials. A number of techniques have been developed to biologically ferment biomass sugar components or chemically convert them to heat and catalytic reactions, but in this case they have the disadvantage of not using other carbon sources except sugars. In order to solve these problems, a pyrolysis process has been proposed as a method utilizing biomass and all the components of organic waste resources. The pyrolysis process decomposes organic matter at a high temperature to obtain liquid low-molecular hydrocarbons, solid fuels, and gaseous products. Among them, liquid low-molecular hydrocarbons can be used as heating and transportation fuels.

Pyrolysis oil, a liquid product obtained by the pyrolysis process, can be used as a heating and transportation fuel as a hydrocarbon, but its value as a high-grade fuel is low due to its high oxygen content and is difficult to use directly in conventional radiators and vehicle engines. In order to utilize it similar to existing petroleum fuels, it is necessary to remove oxygen from pyrolysis oil, which is a mixture of oxygenated hydrocarbon compounds, and the most widely used method is hydrocracking.

In the actual continuous operation, it is difficult to obtain a reaction system capable of commercial use due to rapid coke formation and low catalytic activity occurring in the catalyst bed. Therefore, it is necessary to construct a catalyst and a reaction system that suppresses the formation of coke and increases catalytic activity as a whole so that the continuous reactor can be operated.

Korean Patent Registration No. 10-1571129

In one aspect, the present invention relates to a method for deoxygenating an oxygen-containing hydrocarbon compound in a two-stage reaction in which a deoxygenated fuel is produced from a deoxygenated hydrocarbon compound using a hydrogenation catalyst of the first stage and a hydrocracking oxygen catalyst of the second stage The purpose is to provide.

In one aspect, the techniques disclosed herein include a first stage reaction using a hydrogenation catalyst; And a second stage reaction using a hydrocracking oxygen catalyst. The present invention also provides a method for deoxygenating an oxygen-containing hydrocarbon compound.

In an exemplary embodiment, the method comprises: a first stage reaction using a hydrogenation catalyst comprising palladium (Pd), nickel (Ni) or ruthenium (Ru) supported on a carbon support or a metal oxide support; And a second stage reaction using a hydrocracking oxygen catalyst comprising ruthenium (Ru), palladium (Pd), platinum (Pt), nickel (Ni) or cobalt (Co) carried on a carbon support or a metal oxide support Lt; / RTI >

In an exemplary embodiment, the metal oxide support is selected from the group consisting of silica, alumina, silica-alumina, zirconia, tungstated-zirconia, Lt; / RTI >

In an exemplary embodiment, the hydrogenation catalyst may be one in which palladium (Pd) or nickel (Ni) is supported on a support, and the hydrochemical oxygen catalyst is supported on ruthenium (Ru) on a support.

In an exemplary embodiment, the hydrogenation catalyst comprises nickel (Ni) or ruthenium (Ru) supported on a carbon support or a metal oxide support, and the hydrated oxygen catalyst comprises palladium (Pd) supported on a carbon support .

In an exemplary embodiment, the hydrogenation catalyst comprises palladium (Pd) or nickel (Ni) supported on a carbon support, and the hydrated oxygen catalyst may comprise ruthenium (Ru) supported on a metal oxide support have.

In one exemplary embodiment, the hydrogenation catalyst comprises palladium (Pd) supported on a carbon support, and the hydrated oxygen catalyst comprises platinum (Pt), nickel (Ni), or cobalt (Co) supported on a carbon support May include.

In an exemplary embodiment, the first and second stage reactions may be performed in a continuous reactor.

In an exemplary embodiment, the method comprises the steps of charging an oxygen-containing hydrocarbon compound and hydrogen into a reactor; Performing a hydrogenation reaction by adding a hydrogenation catalyst; And performing a hydrocracking reaction by adding a water-reducing oxygen catalyst.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound and hydrogen may be mixed in a volume ratio of 1: 1 to 1: 10,000.

In an exemplary embodiment, the hydrogenation reaction may be carried out at 100 to 200 < 0 > C.

In an exemplary embodiment, the hydropathic oxygenation reaction may be carried out at 250 to 500 < 0 > C.

In one aspect, the techniques disclosed herein are directed to the use of a first-stage hydrogenation catalyst and a second-stage hydrocracking oxygen catalyst to produce a deoxygenated fuel from a deoxygenated hydrocarbon compound, There is an effect of providing a reaction method. This method has an effect of enhancing the water-scarcity oxygen reactivity of the oxygen-containing hydrocarbon compound.

1 schematically illustrates a conventional one-stage reactor (a) and a two-stage reactor (b) according to the present invention used for the hydrocracking reaction of an oxygen-containing hydrocarbon compound.

Hereinafter, the present invention will be described in detail.

In one aspect, the techniques disclosed herein include a first stage reaction using a hydrogenation catalyst; And a second stage reaction using a hydrocracking oxygen catalyst. The present invention also provides a method for deoxygenating an oxygen-containing hydrocarbon compound.

The process disclosed herein relates to a process for preparing a deoxygenated fuel through hydrogenation and hydrogen deoxygenation of an oxygen-containing hydrocarbon compound such as a pyrolysis oil. More particularly, the present invention relates to a method for the reduction of oxygen atoms in an oxygen-containing hydrocarbon compound by adding hydrogenation and hydrocracking oxygen catalyst to the oxygen-containing hydrocarbon compound in two steps to improve the reactivity . This method has the effect of producing a high-yield deoxygenated hydrocarbon compound from an oxygen-containing hydrocarbon compound.

The oxygen-containing hydrocarbon compound means a hydrocarbon compound containing an oxygen atom in a molecular structure, and includes carbon, hydrogen, and oxygen atoms. For example, it decomposes a variety of biomass including wood, herbaceous organic matter, It may be a mixture of the obtained low-carbon compounds.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound may be pyrolysis oil of biomass.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound may include at least one selected from the group consisting of a guaiacol, diphenyl ether, and benzyl phenyl ether. The guaiacol, diphenyl ether and benzyl phenyl ether may be lignin monomers obtained from pyrolysis oils of woody biomass.

In an exemplary embodiment, the method comprises: a first stage reaction using a hydrogenation catalyst comprising palladium (Pd), nickel (Ni) or ruthenium (Ru) supported on a carbon support or a metal oxide support; And a second stage reaction using a hydrocracking oxygen catalyst comprising ruthenium (Ru), palladium (Pd), platinum (Pt), nickel (Ni) or cobalt (Co) carried on a carbon support or a metal oxide support Lt; / RTI >

In one exemplary embodiment, the carbon support is selected from the group consisting of carbon black, carbon nanotubes (CNT), graphite, graphene, activated charcoal, mesoporous carbon, carbon fiber ) And a carbon nanowire (Carbon nano wire).

In an exemplary embodiment, the metal oxide support is selected from the group consisting of silica, alumina, silica-alumina, zirconia, tungstated-zirconia, Lt; / RTI >

In an exemplary embodiment, the support of the hydrogenation catalyst may be preferably carbon.

In an exemplary embodiment, the support of the hydrochemical oxygen catalyst may be preferably a metal oxide.

In an exemplary embodiment, the support of the hydrated oxygen catalyst may be tungsten zirconia.

In the catalyst disclosed in this specification, the metal supported on the support may be a single metal or two or more metals supported thereon.

In an exemplary embodiment, the hydrogenation catalyst may be one in which palladium (Pd) or nickel (Ni) is supported on a support, and the hydrochemical oxygen catalyst is supported on ruthenium (Ru) on a support.

In an exemplary embodiment, the hydrogenation catalyst comprises nickel (Ni) or ruthenium (Ru) supported on a carbon support or a metal oxide support, and the hydrated oxygen catalyst comprises palladium (Pd) supported on a carbon support .

In an exemplary embodiment, the hydrogenation catalyst comprises palladium (Pd) or nickel (Ni) supported on a carbon support, and the hydrated oxygen catalyst may comprise ruthenium (Ru) supported on a metal oxide support have.

In one exemplary embodiment, the hydrogenation catalyst comprises palladium (Pd) supported on a carbon support, and the hydrated oxygen catalyst comprises platinum (Pt), nickel (Ni), or cobalt (Co) supported on a carbon support May include.

In an exemplary embodiment, the content of the metal catalyst component carried on the support may be 0.01 to 30 wt%, respectively, based on the total weight of the catalyst. In another aspect, the content of the metal catalyst component carried on the support is at least 0.01 wt%, at least 0.1 wt%, at least 1 wt%, at least 3 wt%, at least 5 wt%, at least 8 wt% By weight, not less than 10% by weight, not less than 13% by weight, not less than 15% by weight, not less than 18% by weight or not less than 20% by weight but not more than 30% , 15 wt% or less, 13 wt% or less, 10 wt% or less, 8 wt% or 5 wt% or less.

In an exemplary embodiment, the first and second stage reactions may be performed in a continuous reactor. The deoxygenation reaction of the two-step reaction according to the present invention has the effect of inhibiting the formation of coke and increasing the catalytic activity so that the continuous reactor can be operated.

In an exemplary embodiment, the method comprises the steps of charging an oxygen-containing hydrocarbon compound and hydrogen into a reactor; Performing a hydrogenation reaction by adding a hydrogenation catalyst; And performing a hydrocracking reaction by adding a water-reducing oxygen catalyst.

In an exemplary embodiment, the oxygen-containing hydrocarbon compound and hydrogen may be mixed in a volume ratio of 1: 1 to 1: 10,000.

In an exemplary embodiment, the hydrogenation reaction may be carried out at 100 to 200 < 0 > C.

In an exemplary embodiment, the hydrocracking reaction may be carried out at 250 to 500 占 폚, or 300 to 500 占 폚, or 300 to 450 占 폚, or 300 to 400 占 폚.

In an exemplary embodiment, the hydrogenation reaction and the hydroproxygenation reaction may be carried out at a Liquid Hourly Space Velocity (LHSV) of 0.1-5 h < ^-1 > over the entire catalyst volume.

In an exemplary embodiment, the method may be to produce a deoxygenated hydrocarbon compound from an oxygenated hydrocarbon compound.

In another aspect, the techniques disclosed herein provide a process for preparing hydrogenated and hydrocracked oxygen catalysts of the above-mentioned oxygenated hydrocarbon compounds.

In an exemplary embodiment, the method comprises: mixing a precursor aqueous solution of a catalyst component with a support and impregnating; And reducing and firing a support impregnated with the precursor aqueous solution of the catalyst component.

In an exemplary embodiment, the metal precursor which is a precursor of the catalytic component is selected from the group consisting of metal salt compounds, metal acetate compounds, metal halide compounds, metal nitrate compounds, metal hydroxide compounds, metal carbonyl compounds, metal sulfate compounds and metal fats And an acid salt compound.

In an exemplary embodiment, the calcination process may be carried out at 300 to 600 ° C for 1 to 20 hours under an atmosphere of hydrogen diluted with an inert gas.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example 1.

5 g of the support and 30 g of distilled water were mixed with 5 g of metal precursor (nitric oxide, 6.26 g of each metal precursor, 0.66 g of Pd, 0.35 g of Ru, 2.83 g of Co and 0.70 g of Pt) Stir for 12 hours. The mixture was dried under reduced pressure at 70 캜 and then vacuum dried at 105 캜. The completely dried catalyst was reduced to 5 vol% hydrogen gas mixed with argon gas for 2 hours at 350 ℃ for Pd, Ru, Co, Pt and 550 ℃ for Ni.

Example 2.

The catalyst prepared in Example 1 was subjected to a hydrocracking reaction of pyrolysis oil of pine sawdust using a continuous two-stage reactor (see Fig. 1 (b)). The reaction temperature was maintained at 100-190 ° C for the first stage and 300-450 ° C for the second stage. The amount of the charged catalyst in the reactor was fixed to 5 mL for the first stage and to 10 mL for the second stage, and the pressure in the reactor was maintained at 100 bar in both the first and second stages. When the catalyst was used only in the second stage, 10 mL of the catalyst was added to the second stage. The flow rate of the reactants was fixed at 6 mL / h based on normal temperature and normal pressure. The hydrogen flow rate was fixed at 6 mL / min at normal temperature and atmospheric pressure. The liquid mixture obtained after the reaction was analyzed by mass measurement of the product and gas chromatography. The following Tables 1 and 2 show the results of the two-stage oxygen reduction reaction according to the present invention for the various catalysts prepared in Example 1 above.

catalyst The catalyst bed temperature (캜) Liquid product yield
(g / g of feed oil) Water layer
Except
Oil layer yield (g / g of feed oil) Coke and tar yield
(g / g of feed oil) 1st stage 2nd stage 1st stage 2nd stage 1st stage 2nd stage None 3 wt% Ru / WZr ^a - 313 - 370 0.60 0.30 - 0.07 5 wt% Pd / C 5 wt% Pd / C 146 - 198 335 - 364 0.65 0.48 0.03 0.09 5 wt% Pt / C 112 - 170 323 - 378 0.45 0.27 0.17 0.23 5 wt% Ru / C 119 - 173 323 - 372 0.69 0.49 0.08 0.01 20 wt% Ni / C 114 - 165 331 - 381 0.53 0.33 0.03 0.04 3 wt% Ru / WZr 111 - 151 337 - 398 0.57 0.41 0.31 0.20 5 wt% Pd / C 3 wt% Ru / WZr 108 - 162 312 - 385 0.74 0.42 0.01 0.03 20 wt% Ni / C 114 - 157 328 - 380 0.62 0.24 0.02 0.02 5 wt% Ru / C 119 - 165 350 - 385 0.56 0.24 0.02 0.05 10 wt% Co / C 121 - 176 368 - 386 0.43 0.11 0.03 0.03 5 wt% Ru / Al ₂ O ₃ 117 - 158 367 - 385 0.55 0.24 0.04 0.06 3 wt% Ru / WZr 115 - 160 360 - 384 0.52 0.14 0.12 0.03 5 wt% Ru / TiO ₂ 115 - 160 360 - 384 0.48 0.14 0.02 0.4 5 wt% Pd / C 5 wt% Pt / C 153 - 188 310 - 364 0.73 0.44 0.02 0.03 5 wt% Ru / C 153 - 188 310 - 364 0.32
(Only the water layer
produce) ~ 0 0.04 0.06 20 wt% Ni / C 112 - 161 312 - 371 0.65 0.40 0.03 0.06 10 wt% Co / C 110 - 167 349 - 370 0.61 0.29 0.08 0.13 5 wt% Ru / TiO ₂ 117 - 167 341 - 388 0.33
(Only the water layer
produce) ~ 0 0.10 0.04 5 wt% Ru / Al ₂ O ₃ 108 - 162 312 - 379 0.29
(Only the water layer
produce) ~ 0 0.05 0.06

^a LHSV = 0.72 h ^-1 . For other catalytic reactions, LHSV = 0.42 - 0.52 h ^-1 .

catalyst
C (wt%) H (wt%) N (wt%) S (wt%) O (wt%) ^a O / C (atom / atom) H / C (atom / atom) Water in the oil layer (wt%) HHV calories (MJ / kg) 1st stage 2nd stage Crude bio-oil 55.2 7.2 0.9 ~ 0 ^b 34.9 0.475 1.57 7.00 22.7 Ether extracted bio-oil 56.6 7.2 1.1 ~ 0 ^b 31.7 0.42 1.53 6.2 23.8 None 3 wt% Ru / WZr ^a 85.4 13.6 1.0 ~ 0 ^b 1.2 0.01 1.92 0.4 48.2 5 wt% Pd / C 5 wt% Pd / C 72.0 11.2 1.28 ~ 0 ^b 11.2 0.12 1.88 2.6 38.4 5 wt% Pt / C 67.7 11.3 0.19 ~ 0 ^b 18.0 0.20 2.00 0.3 35.9 5 wt% Ru / C 75.0 12.2 0.44 ~ 0 ^b 10.2 0.10 1.95 3.6 41.0 20 wt% Ni / C 76.7 12.0 0.27 ~ 0 ^b 6.4 0.07 1.88 2.6 42.1 3 wt% Ru / WZr 75.4 12.1 0.38 ~ 0 ^b 5.0 0.09 1.92 1.6 41.1 5 wt% Pd / C 3 wt% Ru / WZr 83.9 12.7 0.07 ~ 0 ^b 0.7 0.01 1.82 0.04 46.5 20 wt% Ni / C 85.0 13.0 0.28 ~ 0 ^b 1.2 0.01 1.83 0.17 47.1 5 wt% Pd / C 5 wt% Pt / C 78.0 11.7 0.08 ~ 0 ^b 6.9 0.07 1.80 0.9 41.8 5 wt% Ru / C Only produce water layer 20 wt% Ni / C 79.3 12.4 0.54 ~ 0 ^b 7.1 0.07 1.87 2.7 43.3 10 wt% Co / C 81.9 12.4 0.32 ~ 0 ^b 5.0 0.05 1.81 0.5 44.6 5 wt% Ru / TiO ₂ Only produce water layer 5 wt% Ru / Al ₂ O ₃ Only produce water layer

^a Measured with ^a separate oxygen metering device.

^b Less than the minimum measurement limit.

As shown in Tables 1 and 2, even when only a two-stage Ru / WZr water-reducing oxygen catalyst was used without a first stage hydrogenation catalyst, a high oil yield of 0.30 g / g was obtained. However, the first stage Pd / C and the second stage Ru / WZr Showed a higher oil yield of 0.42 g / g and a lower oxygen content of 0.7 wt%, indicating that the highly efficient hydrocracking reaction proceeded. In the case of the combination of the first stage Pd / C, the second stage Pt / C, the first stage Pd / C and the second stage Ni / C combination, the oil yields were as high as 0.44 and 0.40 g / , And a high oxygen content of 7.1 wt%, indicating that the hydrocracking reaction did not proceed completely. In addition, when a low-cost Ni catalyst was used instead of a Pd catalyst as a first-stage hydrogenation catalyst and Ru / WZr was used as a two-stage oxygen catalyst, a relatively low oil yield of 0.24 g / g was obtained. And the oxygen content of the solution was high.

Having described specific portions of the present invention in detail, it will be apparent to those skilled in the art that this specific description is only a preferred embodiment and that the scope of the present invention is not limited thereby. It will be obvious. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

10: Hollow oxygen hydrocarbon compound and hydrogen gas
20: furnace, heating device
30: hydrogenation catalyst
40: water-reducing oxygen catalyst
50: Hydrogen oxides and hydrogen gas

Claims (12)

A first stage reaction using a hydrogenation catalyst; And
A second method for the deoxygenation of an oxygen-containing hydrocarbon compound using a water-reducing oxygen catalyst.
The method according to claim 1,
The method comprises: a first stage reaction using a hydrogenation catalyst comprising palladium (Pd), nickel (Ni) or ruthenium (Ru) carried on a carbon support or a metal oxide support; And
A second stage reaction using a hydrocracking oxygen catalyst comprising ruthenium (Ru), palladium (Pd), platinum (Pt), nickel (Ni) or cobalt (Co) supported on a carbon support or metal oxide support, A method for deoxygenation of an oxygen - containing hydrocarbon compound.
3. The method of claim 2,
Wherein the metal oxide support is at least one selected from the group consisting of silica, alumina, silica-alumina, zirconia, tungstated-zirconia, A method for deoxygenation of a compound.
3. The method of claim 2,
Wherein the hydrogenation catalyst is one in which palladium (Pd) or nickel (Ni) is supported on a support, and rhenium (Ru) is supported on a support in the hydrocracking oxygen catalyst.
3. The method of claim 2,
Wherein the hydrogenation catalyst comprises nickel (Ni) or ruthenium (Ru) supported on a carbon support or a metal oxide support, and the hydrated oxygen catalyst comprises palladium (Pd) supported on a carbon support. A method for deoxygenation of a compound.
3. The method of claim 2,
Wherein the hydrogenation catalyst comprises palladium (Pd) or nickel (Ni) supported on a carbon support, and the hydrochemical oxygen catalyst comprises ruthenium (Ru) supported on a metal oxide support. Oxygen reaction method.
3. The method of claim 2,
Wherein the hydrogenation catalyst comprises palladium (Pd) supported on a carbon support, and the hydrochemical oxygen catalyst comprises platinum (Pt), nickel (Ni) or cobalt (Co) A method for deoxygenation of a hydrocarbon compound.
The method according to claim 1,
Wherein the first stage and second stage reactions are carried out in a continuous reactor.
The method according to claim 1,
The method comprises the steps of charging an oxygen-containing hydrocarbon compound and hydrogen into a reactor; Performing a hydrogenation reaction by adding a hydrogenation catalyst; And performing a hydrocracking reaction by adding a water-reducing oxygen catalyst to the deoxygenated hydrocarbon.
10. The method of claim 9,
Wherein the oxygen-containing hydrocarbon compound and hydrogen are mixed in a volume ratio of 1: 1 to 1: 10,000.
10. The method of claim 9,
Wherein the hydrogenation reaction is carried out at 100 to 200 ° C.
10. The method of claim 9,
Wherein the hydrocracking reaction is carried out at 250 to 500 ° C.

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