KR20120009689A - A method for preparing paraffin from ketone - Google Patents

Abstract

PURPOSE: A manufacturing method of paraffin from ketone is provided to have high yield by applying aldol condensation, hydrogenation, and hydrogenated deoxygenation in order. CONSTITUTION: A manufacturing method of paraffin from ketone comprises: a step of forming enone through aldol condensation and dehydration; a step of forming ketone of which length of a carbon chain is increased through the hydrogenation of the enone; and a step of converting the ketone to branched non-polar paraffin through hydrodeoxygenation. The ketone mixture is obtained from volatile fatty acids originated from biomass, or through a typical chemical reaction.

Description

A method for preparing paraffin from ketone

The present invention relates to a process for economically preparing paraffinic compounds that can be used in various applications such as gasoline fuels and lube base oils from various kinds of ketone mixtures. More specifically, by using a ketone mixture obtained from a volatile fatty acid derived from biomass or a ketone mixture obtained through a typical chemical reaction as a raw material, the aldol condensation reaction, the hydrogenation reaction, and the hydrodeoxygenation reaction are applied singly or sequentially through a catalytic reaction. To a method for producing paraffin in high yield.

Volatile Fatty Acid (VFA) can be obtained in high yield by simple fermentation treatment from wood-based, algae, organic waste, etc. without restriction of raw materials, and researches for producing fuel oil for transportation from volatile fatty acids are underway. have. It is generally known to prepare mixed alcohols from mixed organic acids or mixed ketones obtained from fermentation, or further to produce mixed olefins by dehydration of alcohols and to produce gasoline and diesel fractions via oligomerization.

US 5,874,263 suggests that anaerobic fermentation can produce biomass from volatile fatty acids or metal salts thereof. Specifically, it has been described that pretreatment of biomass with calcination in anaerobic conditions and increasing the initial concentration of volatile fatty acids can increase the productivity of volatile fatty acids and calcium salts of volatile fatty acids obtained through fermentation.

Using a metal salt of volatile fatty acids produced through fermentation, a method of preparing volatile fatty acids or ketone mixtures is also presented as follows. US 5,969,189 describes a method for forming calcium carbonate through pyrolysis of calcium salts of volatile fatty acids prepared via the above technique, and for preparing ketone mixtures derived from volatile fatty acids. In US 6,043,392, a metal salt of a volatile fatty acid prepared through an anaerobic fermentation reaction is substituted with an amine to prepare a carboxylic acid amine and pyrolyzed to separate it, thereby preparing a volatile fatty acid and producing aldehyde, alcohol, lactic acid, etc. as a byproduct. It is described.

The following techniques are introduced as a method for producing a fuel for direct transportation using volatile fatty acids prepared through the above technique. US 7,351,559 describes a process for producing ethanol that can be used as fuel by fermenting biomass to produce acetic acid and acetate, esterifying it to produce ethyl acetate, and then hydrogenating. US 20080280338 describes a process for preparing acetylene from alcohols and methane derived from volatile fatty acids, of ethylene, and of ethylene, followed by oligomerization to produce liquid fuels that can be used as transport fuels. US 20090239279 describes a method of increasing the efficiency of liquid fuel production by performing oligomerization reaction by mixing pyrolysis oil and hydrocarbon obtained by pyrolysis treatment of biomass in addition to alcohol and methane.

However, there is a problem of rapid deactivation of the catalyst due to coke generation in the process of obtaining branched fuel through the oligomerization reaction, which requires the use of a fluidized bed reactor having high equipment cost and operation cost.

In addition, bioethanol and biodiesel, which are conventional biofuels, have only physical properties that are different from those of petroleum-based gasoline and diesel. However, the value of the technology is even higher if a transport fuel or lubricating base oil manufactured from a biological origin can produce all or the same or higher quality materials and replace all of the existing petroleum based transportation fuels or lubricating base oils. have.

In addition, using ketone mixtures obtained from volatile fatty acids of biological origin as a raw material, a study on a method for increasing the yield of paraffins by applying a single reaction or a series of aldol condensation reaction, hydrogenation reaction and hydrogenation deoxygenation reaction through catalytic reaction The need exists.

The present invention provides a method for producing a branched nonpolar paraffin in high yield by applying a ketone mixture obtained through a variety of methods as a raw material, by applying the aldol condensation reaction, hydrogenation reaction, hydrodeoxygenation reaction single or sequentially through a catalytic reaction It is about.

The present invention relates to a process for obtaining branched nonpolar paraffins in high yield, including single or sequential aldol condensation, hydrogenation, and hydrodeoxygenation from a ketone mixture raw material via a catalytic reaction.

In order to solve the above technical problem, in the present invention, the catalyst system is configured in the form of physically mixing or molding a binder material using at least one of condensation, hydrogenation, and hydrodeoxygenation functions, or forming a catalyst system in a double layer. It is to provide a method for increasing the yield of paraffins through the configuration.

When the catalyst system is configured by physically mixing a material including at least one of the condensation, hydrogenation, and hydrodeoxygenation functions described in the present invention, or by molding using a binder material, or by configuring a catalyst system in a double layer, In the ketone mixture raw material obtained through various methods, paraffin can be prepared in high yield by applying a single or sequential aldol condensation reaction, hydrogenation reaction and hydrodeoxygenation reaction.

Hereinafter, the technical content of the present invention will be described in more detail.

In the process according to the invention, the route for preparing paraffin from the ketone mixture can be summarized as follows.

<Scheme 1>

Iii) aldol condensation reaction of the ketone mixture to produce a ketone hydroxide ① having an increased length of the carbon chain;

Ii) dehydration of ① to form inon (Enone, ②);

iii) forming a ketone (③) having an increased carbon chain length through the hydrogenation reaction of ②;

iv-1) converting the generated ③ into a hydrophobic deoxygenation reaction to branched nonpolar paraffin (④);

iv-2) The produced ③ is reacted with ketones having the same or different carbon chain lengths to form inon hydroxide having a longer carbon chain length, and a ketone having a longer carbon chain length through hydrogenation reaction. (⑤) forming;

v) converting the generated ⑤ into a branched nonpolar paraffin (⑥) by hydrodeoxygenation.

In the present invention, ketone formation with increased lengths of carbon chains including aldol condensation reaction (i, iv-2), dehydration of aldol condensate (ii), and inon hydrogenation (ii, iv-2) of Scheme 1 Process to hydrogenated deoxygenation reaction (iv-1, v) may be carried out in a separate reactor or two or more reactors, but more preferably through one reactor. Enones produced through the reactions i) and ii) are unstable and easily ketoneized at low temperatures. As a result, the rate of iii) during the reaction is faster than other reactions. If the rate of iii) proceeds rapidly to decrease the concentration of Enone, the reaction of ii) is accelerated and the aldol condensation of equilibrium reaction i) is accelerated for the same reason. Since the reaction of iv-1) is easily carried out within the reaction conditions, the simultaneous progression through one step in one reactor as a whole is performed by dividing the aldol condensation reaction and the hydrodehydrogenation reaction through two or more reactors. The conversion rate is higher than that.

In addition, when the catalyst is configured in the form of physically mixing the catalyst containing at least one of the condensation, hydrogenation, hydrodeoxygenation function or by using a binder material, or by using a catalyst system of the method of configuring the catalyst in a double layer, The yield of the branched nonpolar paraffin according to the present invention can be dramatically increased.

The catalyst having a condensation function may include any substance containing at least one acid function or a salt function. For example, CeZrOx, CuZrOx, hydrotalcite, niobium oxide, alumina, silica, silica-alumina, zirconia, titania, or mixed oxides thereof, or zeolites Molecular sieves and the like.

Useful catalysts for the hydrogenation reaction can be used for all metal materials having a hydrogenation function. Specifically, it may include a metal component selected from Group VIII metal, Group VI metal, and mixtures thereof, more preferably the metal component is Pd, Pt, Rh, Ru, Ni, NiMo, CoMo, NiW It may be selected from the group consisting of, or CoW.

The catalyst having a hydrodeoxygenation function is preferably a catalyst including both a hydrogenation function and a deoxygenation function, and may be prepared in a form in which a metal component having the hydrogenation function is supported on a material including at least one acid or salt function. have.

In addition, step i)? V) can be carried out in a single catalyst system or in a reactor at a temperature in the range of 80 to 500 ° C., a hydrogen pressure in the range of 1 to 200 bar, more preferably at a temperature of 100 to 400 ° C. It may be carried out at hydrogen pressure conditions of 50 bar. Also in the single reactor the WHSV is adjusted to greater than 0 and less than 1 / hr, preferably greater than 0 and less than 0.6 / hr.

The invention is explained in more detail below through the following examples. However, the present invention is not limited to the embodiments described in the embodiments, and the present invention can be freely performed in other ways within the technical contents of the present invention.

Example  One

Ketone mixtures were prepared using known techniques using volatile fatty acids obtained from biomass as a raw material [Journal of Molecular Catalysis A: Chemical 227 (2005) 231-29] and the component ratios are listed in Table 1. 0.25 wt% Pd / Nb ₂ O ₅ for ketone mixtures with the component distributions in Table 1 An experiment was carried out to produce branched paraffin hydrocarbons using a double layer catalyst composed of two materials, Ni-Mo / ZrO ₂ . The 0.25 wt% Pd / Nb ₂ O ₅ catalyst was loaded with Pd (NO ₃ ) ₂ (10 wt% Aldrich) in Niobic acid by Incipient wetness method, dried at 393 K for 3 hours, and then at 533 K for 3 hours. It was prepared by firing in an air atmosphere. Ni-Mo / ZrO ₂ catalyst was prepared using ZrO ₂ as a carrier such that molybdenum was about 10 wt% and Ni was about 3 wt%. Ammonium heptamolybdate tetrahydrate (hereinafter referred to as "AHM") was used as the Mo precursor used in the preparation, and Nickel nitrate hexahydrate (hereinafter referred to as "NNH") was used as the Ni precursor.

First, an aqueous solution prepared by dissolving AHM in distilled water was impregnated in a ZrO₂ carrier, and then dried at 423 K for 2 hours, and then calcined continuously at 732 K for 2 hours to prepare Mo / ZrO₂. Then, NNH was dissolved in distilled water, impregnated with the Mo / ZrO₂ catalyst, dried at 423 K for 2 hours, and then calcined continuously at 732 K for 2 hours to prepare a Ni-Mo / ZrO₂ catalyst.

The reaction was carried out using a high-pressure micro-reactor, the experiment was conducted using a total of 6g of 3g each of the two catalysts prepared by the above method. Reduction of the catalyst was carried out at a rate of 0.5 ° C./min up to 723 K while flowing hydrogen at 200 sccm, then maintained for 2 h, and lowered to 623 K. At 623 K temperature conditions, the ketone mixture was introduced at a WHSV 0.5 h ^-1 condition while hydrogen was adjusted to 50 bar. The conversion and product selectivity of the reactants were analyzed using GC-Mass, and the results shown in Table 2 were obtained.

Carbon count name Composition (wt%) C3 Dimethyl ketone (DMK) 60 C4 Methyl ethyl ketone (MEK) 20 C5 Methyl propyl ketone (MPK) 10 C5 Diethyl ketone (DEK) 5 C6 Ethyl propyl ketone (EPK) 3 C7 Dipropyl ketone (DPK) 2

Temperature ( ^o C) 250 300 350 Conversion (%) 98.5 99.7 100 Selectivity (%) Branched Ketone (C5 ~ C13) 1.5 1.5 0.0 Paraffin (C3 ~ C4) 0.6 1.3 1.5 Paraffin (C5 ~ C12) 77.1 74.7 68.6 Paraffin (C13 ~ C36) 8.5 14.9 0.5 Olefin 0.0 0.6 1.2 Aromatic 3.4 2.3 21.5 Alcohol 6.3 0.0 0.0 Acid 0.0 0.0 0.0 Ether 0.0 0.0 0.5 Unknown 2.7 4.7 6.2

Example  2

0.25 wt% Pd / Nb ₂ O ₅ for ketone mixtures with the component distributions in Table 1 An experiment was performed to prepare branched paraffin hydrocarbons using 6 g of a catalyst prepared by physically mixing 3 g of Ni-Mo / ZrO _{2 and} 3 g. 0.25 wt% Pd / Nb ₂ O ₅ And Ni-Mo / ZrO ₂ catalysts were prepared in the same manner as described in Example 1. Reduction and reaction of the catalyst was carried out in the same manner as in Example 1, to obtain the conversion and product selectivity of the reactants shown in Table 3.

Temperature ( ^o C) 250 300 350 Conversion (%) 97.7 100 100 Selectivity (%) Branched Ketone (C5 ~ C13) 10.0 1.8 0.0 Paraffin (C3 ~ C4) 2.4 0.4 1.4 Paraffin (C5 ~ C12) 69.5 84.2 54.2 Paraffin (C13 ~ C36) 2.1 0.0 0.0 Olefin 0.0 0.4 0.9 Aromatic 11.4 5.9 39.1 Alcohol 1.2 0.0 0.7 Acid 0.2 0.0 0.0 Ether 0.0 0.2 0.0 Unknown 3.1 7.1 3.7

Example  3

For the ketone mixture having the component distribution of Table 1, an experiment was performed to prepare a branched paraffin hydrocarbon using a bilayer catalyst composed of two materials, 0.25 wt% Pd / CeZrOx and Ni-Mo / ZrO ₂ . To prepare a 0.25 wt% Pd / CeZrOx catalyst, a CeZrOx carrier was prepared as follows. The ratio of Ce (No ₃ ) ₃ 6H ₂ O and ZrO (NO ₃ ) ₂ was 1: 1, and the mixture was co-precipitated for 65 hours while maintaining the pH at 10 with NH ₄ OH. The precipitate was filtered and washed, dried at 383 K for a sufficient time and calcined at 723 K for 2 hours. The reaction was carried out using a high-pressure micro-reactor, the experiment was conducted using a total of 6g of 3g each of the two catalysts prepared by the above method. Reduction and reaction of the catalyst was carried out in the same manner as in Example 1, to obtain the conversion and product selectivity of the reactants shown in Table 4.

Temperature ( ^o C) 250 300 350 Conversion (%) 99.8 100 100 Selectivity (%) Branched Ketone (C5 ~ C13) 1.0 0.7 0.1 Paraffin (C3 ~ C4) 3.0 1.2 0.5 Paraffin (C5 ~ C12) 84.0 72.3 72.0 Paraffin (C13 ~ C36) 6.1 19.7 22.7 Olefin 0.0 0.2 0.0 Aromatic 0.0 0.0 0.0 Alcohol 4.7 1.8 1.1 Acid 0.0 0.0 0.0 Ether 0.0 0.2 0.3 Unknown 1.3 3.9 3.3

Example  4

0.25 wt% Pd / CeZrOx for ketone mixtures with component distributions in Table 1 An experiment was carried out to prepare branched paraffin hydrocarbons using 6 g of a catalyst prepared by physically mixing 3 g with 3 g of Ni-Mo / ZrO ₂ . 0.25 wt% Pd / CeZrOx and Ni-Mo / ZrO ₂ catalysts were prepared in the same manner as described in Example 3. Reduction and reaction of the catalyst was carried out in the same manner as in Example 1, to obtain the conversion and product selectivity of the reactants shown in Table 5.

Temperature ( ^o C) 250 300 350 Conversion (%) 99 98 99.4 Selectivity (%) Branched Ketone (C5 ~ C13) 2.3 2.6 1.1 Paraffin (C3 ~ C4) 1.7 2.1 2.9 Paraffin (C5 ~ C12) 59.1 88.9 89.2 Paraffin (C13 ~ C36) 1.2 5.8 4.9 Olefin 0.0 0.0 0.2 Aromatic 0.1 0.4 1.3 Alcohol 34.0 0.0 0.3 Acid 0.0 0.0 0.0 Ether 0.0 0.0 0.2 Unknown 1.5 0.2 0.0

Comparative example  One

For ketone mixtures having the component distributions in Table 1, experiments were carried out to produce branched paraffin hydrocarbons using 6 g of 0.25 wt% Pd / Nb ₂ O ₅ catalyst. 0.25 wt% Pd / Nb ₂ O ₅ catalyst was prepared in the same manner as described in Example 1. Reduction and reaction of the catalyst were carried out in the same manner as in Example 1, to obtain the conversion and product selectivity of the reactants shown in Table 6.

Temperature ( ^o C) 300 Conversion (%) 93 Selectivity (%) Branched Ketone (C5 ~ C13) 20 Paraffin (C3 ~ C4) 5 Paraffin (C5 ~ C12) 42 Paraffin (C13 ~ C36) 5 Olefin 15 Aromatic 4 Alcohol 6 Acid - Ether - Unknown 3

Comparative example  2

0.25 wt% Pd / CeZrOx for ketone mixtures with component distributions in Table 1 An experiment was performed to produce branched paraffin hydrocarbons using 6 g. 0.25 wt% Pd / CeZrOx catalyst was prepared in the same manner as described in Example 3. Reduction and reaction of the catalyst was carried out in the same manner as in Example 1, to obtain the conversion and product selectivity of the reactants shown in Table 7.

Temperature ( ^o C) 300 Conversion (%) 92 Selectivity (%) Branched Ketone (C5 ~ C13) 42 Paraffin (C3 ~ C4) 2 Paraffin (C5 ~ C12) 13 Paraffin (C13 ~ C36) 15 Olefin 20 Aromatic 2 Alcohol 4 Acid - Ether - Unknown 2

Claims (16)

A method for producing a branched nonpolar paraffin, comprising aldol condensation reaction, hydrogenation reaction, and hydrodeoxygenation reaction from a ketone mixture raw material through a catalytic reaction. The method according to claim 1,
Iii) an aldol condensation reaction of the ketone mixture to produce a ketone hydroxide with increased carbon chain length;
Ii) dehydrating the ketone hydroxide to form Enone;
iii) forming ketones having an increased carbon chain length through hydrogenation of the inon;
iv-1) converting the ketone generated in step iii) into a branched nonpolar paraffin by hydrodeoxygenation;
iv-2) The ketones produced in step iii) are reacted with ketones of the same or different lengths of carbon chains to form inon hydroxides having a longer carbon chain length, and the length of the carbon chains is slightly increased through the hydrogenation reaction. Forming an increased ketone;
v) a method of producing paraffin, comprising the step of converting the ketone generated in step iv-2) into a branched nonpolar paraffin by hydrodeoxygenation. The method of claim 1, wherein the ketone mixture is a ketone mixture obtained from volatile fatty acids derived from biomass or obtained through a typical chemical reaction. The method of claim 1, wherein the paraffin is C3 ~ C60 branched non-polar paraffin that can be used as a fuel and lubricating base oil for the production of paraffin. The method of claim 1, wherein the catalyst comprises at least one of condensation, hydrogenation, and hydrodeoxygenation functions. The method of claim 5, wherein the catalyst is physically mixed or formed using a binder material to form a catalyst system. The method of claim 5, wherein the catalyst constitutes a catalyst system in such a manner that the catalysts are composed of double layers. The method for producing paraffin according to claim 5, wherein when the catalyst has a condensation function, the catalyst contains at least one acid function or a salt function. The method of claim 8, wherein the catalyst having a condensation function is CeZrOx, CuZrOx, hydrotalcite, niobium oxide, alumina, silica, silica-alumina, zirconia, titania, or these And a molecular sieve comprising a mixed oxide of zeolite, zeolite or the like. The method of claim 5, wherein the catalyst having a hydrogenation function is a metal component selected from Group VIII metal, Group VI metal, or a mixture thereof having a hydrogenation function. The method of claim 10, wherein the metal component is selected from the group consisting of Pd, Pt, Rh, Ru, Ni, NiMo, CoMo, NiW, or CoW. The method of claim 5, wherein the catalyst having a hydrodeoxygenation function comprises both a hydrogenation function and a deoxygenation function. The method of claim 12, wherein the catalyst having a hydrodeoxygenation function is prepared in a form in which a metal component having the hydrogenation function is supported on a material containing at least one acid or salt function. The method of claim 1, wherein the catalytic reaction is performed in a single reactor or two continuous reactors. The method of claim 1, wherein the aldol condensation reaction, the hydrogenation reaction, the hydrodeoxygenation reaction is carried out at a temperature in the range of 80 ~ 500 ℃, hydrogen pressure range of 1 ~ 200 bar. The method of claim 15, wherein the aldol condensation reaction, the hydrogenation reaction, the hydrodeoxygenation reaction is carried out at a temperature in the range of 100 ~ 400 ℃, hydrogen pressure range of 5 ~ 50 bar.