ES2570231B1 - PROCESS FOR THE PREPARATION OF HIGHER ALCOHOLS FROM ETHANOL AND N-HEXANOL BY GUERBET CONDENSATION - Google Patents

Abstract

Process for the preparation of higher alcohols from ethanol and n-hexanol by condensation of Guerbet. # The present disclosure relates, in general, to integrated processes for the preparation of n-butanol in an n-butanol reactor from a reaction mixture comprising ethanol and hydrogen to produce a stream of n-butanol product by condensation of Guerbet comprising n-butanol and n-hexanol and for the preparation of noctanol in an n-octanol reactor from a mixture A reaction comprising ethanol, n-hexanol and hydrogen to produce a n-octanol product stream by Guerbet condensation comprising n-butanol, n-hexanol and n-octanol. A predominant proportion of the n-hexanol contained in the product streams of n-butanol and n-octanol is isolated and recycled in the reaction mixture of n-octanol. In some aspects, the present disclosure relates to improvements in the performance and selectivity of n-octanol and n-butanol by selecting process reaction conditions such as, but not limited to, the mole ratio of n- hexanol with respect to ethanol and the recovery and recycling of n-hexanol.

Description

Process for the preparation of higher alcohols from ethanol and n-hexanol by Guerbet condensation

Background

The present disclosure relates, in general, to processes for the preparation of higher alcohols from ethanol and n-hexanol by condensation of Guerbet.

The higher alcohols, which have 8 to 16 carbon atoms, are valuable for use as plasticizers such as cold-resistant plasticizers of plastics, anti-foaming agents, dispersing agents, surfactants, mineral separation agents and petroleum additives. Higher alcohols are also valuable for use in other applications such as cosmetics, printing and staining, painting, and photographic film.

Lower alcohols, which have 2 to 4 carbon atoms (ethanol and n-butanol), are useful as fuel additives. However, there are problems associated with the use of ethanol fuel in internal combustion engines, including its water solubility, corrosivity and differences in its combustible properties compared to gasoline. In order to overcome the disadvantages of ethanol as a fuel, the catalytic condensation of ethanol in n-butanol can be carried out. Compared to ethanol, nbutanol has several advantages. For example, n-butanol can be burned in existing gasoline engines without virtually any engine or vehicle modification and has a higher energy content and air ratio to fuel.

The n-butanol can be obtained by means of the well-known Guerbet reaction, which makes it possible to catalytically convert ethanol to n-butanol. The preparation of n-butanol by synthesis of Guerbet from ethanol results problematically in the protection of considerable amounts of n-hexanol. Typically, about 0.05 to about 0.1 moles of n-hexanol are generated in Guerbet's condensation of ethanol per mole of n-butanol produced. In a problematic way, in comparison with ethanol and butanol and also in comparison with higher alcohols having 8 to 16 carbon atoms, n-hexanol has a limited industrial applicability, has a lower value, and usually incinerate to recover energy.

There is a need for improved processes for the generation of higher alcohols by condensing Guerbet from lower alcohols in which the amount produced of n-butanol and n-octanol is maximized and the amount produced of rr hexanol is minimized.

Brief Summary

In one aspect of the present disclosure, a continuous process for preparing n-butanol and n-actane! Is provided. The process comprises (1) forming a gaseous phase nbutanol reaction mixture comprising an ethanol source and a hydrogen source, (2) reacting the gaseous phase n-butanol reaction mixture with a Guerbet catalyst in a gas phase n-butanol reactor at a reaction temperature of 150 pe to 450 pe and a reaction pressure of 10 to 200 bara to form a n-butanol reactor product stream comprising n-butanol and n- hexanol and (3) fractionate the n-butanol reactor product stream to form a nbutanol product stream and a recovered n-hexanol stream. The process further comprises (1) forming a gas phase n-octanol reaction mixture comprising a source of nhexanol comprising at least a part of the n-hexanol recovered from the n-butanol reaction mixture and the mixture of reaction of n-octanol, a source of ethanol and a source of hydrogen, (2) reacting the gas phase n-octanol reaction mixture by contacting a Guerbet catalyst in a gas phase n-octanol reactor at a reaction temperature of 150 pe to 450 pe and a reaction pressure of 10 to 200 bara to form a n-octanol reactor product stream comprising noctanol, n-butanol and n-hexanol and (3) fractionate the current of noctanol reactor product to form a n-octanol product stream, a recovered n-hexanol stream and a n-butane product stream!

In another aspect of the present disclosure, there is provided an installation for manufacturing nbutanol and n-octanol from an ethanol source and a n-hexanol source. The installation comprises an n-butanol reactor system comprising at least one gas phase reactor having a fixed catalyst bed, the reactor (1) comprising an inlet port for the inlet of a reactor system feed stream gas of nbutanol comprising a source of ethanol and a source of hydrogen, (2) a reaction zone containing a heterogeneous catalyst to contact the catalyst to form a stream of n-butanol reactor product, and (3) an exit port for

the discharge of a product stream from the n-butanol reactor system, the reactor product stream comprising n-butanol ethanol, water, n-hexanol, and hydrogen, in which the n-butanol reactor system is operational at a reaction temperature of 150 2e to 450!: and a reaction pressure of 10 to 200 bara. The installation further comprises an n-octanol reactor system comprising at least one gas phase reactor having a fixed catalyst bed, the reactor (1) comprising an inlet port for the input of a reactor feed stream gas of n-octanol comprising a source of ethanol, a source of n-hexanol and a source of hydrogen, (2) a reaction zone containing a heterogeneous catalyst to contact the reactor feed stream to form a stream of n-octanol reactor product, and

(3) an outlet port for the discharge of the n-octanol reactor product stream, comprising the reactor product stream of n-octanol ethanol, water, n-hexanol, noctanol and hydrogen, in which the system n-octanol reactor is operational at a reaction temperature of 150 2C to 450 2C and a reaction pressure of 10 to 200 bara. The installation further comprises a first system for fractionating the n-butanol reactor product stream and the n-octanol reactor product stream, in which the first fractionation system comprises a distillation column or an instantaneous evaporation column forming (1) a first fractional stream comprising at least 95 mole percent of each of the water, ethanol and hydrogen contained in the n-butanol reactor product stream and the reactor product stream of n-octanol and (2) a second fractional stream comprising at least 95 mole percent of each of the n-butanol, n-hexanol and n-octanol contained in the n-butanol reactor stream and the n-octanol reactor product stream. The installation further comprises a second system for fractionating the second fractional stream, in which the second fractionation system comprises a distillation column that forms (1) a stream enriched in n-butanol comprising at least 95 mole percent of the n-butanol contained in the second fractional stream and (2) a fourth fractional stream comprising at least 95 mole percent of each of the n-hexanol and n-octanol contained in the second fractionated stream. In addition, the installation comprises a third system for fractionating the fourth fractional stream, in which the third fractionation system comprises a distillation column that forms (1) a recovered n-hexanol stream comprising at least 95 mole percent of the n-hexanol contained in the fourth fractional stream, in which the recovered n-hexanol stream is interconnected with the n-hexanol source for the n-octanol reactor system and at least a portion of the recovered n-hexanol is recycles into the n-octanol reactor feed stream and (2) an n-octanol stream that

It comprises at least 95 mole percent of the n-octanol contained in the fourth fractional stream.

The installation according to the invention may further comprise a system for fractionating the first fractional stream, in which the first fractional stream comprises steam and the system for fractionating the first fractional stream comprises a condenser and an ethanol dehydration system in which (a) the first fractional stream is passed through the condenser to form a stream of recovered hydrogen gas and a stream of wet ethanol condensate and (b) the stream of wet ethanol condensate is dehydrated to form a stream of ethanol recovered and a water stream in which the recovered ethanol stream comprises at least 95 mole percent of the ethanol and less than 5 mole percent of the water contained in the first fractionated stream, and in which the stream of recovered ethanol and the recovered hydrogen stream are interconnected with the ethanol source and the hydrogen source for the n-butanol reactor system and the n-octanol reactor system and at least a portion of the recovered ethanol and the recovered hydrogen is recycled in each of the n-butanol reactor feed stream and the feed stream of the n-octane reactor!

The process according to the invention may further comprise the following characteristics:

(to)

(1) the product stream of the n-butanol reactor further comprises ethanol and hydrogen, (2) the process further comprises fractionating the product stream of the n-butanol reactor to form a recovered ethanol stream and a recovered hydrogen stream and (3) the source of ethanol and the source of hydrogen in the gas phase nbutanol reaction mixture and the source of ethanol and the source of hydrogen in the gas phase n-octanol reaction mixture comprise (i) the at least a part of the recovered ethanol stream formed from the product stream of the n-butanol reactor and (ii) at least a portion of the recovered hydrogen stream formed from the product stream of the n- reactor butanol; Y

(b)

(1) the product stream of the n-octanol reactor further comprises ethanol and hydrogen, (2) the process further comprises fractionating the product stream of the n-octanol reactor to form a recovered ethanol stream and a recovered hydrogen stream and (3) the source of ethanol and the source of hydrogen in the reaction mixture of n

gas phase butanol and the source of ethanol and the source of hydrogen in the gas phase n-octanol reaction mixture comprise (i) at least a portion of the recovered ethanol stream formed from the reactor product stream of n-octanol and (ii) at least a portion of the recovered hydrogen stream formed from the product stream of the n-octanol reactor.

The process according to the invention may further comprise the following characteristics:

(to)

(1) The yield of ethanol-based n-butanol in the reaction of the n-butanol reaction mixture is 10% to 40%, 10% to 30%, 15% to 30%. % or from 20% to 30% Y (2) the n-butanol selectivity in the reaction of the n-butanol reaction mixture is 65% to 95%, 65% to 85% , from 65% to 80%, or from 65% to 75%; Y

(b)

(1) the n-butanol selectivity in the reaction of the n-octanol reaction mixture is 10% to 40%, 15% to 40% or 15% to 25%, ( 2) the n-octanol selectivity in the reaction of the n-octanol reaction mixture is 20% to 55%, 30% to 50% or 40% to 50% Y (3 ) the conversion of ethanol in the reaction of the n-octanol reaction mixture is from 20% to 60%, from 20% to 40%, 20%, 30% or 40%.

The process according to the invention may further comprise the following characteristics: (a) the source of ethanol for the n-butanol reaction mixture and for the n-octanol reaction mixture each comprises at least 50 percent in moles, at least 60 mole percent, at least 65 mole percent or at least 70 mole percent recovered ethanol; (b) the source of hydrogen for the n-butanol reaction mixture and for the n-octanol reaction mixture each comprises at least 50 mole percent, at least 60 mole percent, at least one 65 mole percent or at least 70 mole percent of hydrogen recovered; and (c) the source of n-hexanol for the n-octanol reaction mixture comprises at least 50 mole percent, at least 60 mole percent, at least 65 mole percent, at least one 70 mole percent, or consists of recovered n-hexanol.

The process according to the invention may further comprise the following characteristics: (a) the mole ratio of ethanol to n-hexanol in the mixture

The reaction of n-octanol is 0.3: 1 to 3: 1, 1.1: 1 to 2: 1, 1.1: 1 to 1.5: 1, or 1.3: 1; (b) the

mole ratio of hydrogen to ethanol in the reactor mixture of n

Butanol is 0.1: 1 to 5: 1, 0.1: 1 to 0.6: 1, 0.1: 1 to 0.4: 1, 0.5: 1 to 3: 1, or 0.75: 1 a

1.5: 1; and (e) the mole ratio of hydrogen with respect to the sum of ethanol and n-

S

Hexanol in the n-octanol reaction mixture is 0.1: 1 to 5: 1, 0.1: 1 to 1: 1, 0.1, 1 to 1

0.5: 1, 00.3: 1.

The process according to the invention may further comprise the following

characteristics: (a) the n-butanol reaction mixture further comprises a source of

10

acetaldehyde and the mole ratio of acetaldehyde with respect to ethanol in the mixture

The reaction of n-butanol is from 0.001: 1 to 0.1: 1, from 0.001: 1 to 0.005: 1, from 0.001: 1 to 0.003: 1,

from 0.005: 1 to 0.1: 1, or from 0.01: 1 to 0.04: 1; (b) the n-butanol product stream comprises

in addition acetaldehyde and the product stream of the n-butanol reactor is fractionated to

recover at least part of the acetaldehyde and form a stream of acetaldehyde

fifteen

recovered; and (c) at least a part of the source of acetaldehyde in the reaction mixture

of n-butanol comprises recovered acetaldehyde.

The installation according to the present invention may further comprise:

twenty

(a) flow control for the ethanol source in the n-octanol reactor system and control of

flow for the n-hexanol source in the n-octanol reactor system, in which the proportion

in moles of ethanol with respect to n-hexanol in the reactor feed stream of

n-octanol is controlled by a flow rate of 0.3: 1 to 3: 1, from 1.1: 1 to 2: 1, of

1.1: 1 to 1.5: 1, or 1.3: 1;

25

(b) flow control for the hydrogen source in the n-octanol reactor system, in which

the mole ratio of hydrogen with respect to the sum of ethanol and n-hexanol in the

n-octanol reactor feed current is controlled by a proportion of

0.1: 1 a5: 1, deO, 1: 1 to 1: 1, deO, 1: 1 aO, 5: 1, oO, 3: 1 flow; Y

30

(c) flow control for the source of ethanol in the n-butanol reactor system and control of

flow to the hydrogen source in the n-butanol reactor system, in which the proportion

in moles of hydrogen with respect to ethanol is controlled by a flow control of

0.1: 1 a5: 1, deO, 1: 1 aO, 6: 1, deO, 1: 1 a0.4: 1, deO, 5: 1 a3: 1, odeO, 75: 1 to 1.5: one.

35

The installation according to the present invention may further comprise the following characteristics:

(to)

at least 50 percent by mole, at least 60 percent by mole, at least 70 percent by mole, at least 80 percent by mole, at least 90 percent by mole, at least 95 percent mole percent, or at least 99 mole percent of the nhexanol present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and recycled into the feed stream of the n-octanol reactor;

(b)

at least 50 percent by mole, at least 60 percent by mole, at least 70 percent by mole, at least 80 percent by mole, at least 90 percent by mole or at least 95 percent mole percent of the ethanol present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and recycled in the n-octanol reactor feed stream and in the stream of n-butanol reactor feed; Y

(C)

at least 50 percent by mole, at least 60 percent by mole, at least 70 percent by mole, at least 80 percent by mole, at least 90 percent by mole or at least 95 percent mole percent of the hydrogen present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and recycled in the n-octanol reactor feed stream and in the stream of n-butanol reactor feed.

The installation according to the present invention may further comprise the following characteristics:

(to)

The n-octanol stream is a crude n-octanol stream which further comprises n-decanol, the installation further comprising a distillation column to fractionate the raw n-octanol stream to form (1) a product stream of n-octanol comprising at least 95 mole percent of the n-octanol contained in the crude noctanol stream and (ii) a stream enriched in n-decanol comprising at least 95 mole percent of the n-decanol content in the crude n-octanol stream;

(b)

The n-butanol enriched stream further comprises β-butanol, the installation further comprising a distillation column to fractionate the enriched stream into

n-butanol to form a stream of n-butanol product having a purity exceeding 99 mole percent of n-butanol and a stream of impurities comprising β-butanol;

(and)

The installation further comprises a distillation column for purification of the n-octanol product stream, said distillation column fractionating the n-octanol product stream to form a finished n-octanol product stream having a purity exceeding of 99 mole percent of n-octanol; Y

(d)

The installation further comprises a distillation column of the ndecanol stream to fractionate the n-decanol-enriched stream to form (i) a stream of n-decanol product comprising at least 90 mole percent or at least 95 mole percent of the n-decanol contained in the raw n-channel enriched stream and (ii) a bottom stream of the distillation column of the ndecanol stream enriched in compounds that boil at a temperature greater than the point of boiling of n-decanol compared to the current enriched in n-decane !.

The installation according to the present invention may also lack a process output current comprising an excess of 0.001, 0.005 or 0.01 mole percent of n-hexanol.

Brief description of the figures

Figure 1 is a process flow diagram of a first aspect of the present disclosure.

Figure 2 is a process flow diagram of a second aspect of the present disclosure.

Figure 3 is a process flow diagram of a third aspect of the present disclosure.

Figure 4 is a process flow diagram of a fourth aspect of the present disclosure.

Figure 5 is a process flow diagram of a fifth aspect of the present

divulgation.

Figure 6 is a process flow diagram of a sixth aspect of the present disclosure.

Figure 7 is a process flow diagram of a seventh aspect of the present disclosure.

Figure 8 is a process flow diagram of an eighth aspect of the present disclosure.

Figure 9 is a process flow diagram of a ninth aspect of the present disclosure.

Figure 10 is a process flow diagram of a tenth aspect of the present disclosure.

Figure 11 is a process flow diagram of an eleventh aspect of the present disclosure.

Detailed description

The present disclosure relates, in general, to an integrated catalytic process to simultaneously produce C4 alcohols and higher Ca to C16 alcohols by condensing Guerbet by catalytic condensation of alcohols under elevated temperature and pressure conditions by dehydrogenation, aldol condensation and hydrogenation. In accordance with the present disclosure, (1) n-butanol is prepared in an n-butanol reactor from a reaction mixture comprising ethanol and hydrogen to produce a stream of n-butanol product by Guerbet condensation comprising n-butanol, n-hexanol, ethanol and hydrogen and (2) n-octanol is prepared in an n-octanol reactor from a reaction mixture comprising ethanol, n-hexanol and hydrogen to produce a product stream of n-octanol by Guerbet condensation comprising n-butanol, n-hexanol, ethanol, hydrogen and n-octane! In some aspects of the disclosure, a predominant part of the n-hexanol contained in the product streams of n-butanol and n-octanol is isolated and recycled into the noctane reaction mixture! In some other aspects of the disclosure, a predominant part of the

ethanol contained in the product streams of n-butanol and n-octanol and is recycled in the reaction mixture of n-butanol and n-octanol. In some other aspects of the disclosure, the hydrogen contained in the product streams of n-butanol and n-octanol is isolated and recycled in the reaction mixture of n-butanol and n-octanol.

For the preparation of butanol from ethanol, the reaction sequence can be described as follows:

CH3CH20H -7 CH3CHO + H2 (1)

CH3CH20H + CH3CHO + H2 -7 C, H, OH + H20 (2)

and the overall reaction is as follows:

2 CH3CH20 H -7 C, H, OH + H20 (3)

N-Hexanol can be generated by condensing n-butanol and ethanol according to the overall reaction CH3 (CH2hOH + CH3CH20H ~ CSH130H + H20.

N-octanol can be generated by: (i) the condensation of n-hexanol and ethanol according to the global reaction CH3CH20H + CSH130H ~ CSH170 H + H20, (ii) the condensation of two n-butanol molecules according to the global reaction 2 CH3 (CH2hOH -7 CSH170H + H20 and / or (iii) by successive condensation of n-butanol with ethanol.

N-Decanol can be generated by: (i) the condensation of n-hexanol and ethanol according to the global reaction CH3CH20 H + CSH170H ~ ClOH210H + H20 and / or (ii) the condensation of n-butanol and n-hexanol according to the overall reaction CH3 (CH2hOH + CSH130H -7 ClOH2, OH + H20.

In accordance with the present disclosure, it has been found that the conversion rate of the mixture of starting alcohols (for example, ethanol and n-hexanol), the selectivity of Guerbet alcohols (for example, n-butanol, n-hexanol , n-octanol and n-decanol) and the performance of Guerbet alcohols are generally affected by numerous factors. It has also been discovered that the optimization of these factors, and combinations thereof, allows the preparation of n-butanol, n-octanol and n-decanol with high selectivity and yield. For example, it has been found that the following list of non-limiting factors affects the effectiveness of the Guerbet reaction of the present disclosure: (i) the catalyst, catalyst load and catalyst life, (ii) the proportion of ethanol with respect to n-hexanol in the reaction mixture, (jii) the concentration of various impurities and thickeners in the reactor feed stream and various recycle streams, for example and without restriction, water and hydrogen, (iv) the proportions of said impurities and thickeners in the starting alcohol, (v) the reaction temperature, (vi) the reaction pressure, (vii) the velocity of liquid reactor time ("LHSV"), in which LHSV is refers to the ratio of the incoming volumetric flow rate of the reactants divided by the reactor volume and is an indication of the number of reactant feed reactor volumes that can be treated in a unit of time; and (viii) selected combinations of one or more of (i) to (vii).

As used herein, it is understood that the term "C3 to C16 higher alcohols" means any linear or branched alkyl chain with at least one hydroxyl functional group having between 3 and 16 carbon atoms. Non-limiting examples are propanol, isopropanol, n-butanol, 2-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol-1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl- t -propanol, 3-methyl-2-butanol, t, S-pentanediol, 2,4pentanediol, 2,2-dimethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-2-hexanol, 2,2-dimethyl-3pentanol-1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-ethyl-n-hexanol, 3-ethyl-1-hexanol, 2,2-dimethyl-3-hexanol, n-decanol, 2-decanol, 3-decanol, 4-decanol. As used herein, "condensate" refers to a process stream that predominantly contains condensed liquids at the temperature and pressure thereof, but not excluding the presence of a certain amount of gas or steam. As used herein, "gas" and "steam" are used interchangeably and may comprise condensable compounds (for example, ethanol) and basically non-condensable compounds (for example, hydrogen), and the possibility of Some liquid drag. As used herein, "predominantly" means greater than 50%, at least 75%, at least 90% or at least 95% in a% of population, based on% plp,%%% v / v. As used herein, "trace amount" and "basic absence" refer to a detectable, but minor amount, such as less than 0.05 mol% or less than 0.01 mol%. As used herein, "n-butanol", "n-hexanol", "n-octanol" and "n-decanol" refer to 1-butanol, 1hexanol, 1-octanol and 1-decanol, respectively.

3S Various non-limiting aspects of this disclosure are represented in Figures 1 to

eleven.

Figure 1 depicts a first aspect of the process of the present disclosure in which a reaction mixture 340 is formed by combination of soda ethanol 330, recycled ethanol 201, recycled n-hexanol 301, optional soda n-hexanol 320, hydrogen of soda 310 and recycled hydrogen 350. The reaction mixture is vaporized and contacted with a heterogeneous catalyst under elevated temperature and pressure conditions in an octanol reactor system 230 to form a reactor product stream 232 comprising water, hydrogen, ethanol, n-butanol, n-hexanol and aliphatic Ca Y ClO alcohols that include n-octanol and n-decanol. The reactor product stream 232 is fractionated into a separator column 50 to form (i) a separator column bottom stream 58 predominantly comprising high boiling compounds including n-butanol, butane, n-hexanol and heavier aliphatic alcohols that include n-octanol and n-decanol and (ii) a separating column header stream predominantly comprising ethanol, water and hydrogen. The separating column header stream is processed to form a stream of recycled hydrogen 350 and a stream of wet ethanol 360. The stream of wet ethanol 360 is processed by dehydration of ethanol 200 to form a stream of recycled ethanol 201 and a stream of Water

202. The separating column bottom stream 58 is fractionated in a multi-stage distillation operation 300 to form a mixed stream of butanol isomers 303, n-hexanol for recycling 301 and aliphatic alcohols 302 comprising n-octanol and ndecane! . The mixed stream of butanol isomers 303 is optionally fractionated to produce a first stream that predominantly comprises n-butanol and a second stream that predominantly comprises β-butanol.

In another aspect of the disclosure, depicted in Figure 2, the hexanol 105 generated as a secondary product is isolated in a Guerbet condensation reaction of ethanol in butanol and reacted in a Guerbet condensation with a hydrogen source 231 and a source of ethanol 193 to form n-octanol 252 and n-decanol 271 as generally represented in system 211. In particular, the soda ethanol feed 1 is optionally divided into a fusel column 190 to form a stream of distillate soda ethanol feed 191 and a fusel oil stream 192 predominantly comprising amyl alcohol. The ethanol feed of soda 1 or the stream of ethanol of distilled soda 191 can optionally be passed through a purification bed (not shown in Figure 2) for removal of impurities (eg salts and ions). The ethanol feed stream of soda 191 can optionally be processed in molecular sieves 80 for water removal. The soda ethanol feed stream 191 is combined with the dry recovered ethanol stream 85 which is characterized by the basic absence of water to form an ethanol source 193 for the butanol reactor system 40 and the octanol reactor system

230. A reaction mixture formed from an ethanol stream 193 and a gas stream 33 comprising recovered hydrogen and optional cooling hydrogen 310 is heated to form the reactor feed gas stream 37. In some optional aspects of the disclosure, the reaction mixture further comprises recovered n-hexanol 222 and / or refreshment n-hexanol 320. The reactor feed gas stream 37 is contacted with a heterogeneous catalyst under elevated temperature and pressure conditions in the butanol reactor system 40 to form a reactor product stream 45 comprising water, hydrogen, acetaldehyde, ethyl acetate, n-butanol, butanol, n-hexanol, aliphatic Cs and ClO alcohols including n-octanol and n -decanol, and C10 + alcohols. In any of the various aspects of the present disclosure represented in the figures and described herein, a butanol reactor system 40 may comprise two or more reactors arranged in series or in parallel fed by one or more streams of feed gas of reactor 37. The reactor product stream 45 is fractionated on a separator column 50 to form

(i) a separating column bottom stream 58 predominantly comprising high boiling compounds that include n-butanol, -butanol, n-hexanol, noctanol and n-decanol and (ii) a first column header stream separator 51 comprising ethanol, acetaldehyde, ethyl acetate and hydrogen. The header current of the first separating column 51 is passed through a condenser to form (i) a first condensate stream 52 which is divided between separating column reflux 50 Y ethyl acetate column feed 60 and (ii) Separator column gas supply 53. The separator column gas stream 53 is passed through a second condenser to form a header condensate stream of second separator column 54 and a gas stream of second separator column 55. The gas stream of second separator column 55 is pressurized in a recycle compressor 20 to form a compressed gas stream of second separator column 21 which may be the gas source for the gas stream 33. In some other aspects of the present disclosure , the compressed gas stream of second separator column 21 can be processed by pressure change adsorption 30 to form a gas stream hydrogen 32 which is the gas source for the gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and ethane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the hydrogen gas stream 32 forms the gas stream 33. The condensate stream of the second separator column header 54 and the at least a part of the condensate stream of the first separating column 52 is directed to the ethyl acetate column 60 where the streams are fractionated to form a column bottom stream of ethyl acetate 65 comprising predominantly ethanol and water and a stream of column header purge of ethyl acetate 64 comprising predominantly acetaldehyde, hydrogen and ethyl acetate. In an optional aspect not shown in Figure 2, the ethyl header column purge stream 64 can be partially condensed and a portion of the condensate can be recycled in the ethyl acetate column 60 and purged from the process A part of the condensate. The bottom stream 65 of the ethyl acetate column 60 comprising wet ethanol is sent to an inlet port of molecular sieves 80. The bottom stream of ethyl acetate column 65 and the wet ethanol stream 92 of the column of regeneration are combined and processed in molecular sieves 80 to form a stream rich in water 88 and a stream of dry ethanol 85. The water-rich feed stream of molecular sieves 88 comprises ethanol and is processed in the regeneration column 90 where water and isoamyl alcohol (if present) are separated from ethanol to form a regeneration column bottom stream 95 comprising water that is sent to the wastewater treatment and a stream of wet ethanol 92 that is sent to the port input of the molecular sieves 80. The separating column bottom stream 58 is fractionated in the hexanol column 00 to form a hex bottom bottom stream anol1 05 predominantly comprising n-hexanol, n-octanol and n-decanol as major components and a header current of hexanol column condenser 106 comprising n-butanol and -butane !. In some optional aspects of the disclosure, a separating column bottom stream 58 can be fractionated according to the system 210 depicted in Figure 3 (described elsewhere herein) to generate various streams that include n- Hexanol for conversion into n-octanol in a 230 octanol and n-octane reactor system! Hexanol column condenser header stream 106 is fractionated into an isobutanol column 110 to form a hexanol column bottom stream 115 comprising basically pure n-butanol and a condensed hexanol column header stream 116 comprising -butane!. The hexaneol column bottom stream 105 is fractionated on a hexaneol purification column 220 to form a header stream 221 that is fractionated on a hexanol finish column 280 to form a bottom stream 282 predominantly comprising n-hexanol purified and a header stream 281 predominantly comprising 2-ethyl butanol. The purified n-hexanol stream 282 is combined with a source of ethanol 193 and a stream of gas 231 (corresponding to the stream of gas 33) comprising recovered hydrogen, and optionally a source of refresh hydrogen 310 (not represented) to form a feed gas stream for the octanol reactor 230. In the octanol reactor 230, the feed gas stream is contacted with a heterogeneous catalyst at elevated temperature and pressure to form a product stream of Octanol 232 reactor comprising ethanol, -butanol, n-butanol, n-hexanol, hexanal (hexanaldehyde), n-octanol, ndecanol, 2-ethyl-hexanol, ¡-decanol, and various compounds having a boiling point greater than the decanol isomers. The octanol reactor product stream 232 is refluxed in the separator column 50. The components comprising ethanol, water, hydrogen and acetaldehyde are fractionated in a header stream 51 and the organic compounds having four or more carbon atoms are fractionated in a background stream 58. Background stream 225 of the hexaneol purification column 220, comprising n-octanol, n-decanol, 2-ethyl-hexanol, and ¡-decanol is directed to the octanol column 240 and it is fractionated to form a bottom stream 242 comprising ndecanol, 2-ethyl-t-octanol (i-decanol), and high boiling compounds and a header stream 241 comprising n-octanol and 2-ethyl-hexanol . The header stream 241 is directed to a purification column of n-octanol 250 and fractionated to form a header stream 251 predominantly comprising 2-ethyl-hexanol and a bottom stream 252 predominantly comprising n-octanol. The bottom stream 242 is directed to a column of ¡-decanol 260 and fractionated to form a header stream 261 predominantly comprising 2-ethyl-n-octanol and a bottom stream 262 comprising n-decanol and high compounds Boiling point. The bottom stream 262 is directed to a n-decanol column 270 to form a header stream 271 predominantly comprising n-decaneol and a bottom stream 272 comprising predominantly high boiling compounds.

In another aspect of the present disclosure represented in Figure 3, the ethanol feed stream of soda 1 is optionally passed through a purification bed (not shown in Figure 3) for removal of impurities (e.g., salts and ions) to form a feed stream of soda ethanol comprising ethanol and water. In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. In such aspects, the feed stream 1 can be divided into a regeneration column 90 to separate the water and the isoamyl alcohol from the ethanol to form a regeneration column bottom stream 95 comprising water that is sent to the wastewater treatment , an isoamyl alcohol stream 93 and a regeneration column header stream 91 enriched in ethanol which is passed through a condenser to form a reflux stream and a wet ethanol stream which is then sent to the inlet port of molecular sieves 80. The wet ethanol stream 91 is combined with a recovered ethanol stream 56 and processed in molecular sieves 80 to form a dry ethanol stream 85 and a water-rich ethanol stream 88. The stream of recycled seca 85 is fed to the octanol reactor system 230 and the stream of water-rich ethanol 88 is fed to the Regenerac Column ion 90. The stream of dry ethanol 85 is combined with the stream of gas 33 comprising recovered hydrogen, recovered n-hexanol 282, optional soda hydrogen 310 and soda n-hexanol 320 to form a reactor feed stream that is heats to form a reactor feed gas stream 223. The reactor feed gas stream 223 is contacted with a heterogeneous catalyst under elevated temperature and pressure conditions in a reactor system 230 to form a reactor product stream 232 comprising water, hydrogen, acetaldehyde, ethyl acetate, n-butanol, ¡-butanol, n-hexanol, aliphatic Ca Y ClO alcohols including n-octanol and n-decanol, and ClO • alcohols. The reactor product stream 232 is fractionated into a separator column 50 to form (i) a separator column bottom stream 58 predominantly comprising components having four or more carbon atoms including n-butanol, -butanol, n -hexanol, n-octanol and n-decanol and (ii) a separating column header stream 51 predominantly comprising ethanol, acetaldehyde, ethyl acetate and hydrogen. The separator column header stream 51 is passed through a condenser to form (i) a gas stream 33 and (ii) a separator column header condensate stream 56 comprising recovered ethanol and water. In some optional aspects, not shown in FIG. 3, the separator column header stream 56 may optionally further be divided into one or more distillation and / or condensation columns to separate certain organic compounds, such as acetaldehyde and ethyl acetate, from ethanol. The separator column header current 56 is processed together with the regeneration column header current 91 in the molecular sieves 80 to generate a dry ethanol stream 85. The separator column bottom current 58 is fractionated in a distillation system 210 to form process streams including recycled n-hexanol 282, n-octanol 291 and n-decanol 271. In distillation system 210, the separator column bottom stream 58 is directed to the butanol column 100 and fractionated to form a header stream 101 predominantly comprising n-butanol e; -butanol and a bottom stream 105 which It comprises nhexanol, n-octanol and n-decane! In optional aspects of the present disclosure not shown in Figure 3, the header stream 101 can be processed in a -butanol 110 column to fractionate the -butanol (in a condensed header stream) of the n-butanol (in a background current). Hexanol105 column bottom stream is fed to the hexaneol purification column 220 and fractionated to

forming a header stream 221 comprising n-hexanol and 2-ethyl-butanol and a bottom stream 225 comprising 1-2-ethyl-hexanol, n-octanol and n-decanol. The header stream 221 is fed to a 2-ethyl-butanol column 280 and fractionated to form a header stream 281 predominantly comprising 2-ethyl-butanol and a bottom stream 282 predominantly comprising recovered n-hexanol for recycling in the octanol reactor system 230. The bottom stream 225 is fed into a 2-ethyl-hexanol column 245 and fractionated to form a header stream 247 comprising predominantly 2-ethyl-hexanol and a bottom stream 246 which It predominantly comprises n-octanol, n-decanol, 2-ethyl-1-octanol (i-decanol) and high boiling compounds. The bottom stream 246 is fed to an n-octanol column 290 and fractionated to form a header stream 291 predominantly comprising n-octanol and a bottom stream 292 predominantly comprising n-decanol and high boiling compounds such as hexadecanol. The bottom stream 292 is fed to an n-decanol column 270 and fractionated to form a header stream 271 predominantly comprising ndecanol and a bottom stream 272 comprising predominantly high boiling compounds (eg, hexa- decanol).

In another aspect of the present disclosure depicted in Figure 4, ethanol is generally condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol. The nbutanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octanol. In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 4) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and what can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is then divided into a regeneration column 90. A water-rich feed stream 88 of the molecular sieves 80 comprising ethanol in the regeneration column 90 is also fractionated. The regeneration column 90 separates the water and the isoamyl alcohol of ethanol to form a regeneration column bottom stream 95 comprising water that is sent to the wastewater treatment, an isoamyl alcohol stream 93 and a regeneration column header stream 91 that is passed to through a condenser to form a reflux stream 94 and a wet ethanol stream 92 which is then sent to the inlet port of the molecular sieves 80. The bottom stream 65 of the ethyl acetate column 60 comprising wet ethanol It is also sent to the inlet port of molecular sieves 80. The column bottom stream of ethyl acetate 65 and the current Wet ethanol 92 is processed in molecular sieves 80 to form a stream rich in water 88 and a stream of dry ethanol 85 in which stream 85 is characterized by the basic absence of acetaldehyde and a very low water content. The dry ethanol stream 85 is combined with a header stream of second separator column 54 comprising ethanol and acetaldehyde to form a mixed stream of ethanol feed

35. In some aspects of the present disclosure, the dry ethanol stream 85 is the source of ethanol for the octanol reactor system 230. The mixed alcohol feed stream 35 is combined with a stream of gas 33 comprising hydrogen. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) and / or n-hexanol of Cooling to the reactor feed stream 36. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. The reactor feed stream 36 is heated to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The reactor product stream 45 is fractionated into a separator column 50 to form a separator column bottom stream 58 predominantly comprising high point compounds

of boiling which include n-butanol, ¡-butanol, n-hexanol, n-octanol and n-decanol and a header current of the first separating column 51 comprising ethanol, acetaldehyde, ethyl acetate, hydrogen and carbon monoxide. In some aspects of the disclosure, the octanol reactor product stream 232 may be divided into a separator column 50. The header current of the first separator column 51 is passed through a capacitor to form (i) a first stream of condensate 52 which is divided between separator column reflux 50 and ethyl acetate column feed 60 and (ii) a first separator column gas stream 53. The separator column gas stream 53 is passed through a second condenser to form a header condensate stream of second separator column 54 and a gas stream of second separator column 55. The gas stream of second separator column 55 is pressurized in a recycle compressor 20 to form a compressed gas stream of the second separating column 21 which may be the gas source for the gas stream 33. In some other aspects of the present disclosure, the stream of compressed gas of second separator column 21 can be processed by adsorption with pressure change 30 to form a hydrogen gas stream 32 which is the gas source for the gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide carbon, carbon monoxide and ethane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the hydrogen gas stream 32 forms the gas stream 33. In some additional aspects of the present disclosure not shown in Figure 4 , at least a part of the hydrogen present in the reaction mixture is provided by compensating a source of soda hydrogen. At least a part of the condensate stream of the first separating column 52 is directed towards an ethyl acetate column 60 where it is fractionated to form a column bottom stream of ethyl acetate 65 and a column header stream of acetate acetate. ethyl 61. The ethyl acetate column header stream 61 is passed through a condenser to form an ethyl acetate column header gas purge stream 62 comprising acetaldehyde, hydrogen and ethyl acetate as major components and a condensate stream of ethyl acetate column header 63 comprising acetaldehyde, ethanol and ethyl acetate as major components. A part of stream 63 is recycled in the ethyl acetate column 60 and a portion of stream 63 is purged from the process. In an optional aspect of the present disclosure, the stream 63 can be purified, such as by a distillation column 70, to form a stream of purified ethyl acetate 72. The bottom column stream stream 58 is fractionated into a column

of hexanol 100 to form a hexaneol column bottom stream 105 comprising n-hexanol, n-octanol and n-decanol as major components and a condensed header stream of hexanol column 106 comprising n-butanol and minor amounts of n-propanol, ¡-butanol and 2-butanol. As described elsewhere herein, the hexaneol105 column bottom stream is fractionated in a hexane / octanol / decanol 210 purification system (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a recovered n-hexanol stream 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in an octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decane! The condensed header stream of hexanol column 106 is fractionated into an isobutanol column 110 to form an isobutanol column bottom stream 115 which basically comprises pure n-butanol and a condensed header stream of

Isobutanol column 116 comprising n-propanol, ¡-butanol, 2-butanol and n-butanol as major components.

In another aspect of the present disclosure, depicted in Figure 5, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol. The n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octane! In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 5) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and / or which can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is combined with a second separator column gas stream 55 comprising hydrogen (described above), and a recovered ethanol feed stream 35 (described above) to form a reactor feed stream 36. In some Optional aspects of the present disclosure, at least a portion of the recovered nhexanol 282 (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) and / or n-hexanol of soda can be added to the stream reactor feed. The reactor feed stream 36 is heated to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The reactor product stream 45 is fractionated into a separator column 50 to form a separator column bottom stream 58 predominantly comprising high boiling compounds including Ir butanol, butanol, n-hexanol, n-octanol and n-decanol and a header stream of first separator column 51 which it comprises low boiling compounds that include ethanol, acetaldehyde, ethyl acetate, hydrogen and carbon monoxide. In some aspects of the disclosure, the octanol reactor product stream 232 may be divided into a separator column 50. The header current of the first separator column 51 is passed through a capacitor to form (i) a first stream of condensate 52 which is divided between separator column reflux 50 and ethyl acetate column feed 60 and (ii) a first separator column gas stream 53. The separator column gas stream 53 is passed through a second condenser to form a header condensate stream of second separator column 54 and a gas stream of second separator column

55. The second separator column gas stream 55 is pressurized in a recycle compressor 20 before the combination with the soda feed stream 15 and the ethanol feed stream recovered 35. In some additional aspects of the present Disclosure not shown in Figure 5, at least a portion of the hydrogen present in the reaction mixture is provided by offsetting a source of hydrogen from soda. In some other aspects of the present disclosure, the gas stream 55 is the source of hydrogen for the octanol reactor system as described elsewhere herein. At least a part of the condensate stream of the first separating column 52 is directed to an ethyl acetate column 60 where it is fractionated to form a column bottom stream of ethyl acetate 65 and a column header stream of acetate 61. The ethyl acetate column header stream 61 is passed through a condenser to form an ethyl acetate column header gas purge stream 62 comprising acetaldehyde, hydrogen and ethyl acetate as major components and a condensate stream of ethyl acetate column header 63 comprising acetaldehyde, ethanol and ethyl acetate as major components. A part of stream 63 is recycled in the ethyl acetate column 60 and a portion of stream 63 is purged from the process. In an optional aspect of the present disclosure, the stream 63 can be purified, such as by a distillation column 70, to form a stream of purified ethyl acetate 72. The bottom stream 65 of the ethyl acetate column 60 which It comprises and the wet recovered ethanol stream 92 is processed in molecular sieves 80 to form a stream rich in water 88 and a dry recovered ethanol stream 85 in which stream 85 is characterized by the basic absence of acetaldehyde and a water content very low The dry recovered ethanol stream 85 is combined with the second separator column header stream 54 comprising ethanol and acetaldehyde to form a recovered ethanol feed stream 35. In some aspects of the present disclosure, the dry ethanol stream 85 is the ethanol source for the octanol 230 reactor system. The water-rich feed stream 88 of the molecular sieves 80 comprising ethanol is fractionated in the regeneration column 90. The regeneration column 90 separates the water and the isoamyl alcohol from the ethanol to form a regeneration column bottom stream 95 comprising water that is sent to the wastewater treatment, an isoamyl alcohol stream 93 and a regeneration column header stream 91 that is passed through a condenser for form a reflux stream 94 and a stream of wet ethanol 92 which is then sent to the inlet port of the s molecular sieves 80. The separating column bottom stream 58 is fractionated into a hexanol column 00 to form a hexanol column bottom stream 105 comprising n-hexanol, n-octanol and n-decanol as major components and a Hexanol column condenser header current 106 comprising n-butanol and minor amounts of n-propanol, β-butanol and 2-butanol. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a stream of n- Hexanol recovered 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decanol. The condensed header stream of hexanol column 106 is fractionated into an isobutanol column 110 to form an isobutanol column bottom stream 115 comprising basically pure n-butanol and a condensed header stream of hexanol column 116 comprising n- Propanol, ¡-butanol, 2butanol and n-butanol as major components.

In another aspect of the present disclosure, depicted in Figure 6, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol. The n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octanol. In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 6) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and / or which can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is sent to the input port of an extractive distillation column 130. The bottom stream of ethyl acetate column 65 (comprising ethanol and water) is also sent to the input port of the extractive distillation column 130 The combined streams are contacted with an extractive solvent in the extractive distillation column 130 to form a header stream 131 and a bottom stream 135 of the extractive distillation column. The header current 131 is passed through a condenser to form a dry ethanol feed stream 133 and a purge stream 132. The bottom stream 135 comprising contaminated extractive solvent is fractionated in a regeneration column 90 to generate a bottom stream comprising recovered extractive solvent 98 that is transferred to the extractive distillation column 130. The recovery of extractive solvent in the extractive distillation column 130 is done through a feed of extractive solvent of soda

136. The regeneration column header current 91 is passed through a condenser to form a condensed regeneration column header current 94 that is rich in water. At least a part of the stream 94 can be refluxed in column 130 and at least a portion is fed to a water eliminating column 150 for the removal of organic components thereof in the form of a header stream of water eliminating column 151 which is passed through a condenser to form the current 152. At least a part of the current 152 can be refluxed in the water eliminating column 150 and at least a part is transferred to a separating column 50. The current of Bottom of water eliminating column 155 is discharged to the wastewater treatment. Dry ethanol feed stream 133 is combined with the header stream of second separator column 54 comprising ethanol and acetaldehyde to form a mixed stream of ethanol feed

35. In some aspects of the present disclosure, the dry ethanol stream 133 is the source of ethanol for the octanol reactor system 230. The mixed alcohol feed stream 35 is combined with a stream of gas 33 comprising hydrogen to form a reactor feed stream 36. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3 can be added ) and / or n-hexanol soda to the reactor feed stream. In some additional aspects of the present disclosure not shown in Figure 6, at least a portion of the hydrogen present in the reaction mixture is provided by compensating for a source of soda hydrogen. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. The reactor feed stream 36 is heated to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The reactor product stream 45 is fractionated into a separator column 50 to form a separating column bottom stream 58 predominantly comprising high boiling compounds that include n-butanol, -butanol, n-hexanol, noctanol and n-decanol and a first separating column header stream 51 comprising low boiling compounds that include ethanol, acetaldehyde, ethyl acetate, hydrogen and carbon monoxide. In some aspects of the disclosure, the octanol reactor product stream 232 can be divided into a separator column 50. The header current of the first separator column 51 is passed through a capacitor to form a condensate stream 52. At least a part of the condensate stream 52 can be refluxed in a separator column 50 and at least a portion is fed into an ethyl acetate column 60 where it is fractionated to form a column bottom stream of ethyl acetate 65 and a column header stream of ethyl acetate 61. In some optional aspects of the present disclosure, at least a part of the condensate stream 52 can be purged from the process. The separator column gas stream 53 is passed through a heat exchanger to form a second separator column header stream 54 and a second separator column gas stream 55. The second separator column gas stream 55 is pressurizes in a recycle compressor 20. In some aspects of the present disclosure, the compressed gas stream of second separator column 21 may be the source of gas for the gas stream 33. In some other aspects of the present disclosure, the stream Compressed gas of second separator column 21 can be processed by pressure change adsorption 30 to form a gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and ethane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the gas stream 33 is the gas source for the butanol reactor system 40. The column header current of acetate acetate ethyl 61 is passed through a condenser to form a stream gas purge of ethyl acetate column head 62 comprising acetaldehyde, hydrogen and ethyl acetate as major components and a condensate stream of acetate column header of ethyl 63 comprising acetaldehyde, ethanol and ethyl acetate as major components. A part of stream 63 is recycled in the ethyl acetate column 60 and a portion of stream 63 is purged from the process. In an optional aspect of the present disclosure, the stream 63 can be purified, such as by a distillation column 70, to form a stream of purified ethyl acetate 72. The bottom column stream current 58 is fractionated into a column of hexanol 100 to form a column bottom stream of hexanol 105 comprising n-hexanol, n-octanol and ndecanol as major components and a column header current of hexanol 106 comprising n-butanol and minor amounts of n-propanol, -Butanol and 2-butanol. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a recovered hexanol stream 282 (FIG. 2)

or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decane! Hexanol column header stream 106 is fractionated on an isobutanol column 110 to form an isobutanol column bottom stream 115 comprising basically pure n-butanol and a condensed isobutanol column header stream 116 comprising npropanol, -Butanol, 2-butanol and n-butanol as major components.

In another aspect of the present disclosure, depicted in Figure 7, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol, the n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octanol. In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 7) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and / or which can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is sent to the inlet port of the molecular sieves 80. The intermediate stream 59 of the separator column 50 (comprising ethanol and water) and the wet ethanol stream 92 of the regeneration column 90 are also sent to the port input of the molecular sieves 80. The combined streams are processed in the molecular sieves 80 to form a water-rich feed stream 88 and a dry ethanol stream 85. The water-rich feed stream of the molecular sieves 88 is fractionated in the regeneration column 90 for the separation of the water and the isoamyl alcohol from the ethanol to form a regeneration column bottom stream 95 comprising water that is sent to the wastewater treatment, an isoamyl alcohol stream 93 and a stream of regeneration column header 91 that is passed through a capacitor to form a reflux stream 94 and a stream of wet ethanol 92 which is then sent to the inlet port of the molecular sieves 80. The stream of dry ethanol 85 is combined with a header current of the second separating column 54 comprising ethanol and acetaldehyde to form a mixed feed stream of ethanol 35. In some aspects of the present disclosure, the dry ethanol stream 85 is the source of ethanol for the octanol reactor system 230. The mixed alcohol feed stream 35 is combined with a gas stream 33 comprising hydrogen for forming a reactor feed stream 36. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 can be added (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) and / or nhexanol soda to the reactor feed stream. In some additional aspects of the present invention not shown in Figure 7, at least a portion of the hydrogen present in the reaction mixture is provided by compensating for a source of soda hydrogen. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. The reactor feed stream 36 is heated to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The reactor product stream 45 is fractionated into a preflash column 120 to form a preflash column bottom current 125, a mid-cut preflash column current 124 and a preflash column header column 121. The preflash column header current 121 is passed through a capacitor to form a current of condensate 122 and a preflash column gas stream 123. In some aspects of the present disclosure not shown in Figure 7, at least a portion of the condensate stream 122 and / or the preflash column gas stream 123 can be purge from the process. The bottom stream 125 and the mid-cut stream 124 of the pref / ash column are sent to a separator column 50 to form a bottom column stream 58 which predominantly comprises high boiling compounds that include n-butanol; butanol, n-hexanol, n-octanol and n-decanol, a middle cut-off current of separating column 59 comprising ethanol and water, and a header current of first separating column 51 comprising low boiling compounds that include ethanol, acetaldehyde, ethyl acetate, hydrogen and carbon monoxide. In some aspects of the disclosure, the octanol reactor product stream 232 can be divided into a separator column 50. The header current of the first separator column 51 is passed through a condenser to form a condensate stream 52 which it is recycled in a preflash column 120 and / or in a separator column 50. In some optional aspects of the present disclosure, at least a part of the condensate stream 52 can be purged from the process. The separator column gas stream 53 is combined with the preflash column gas stream 123 and is further condensed to form a second column header stream.

separator 54 and a gas stream of second separator column 55. The gas stream of second separator column 55 is pressurized in a recycle compressor 20. In some aspects of the present disclosure, the compressed gas stream of second separator column 21 may being the source of gas for the gas stream 33. In some other aspects of the present disclosure, the compressed gas stream of second separator column 21 can be processed by pressure change adsorption 30 to form a gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and ethane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the gas stream 33 is the gas source for the butanol reactor system 40. The separator column bottom stream 58 is fractionating into a hexanol 100 column to form a hexanol column bottom stream 105 comprising n-hexanol, n-octanol and n-decanol as major components and a condensed header stream of hexanol column 106 comprising n-butanol and minor amounts of n-propanol, ¡-butanol and 2-butanol. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a stream of n- Hexanol recovered 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decanol. Optionally, and not shown in Figure 7, the condensed header stream of hexanol column 106 can be fractionated into an isobutanol column to form a hexanol column bottom stream comprising basically pure nbutanol and a column header stream of condensed hexanol comprising n-propanol, ¡-butanol, 2-butanol and n-butanol as major components.

In another aspect of the present disclosure, depicted in Figure 8, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol. The n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is

condenses with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octanol. In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 8) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and / or which can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is sent to the input port of an extractive distillation column 130. The intermediate stream of separator column 59 (comprising ethanol and water) is also sent to the input port of the extractive distillation column 130. the combined streams they are fractionated by contact with an extractive solvent in the extractive distillation column 130 to form a header stream 131 and a bottom stream 135 of the extractive distillation column. The header current 131 is passed through a condenser to form a dry ethanol feed stream 133 and a purge stream 132. The bottom stream 135 comprising contaminated extractive solvent is sent to a regeneration column 90 to generate a bottom stream comprising recovered extractive solvent 98 that is transferred to the extractive distillation column 130. The compensation of extractive solvent in the extractive distillation column 130 is made through feed of soda solvent 136. The header stream of column 91 is passed through a condenser to form a condensed header current of regeneration column 94 that is rich in water. At least a part of the stream 94 can be refluxed in column 90 and at least a portion can be discharged to the wastewater treatment 95. A settling rectifier column 140 receives various streams containing organic components that include the condensed header stream of regeneration column 94, the hexaneol column bottom stream 105, and the decanter rectifier column bottom stream 145, represented as a combined stream 99, and removes the organic components thereof in the form of a column header stream decanter grinder 141 that is passed through a condenser and recycled into a preflash column 120 in the form of stream 142. At least a portion of the stream

rectifier column bottom 145 is discharged to the wastewater treatment 95. The dry ethanol feed stream 133 is combined with the header stream of the second separator column 54 comprising ethanol and acetaldehyde to form a mixed stream of ethanol feed 35 In some aspects of the present disclosure, the dry ethanol stream 133 is the source of ethanol for the octanol reactor system 230. The mixed alcohol feed stream 35 is combined with a stream of gas 33 comprising hydrogen to form the reactor feedstream 36. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) can be added and / or n-hexanol soda to the reactor feed stream. In some additional aspects of the present invention not shown in Figure 8, at least a portion of the hydrogen present in the reaction mixture is provided by compensating a source of soda hydrogen. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. The reactor feed stream 36 is heated to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The reactor product stream 45 is fractionated into a preflash column 120 to form a preflash column bottom current 125, a mid-cut preflash column current 124 and a preflash column header current 121. The preflash column header current 121 is passed through a capacitor to form a current of condensate 122 and a gas stream 123 of the preflash column. In some aspects of the present disclosure not shown in Figure 8, at least a portion of the condensate stream 122 and / or the preflash column gas stream 123 can be purged from the process. The bottom stream 125 and the mid-cut stream 124 of the preflash column are sent to a separator column 50 and fractionated to form a bottom column stream 58 which predominantly comprises high boiling compounds that include n-butanol, Butanol, n-hexanol, n-octanol and n-decanol, a middle cutoff current of separating column 59 comprising ethanol and water, and a header current of first separating column 51 comprising low boiling compounds including ethanol , acetaldehyde, ethyl acetate, hydrogen and carbon monoxide. In some aspects of the disclosure, the octanol reactor product stream 232 can be divided into a separator column 50. A header current of the first separator column 51 is passed through a condenser to form a condensate stream 52 which it is recycled in the preflash column 120 and it in the separator column 50. In some optional aspects of the present disclosure, at least a part of the condensate stream 52 can be purged from the process. The separator column gas stream 53 is combined with the preflash column gas stream 123 and is further condensed to form a header current of the second separator column 54 and a gas stream of the second separator column 55. The gas stream of Second separator column 55 is pressurized in a recycle compressor 20. In some aspects of the present disclosure, the compressed gas stream of second separator column 21 may be the gas source for the gas stream 33. In some other aspects of the In the present disclosure, the compressed gas stream of second separator column 21 can be processed by pressure change adsorption 30 to form the gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and ethane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the gas stream 33 is the gas source for the butanol reactor system 40. A separator column bottom stream 58 is fractionating into a hexanol 100 column to form a hexanol column bottom stream 105 comprising n-hexanol, n-octanol and n-decanol as major components and a condensed header stream of hexanol column 106 comprising n-butanol and minor amounts of n-propanol, ¡-butanol and 2-butanol. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a stream of n- Hexanol recovered 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decanol. Optionally, and not shown in Figure 8, the condensed header stream of hexanol column 106 can be fractionated into an isobutanol column to form a hexanol column bottom stream comprising basically pure nbutanol and a column header stream of condensed hexanol comprising n-propanol, ¡-butanol, 2-butanol and n-butanol as major components.

In another aspect of the present disclosure, represented in Figure 9, a current of

Bottom column bottom 58 can be processed in an alternative fractionation aspect to form streams of n-butanol, -butanol, n-hexanol, n-octanol and n-decane! Although Figure 9 is represented by reference to the arrangement of the process of Figure 4, the fractionation aspect of Figure 9 of the present disclosure can be applied to any aspect of the present disclosure for the fractionation of a process stream comprising n-butanol, -butanol, n-hexanol, n-octanol and n-decanol such as the aspects of the present disclosure represented in Figures 5 to 8. In the fractionation aspect Figure 9 of the present disclosure, the current Bottom of separator column 58 is processed in an isobutanol column 110 to form an isobutanol column bottom stream 111 comprising n-butanol and hexanol as major components and an isobutanol column capacitor header stream 112 predominantly comprising -butane!. At least a part of the isobutanol column capacitor header stream 112 can be refluxed into an isobutanol column 110 And at least a portion can be purged from the process. The isobutanol column bottom stream111 is processed in a butanol column 180 to form a butanol column bottom stream 185 predominantly comprising hexanol and a butanol column header stream 186 comprising basically pure n-butanol. At least a portion of the butanol column header stream186 can be refluxed in the butanol column 180.

In another aspect of the present disclosure, depicted in Figure 10, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol, the n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octane! In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol further comprises isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 10) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and / or which can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is sent to the input port of an extractive distillation column 130. The reactor condensate stream 47 and the extractive distillation column header stream 162 are also fed to the extractive distillation column 130. The streams combined, they are contacted with glycerol in the extractive distillation column 130 at a pressure greater than the pressure used in the low pressure extractive distillation column 160 to form a header stream 131 and a bottom stream 135 of extractive distillation column . For example, the pressure in the extractive distillation column 130 may be at least 3 bara higher than the pressure in the low pressure extractive distillation column

160. The header current 131 is passed through a first condenser to form an extractive distillation column condensate stream 132 and a gas stream. Figure 10 depicts the passage of the gas stream through a second condenser to form a condensate stream of the second extractive distillation column 133. The condensate stream 132 may optionally be refluxed in the extractive distillation column 130 and / or combined with a second condensate stream of extractive distillation column 133. Although not shown in Figure 10, one or more streams of gas purge and / or liquid purge may be present in the header system of the extractive distillation column 130 to purge ethyl acetate and acetaldehyde from the process. The condensate stream of second extractive distillation column 133 basically comprises pure dry ethanol and is the ethanol feed for the butanol reactor system 40. In some aspects of the present disclosure, the condensate stream of second extractive distillation column 133 is the ethanol source for the octanol reactor system 230. The reactor product stream 45 generated in the butanol reactor system 40 can be passed through one or more condensers and fed to a separation tank system 46 to form a gas stream 48 comprising hydrogen, water, carbon dioxide, carbon monoxide and acetaldehyde and a condensate stream 47 comprising n-butanol, ethanol, water, acetaldehyde and ethyl acetate. The gas stream 48 is pressurized in a recycle compressor 20 to form a compressed gas stream of second separator column 21. In some aspects of the present disclosure, the compressed gas stream of second separator column 21 may be the gas source for the gas stream 33. In some other aspects of the present disclosure, the compressed gas stream of second separator column 21 it can be processed by pressure change adsorption 30 to form the gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and methane. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the gas stream 33 is the gas source for the butanol reactor system 40. The condensate stream of the second distillation column Extraction 133 is combined with the gas stream 33 comprising hydrogen to form the reactor feed stream 36. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 can be added (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) and / or nhexanol soda to the reactor feed stream. In some additional aspects of the present invention not shown in Figure 10, at least a portion of the hydrogen present in the reaction mixture is provided by compensating for a source of soda hydrogen. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. The reactor feed stream 36 is heated and pressurized to form a reactor feed vapor stream 37 that is sent to the butanol reactor system 40 containing a reactor, or two or more reactors. In the butanol reactor system 40, the ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The bottom stream 135 of the extractive distillation column 130 comprising Glycerol and n-butanol are fed to a low pressure extractive distillation column 160 where the mixture is subjected to a second low pressure distillation. The header stream 161 is passed through a condenser to form a stream 162 that is refluxed in the low pressure extractive distillation column 160 and / or refluxed in the extractive distillation column 130. The distillation column bottom Low pressure extractor 165 is fed to a regeneration column 90 where the organic materials are removed in the header stream 96 And glycerol is recovered in the bottom stream 95. The bottom stream 95 is recycled into the extractive distillation columns 130 and / or 160 and compensation of soda glycerol 146 is added as required. In some aspects of the disclosure, not represented in FIG. 10, the octanol reactor product stream 232 can be fractionated in the extractive distillation column 130 or in the extractive distillation column 160. The regeneration column header stream 96 is passed through a condenser to form a Condensate stream of regeneration column header 97 comprising n-butanol, hexanol and water. At least a part of the condensate stream 97 can be refluxed in the regeneration column 90 and at least a part is fed to an isobutanol column 110. In the isobutanol column 110, a header stream 116 is formed comprising a butanol and water azeotrope that is collected in a separation vessel 117 in the form of a butanol phase 119 and water phase 118. The butanol phase119 is refluxed in the isobutanoll column 10 and the water phase 118 is fed to the water eliminator column 150. The organic compounds are removed from the water phase 118 to form a header current 151 that is passed through a condenser to form a header stream 152. At least a portion of the header stream 152 is refluxed in the water eliminator column 150 and at least a portion is fed to the low pressure extractive distillation column 160. The bottom column stream of Extractive distillation 155 is processed in the wastewater treatment. The isobutanol column bottom stream 115 is fed to a hexanol 100 column for the separation of butanol from n-hexanol. In the hexanol 100 column, a bottom stream 105 is formed comprising n-hexanol, n-octanol and n-decanol and an intermediate cutoff stream 108 comprising basically pure butanol. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a stream of n- Hexanol recovered 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and n-decanol. A header stream 106 is formed which comprises water and low-boiling organic compounds that is passed through a condenser to form a header stream 107. The header stream 107 can be fed to the extractive distillation column of low pressure 160 and / or water elimination column 150.

In another aspect of the present disclosure, depicted in Figure 11, generally, ethanol is condensed in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-butanol and n-hexanol. The n-butanol and n-hexanol are isolated by fractionation and the recovered n-hexanol is condensed with ethanol in the presence of hydrogen by contact with a Guerbet catalyst to form a reactor product stream comprising n-octanol. In particular, the soda ethanol feed 1 is optionally passed through a purification bed 10 for removal of impurities (eg salts and ions) to form a stream of soda ethanol feed 15 comprising ethanol and water . In some aspects of the present disclosure, soda ethanol may comprise isoamyl alcohol. Optionally, the soda ethanol feed 1 or the soda ethanol feed stream 15 can be split into a spindle oil column (not shown in Figure 11) to generate a stream of distilled soda ethanol feed that can be directly feed the butanol reactor system 40 and the octanol reactor system 230 and what can be combined with a stream of recovered alcohol and dehydrated (such as by molecular sieves, a regeneration column and / or extractive distillation). The feed stream 15 is sent to the input port of an extractive distillation column 130. The water eliminator column header current 152 and the hexanol column header stream 107 are also fed to the extractive distillation column 130. Combined streams are contacted with ethylene glycol in the extractive distillation column 130 to form a header stream 131 and a bottom stream 135 of the extractive distillation column. The header current 131 is passed through a first condenser to form an extractive distillation column condensate stream 132 and a gas stream. Figure 11 depicts the passage of the gas stream through a second condenser to form a condensate stream of the second extractive distillation column 133. The condensate stream 132 may optionally be refluxed in the extractive distillation column 130 and / or combined with a second stream of extractive distillation column condensate 133. Although not shown in Figure 11, one or more streams of day purging and / or liquid purging may be present and in the header system of the distillation column extractive 130 to purge ethyl acetate and acetaldehyde from the process. In some aspects of the disclosure, not represented in FIG. 10, the octanol reactor product stream 232 can be fractionated in the extractive distillation column 130. The condensate stream of the second extractive distillation column 133 comprises ethanol and acetaldehyde, and is the ethanol feed for the butanol reactor system 40. In some aspects of the present disclosure, the second extractive distillation column condensate stream 133 is the source of ethanol for the octanol reactor system 230. The reactor product stream 45 generated in the butanol reactor system 40 is it passes through a condenser and is fed to a separation tank 46 to form a gas stream 41 passing through an aldehyde reactor 170 to form a stream 171 that is combined with a condensed stream 42 (if present ). The combined currents 171 and 42 (optionally) pass through one or more condensers and a separation tank system 46 to form a gas stream 48 comprising hydrogen, carbon dioxide, carbon monoxide and ethanol and a condensate stream 47. The gas stream 48 is pressurized in a recycle compressor 20 to form a compressed gas stream of second separator column 21. In some aspects of the present disclosure, the compressed gas stream of second separator column 21 may be the gas source for the gas stream 33. In some other aspects of the present disclosure, the compressed gas stream of second separator column 21 it can be processed by pressure change adsorption 30 to form the gas stream 33 and a purge stream 31 comprising hydrogen, carbon dioxide, carbon monoxide and methane. In some optional aspects of the present disclosure, at least a portion of the recovered n-hexanol 282 (see FIG. 2) or the recovered n-hexanol 282 (see FIG. 3) and / or n-hexanol of soda to reactor feed stream. In some additional aspects of the present invention not shown in Figure 11, at least a portion of the hydrogen present in the reaction mixture is provided by compensating a source of hydrogen from soda. In some other aspects of the present disclosure, the gas stream 33 is the source of hydrogen for the octanol reactor system as described elsewhere herein. In some other aspects of the present disclosure, a combination of the compressed gas stream of the second separator column 21 and the gas stream 33 is the gas source for the butanol reactor system 40. The condensate stream of the second distillation column Extraction 133 is combined with the gas stream 33 comprising hydrogen and the recovered n-hexanol stream 282 to form a reactor feed stream 36. The reactor feed stream 36 is heated and pressurized to form a vapor stream of reactor feed 37 that is sent to the butanol reactor system40 containing a reactor, or two or more reactors. In the butanol reactor system 40, ethanol is contacted with a Guerbet catalyst under elevated pressure and temperature conditions to form a reactor product stream 45. The condensate stream 47 is fed to the extractive distillation column 130 to form a bottom stream 135 comprising ethylene glycol and n-butanol that is fed to a regeneration column 90 where the organic materials are removed in the header stream 96 and the ethylene glycol is recovered in the bottom stream 95. The stream of Bottom 95 is recycled in extractive distillation column 130 and ethylene glycol soda compensation 146 is added as required. The regeneration column header stream 96 is passed through a condenser to form a regeneration column header condensate stream 97 comprising nbutanol, hexanol and water. At least a part of the condensate stream 97 can be refluxed in the regeneration column 90 and at least a portion is fed to an isobutanol column 110. In the isobutanol column 11 O, a header stream 116 is formed comprising a butanol and water azeotrope that is collected in a separation vessel 117 in the form of a butanol phase 119 and a water phase 118. The butanol phase119 is refluxed in the isobutanol column 110 and the water phase 118 is fed to a water eliminating column 150. The organic compounds are removed from the water phase 118 to form a header stream 151 that is passed through a condenser to form a header stream 152. At least a portion of the stream of header 152 is refluxed in the water eliminator column 150 and at least one part is fed to the extractive distillation column 130. The isobutanol column bottom stream 115 is fed to a hexanol column 00 don A bottom stream 105 comprising n-hexanol, n-octanol and n-decanol and an intermediate cutting stream 108 comprising basically pure butanol are formed. The hexaneol column bottom stream 105 is fractionated in a hexanol / octanol / decanol purification system 210 (as depicted, for example and without limitation, in FIGS. 2 and 3) to form a stream of n- Hexanol recovered 282 (FIG. 2) or 282 (FIG. 3). As described further elsewhere herein (as depicted, for example, in FIGS. 2 and 3), the recovered n-hexanol is combined with an ethanol source and a hydrogen source and placed in contact with a heterogeneous catalyst in the octanol 230 reactor system under conditions of elevated temperature and pressure to form n-octanol and ndecanol. A header stream 106 is formed which comprises water and low-boiling organic compounds that is passed through a condenser to form a header stream 107. The header stream 107 can be fed to the extractive distillation column 130 and / or a water elimination column 150 (not shown in Figure 11).

In some optional aspects of the present disclosure not shown in the Figures, the second header condensate stream 54 may be partially or totally refluxed optionally in the ethyl acetate column 60 (Figures 4 to 6 or 9) or in the 50 separating column (Figures 7 and 8). In some of these aspects, such as after commissioning, the second header condensate stream 54 can be partially or totally refluxed in the ethyl acetate column 60 or in the separator column 50 until steady state conditions are achieved . In some other aspects, at least a portion of stream 54 can be refluxed in column 60 or column 50 in order to control the content of ethyl acetate, water and / or acetaldehyde in the feed stream of reactor 37. In some other optional aspects of the present disclosure not shown in the Figures, the second header condensate stream 54 may be partially or totally refluxed optionally in the octanol reactor system 230. The selection of a suitable proportion of reflux for food is within the scope of those skilled in the art.

In some other optional aspects of the present disclosure not shown in Figures 4 to 11, the recycle compressor 20 can be located and positioned so that the reactor feed stream 37 or 38 is compressed and pressurized, and not the stream of second separator column gas 55 or gas stream 21.

The process of the present disclosure, as depicted in Figures 1 to 11, can be implemented on a continuous basis. However, the present disclosure is not limited to continuous processes and can be implemented in batch or semi-batch or batch processes.

Numerous Guerbet catalysts are known in the art. Homogeneous and heterogeneous catalysts are within the scope of the present disclosure. Such catalysts include metal alkoxides, such as sodium ethoxide (NaOEt) (M. Guerbet,

Compt Yield 128, 511 (1899) 1002); copper bronze (C. Weizmann, al., J. Org. Chem 15 (1950) 54); a mixture of potassium hydroxide and boric oxide (M. Sulzbacher, J. Appl.

Chem 5 (1955) 637); a mixture of magnesium oxide, potassium carbonate and chromite of

copper (M. N. Dvornikoff, et al., J. Org. Chem 22 (1957) 540); CaO, MgO and Na, CO, lCuO (M.

N. Dvornikoff, al., J. Org. Chem 22 (1957) 540); Ni-Raney, MnCrO "CuOx and Zn / CrO, (M.

N. Dvornikoff, the a /., J. Org. Chem 22 (1957) 540); an alkali metal alcoholate / ester of

boric acid (US Patent No. 2,861,110 (1958)); the adition of

a nickel catalyst to a metal alkoxide (J. Am Chem Soc 76 (1953) 52); And alkoxide

sodium mixed with 5% by weight of Ah on alumina (P. L. Surk, et aJ., J. Mol. Catal. 33 (1985) 15). Some other Guerbet catalysts include zeolites with cation exchange, such as Metal-L (where Metal = K, Na, Ba, Cs, etc.) and Metal-X (where Metal = K, Na, Sa, Cs, among others) (US Patent No. 5,300,695; and C. Yang, Z. Meng, J. Catal. 142 (1993) 37). Still other Guerbet catalysts include multiple basic oxides containing Cu such as Cu / ZnO / AI20 3, Cu-Co / ZnAI204 and with K or Cs CuzMgyCeOx as promoters (J. G. Nunan, C. E. Bogdan, K. Klier, C. Young, R. G.

Herman, J. Catal. 116 (1989) 195; US Patent No. 5,387,570; And M. J. L. Gines, E_ Church, J. Catal. 176 (1998) 155). Further Guerbet catalysts include Au / AI20 3, Ah / AI20 3, PdlAI20 3, PUAI20 3, Au / AI20 3, Ni / AI20 3, and Ag / AI20 3. Yet another group of Guerbet catalysts includes transition metals ( for example, Mn, Cr, Zn, Al, etc.) supported on MgO (W. Ueda, T. Kuwabara, T. Oshida, Y. Morikawa, J. Chem Soc, Chem Commun. (1990) 1558, and Catal. Let! 12 (1992) 971). Another group of Guerbet catalysts is based on calcium phosphate of the hydroxyapatite type (United States Patent Document No. 6,323,383, United States Patent Document No. 2007/0255079, and Patent Document WO 2011/031928). Another group of Guerbet catalysts includes a Group VIII metal with a phosphine ligand (US Pat. No. 2013/0116481).

Recently, hydrotalcite-based catalytic materials have been reported (Patent document WO 2009/026510 A1, United States Patent Document No. 2010/0160693 and United States Patent Document No. 2010/0160692). As the technique is known, hydrotalcite has the general formula Mg6AI2 (C03) (OH) 16 "4 (H20). Studies conducted with these mixed oxides of Mg and Al show although the catalytic activity of these materials depends on nature, the density and strength of the basic superlicie sites, and, in turn, the molar composition of Mg / AI (J. l. Di Cosimo, et al.,

J. Catal. 178 (1998) 499; And J. 1. Di Cosimo, the a /. , J. Catal. 190 (2000) 261). The prior art has also established that mixed oxides derived from Cu / Mg / AI based hydrotalcites show improved catalytic activity (C. Carlini, al., J. Mol. Catal. A: Chem 232 (2005) 13) or the copper chromite-type catalyst systems + mixed oxides of Mg and Al (derivatives of hydrotalcite precursors). In addition, hydrotatite type materials have been developed (Patent document WO 2009/026510) as well as materials derived from hydrotalcites modified by inclusion of metal carbonates (Patent document WO 2009/026523) and ethylenediamine tetraacetates (Patent document WO 2009/026483) . It has been found that improved hydrotalcite-derived mixed oxide catalysts which further comprise Ga in combination with Pd and / or Pt produce a high yield of n-butanol due to a synergistic effect of Ga-Metal on the metal oxide. This improvement is even more pronounced than in the case of catalysts containing Pd and Ga.

In some aspects of the present disclosure, the catalyst is a metal oxide catalyst (called "Catalyst A") comprising: (i) at least one divalent metal, M1, selected from Mg, Zn, Cu, Ca, Mn, Fe , Ni and Ca, (ii) at least one trivalent metal, M2, selected from Al, La, Fe, Cr, Mn, Ca, Ni and Ga, (iii) at least one noble metal selected from Pd, Pt, Ru, Rh and Re, and, optionally, (iv) V, with the proviso that the catalyst comprises V, Ga or a combination thereof. In some aspects, the catalyst comprises V and / or Ga in combination with Pd.

In some other aspects of Catalyst A, the Guerbet catalyst is a metal oxide comprising (i) at least one divalent metal selected from the list comprising Mg, Zn, Cu, Ca, Mn, Fe, Ni and Ca, (ii ) Trivalent Ga, and (iii) a noble metal selected from the list comprising Pd, Pt, Ru, Ah and Re, preferably Pd. In some aspects, the Guerbet catalyst further comprises an additional trivalent metal selected from the list comprising Al, La, Fe, Gr, Mn, Ca and Ni.

In some aspects of Catalyst A, the catalyst is obtained by the total or partial decomposition of a hydrotalcite of formula [Ml "." M2, (OH) cl [Am. , .m, 'nH, OI which is impregnated with a metal oxide comprising at least one noble metal selected from Pd, Pt, Ru, Ah and Re and, optionally, V, in which the catalyst comprises V, Ga, or A combination of them. In some other aspects, V Y at least one noble metal selected from Pd, Pt, Ru, Rh and Re is added to the hydrotalcite after total or partial decomposition of it. In this aspect: M1 and M2 are as described above; A is at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, p-toluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate ( 111) and hexacyanoferrate (11); x is a value between O and 1 or between 0.1 and 0.8; m is an integer between 1 and 4; And n is greater than O, between O and 100 or between Oy 20.

In some aspects of Catalyst A, the hydrotalcite described herein is obtained by coprecipitation of the compounds of M1 and M2.

Preferably, coprecipitation is carried out in the aqueous phase. The coprecipitation of the compounds can be preferably carried out by following the addition of a solution of at least one anion selected from hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, ptoluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate

(111) and hexacyanoferrate (11) to a solution of at least one compound of M1 and at least one compound of M2. This anion can be introduced between the sheets of the resulting hydrotalcite. In order to obtain anion solutions, sodium and / or potassium salts thereof can be used. Preferably, the at least one anion selects between carbonate, bicarbonate and hydroxide. The best results are obtained when coprecipitation is carried out at a pH greater than 7, preferably between 10 and 14. In addition, in order to regulate the pH, sodium and / or potassium hydroxide are preferably used.

In some aspects of Catalyst A, before the precipitation of said compounds, there is a solution of at least one compound of M1 and at least one compound of M2. Be

It is understood that soluble compounds of M1 and M2 means any salt which, when contacted with a solvent, preferably dissociates a polar solvent, more preferably water. Examples of soluble compounds of M1 and M2 can be nitrates, halides, sulfates, carboxylates and, in general, oxoacids comprising M1 or M2; preferably the soluble compounds of M1 and M2 are nitrates.

In some aspects of Catalyst A of the present disclosure, M1 comprises Mg or basically consists of Mg. In some other aspects, M2 is Al, Ga, or a combination thereof. In other aspects, the catalyst comprises V. In some other aspects, M2 comprises Al, Ga or any combination thereof. In other aspects, M2 comprises Al. In other aspects, M2 comprises Al and Ga. In other aspects, M1 is Mg, M2 is Al and Ga and the catalyst comprises V. In other aspects, M1 is Mg, M2 is Al and the calalizer comprises V. In other aspects, Mt is Mg, M2 comprises Ga and the catalyst does not comprise V.

In still other aspects of Catalyst A, A is at least one anion selected from the list comprising CO, '·, HCOi, Oi, OH, cr, NO,' ", cr, F, Br, r, CIO" CH, COO ·, C, H-COO ·, and SO / '; among the list comprising e032-, HC03-, O2- and OH-; or among the list comprising CO, '·, HCOi, Oi and OH ·.

Catalyst A gels resulting from the coprecipitation described above are filtered, washed with water and dried properly. The presence of a hydrotalcite-like structure can be corroborated by means of X-ray diffraction analysis (XAD), while that the composition (quantity and type of constituents) of the hydrotalcite or the corresponding mixed oxide obtained by thermal decomposition of the aforementioned hydrotalcite can be determined by means of mass spectrometry with inductive coupling plasma (Iep-MS) and chemical analysis, among others_

In another aspect of Catalyst A of the present disclosure, the thermal decomposition of the hydrotalcite is carried out by means of calcination in an atmosphere of oxygen, nitrogen or any mixture thereof at a temperature that varies between 250 "e and 650" e, preferably between 350 "e and 550" e_ The thermal decomposition of the hydrotalcite is preferably carried out over a range of 0.5 to 48 hours, preferably between 1 and 24 hours. This process can be carried out by heating the hydrotalcite in a gaseous atmosphere and can be carried out in a static furnace or a calcination reactor with a controlled gas flow, the latter being preferred. The gas can be a

oxidizing gas or a non-oxidizing gas. Examples of oxidizing gases may include air and oxygen. Examples of non-oxidizing gases may be inert gases, such as nitrogen, argon, helium and reducing gases, such as, for example, carbon dioxide, hydrogen and ammonia. Preferably, the calcination is carried out in the presence of oxygen, nitrogen or mixtures thereof, and even more preferably, in the presence of oxygen and nitrogen.

In another aspect of Catalyst A of the present invention, V and the noble metal are added to the metal oxide by wet impregnation, impregnation of incipient volume or deposition-precipitation, preferably V and the noble metal are added to the metal oxide by wet impregnation , impregnation of incipient volume or deposition precipitation, more preferably by impregnation of incipient volume. The incipient volume impregnation method, also called the incipient moisture impregnation method, is based on the use of a minimum amount of liquid for the impregnation, only that which is necessary to reach the maximum saturation of the corresponding solid.

In another aspect of Catalyst A of the present invention, the noble metal comprises Pd, or the noble metal is Pd. It has been found that the best yields in n-octanol are obtained when calcined hydrotalcites containing Ga and / or V are impregnated with Pd. It has also been discovered that, for a given concentration of palladium, catalysts derived from hydrotalcite comprising gallium and / or vanadium in their structure provide higher yields of n-octanol in a nitrogen atmosphere than their analogs without gallium / vanadium.

In another aspect of Catalyst A of the process described above, the concentration of the noble metal in the catalyst is between 0.001% by weight and 10% by weight or between 0.01% by weight and 5% by weight with respect to the total catalyst, and the concentration of V is between 0.001% by weight and 10% by weight or between 0.01% by weight and 5% by weight with respect to the total catalyst.

In another aspect of Catalyst A of the present disclosure, a calcination step is performed following the addition of the noble metal. The calcination is preferably carried out in a static furnace or a reactor with a controlled gas flow in the presence of an oxidizing gas (for example, air and / or oxygen), an inert gas (for example, nitrogen, argon and / or helium) or a reducing gas (for example, carbon dioxide, hydrogen and / or ammonia), or

a combination thereof, at a temperature between 250 pe and 650 2C or between 350 2C and 550!: le, and for a period of time between 0.5 and 48 hours, between 1 and 24 hours or between 1 and 6 hours. In some of these aspects, calcination is performed in the presence of oxygen, nitrogen, or mixtures thereof, or in the presence of oxygen and nitrogen.

In some aspects of Catalyst A of the present disclosure, a reduction step is carried out after calcination for the reduction of the active sites of the noble metal in which the catalyst is exposed to an atmosphere of H2 at a temperature between 200 2C and 500 pe or between 250 2C and 450 pe and for a period of time between 0.5 and 48 hours, between 1 and 24 hours or between 1 and 6 hours.

In some additional aspects of the present disclosure, the catalyst may suitably be a partially or totally thermally decomposed hydrotalcite as described in US Patent No. 8,071,822 (called "Catalyst B") having the empirical formula:

wherein M2 + is divalent Mg, or a combination of divalent Mg and at least one divalent member selected from the group consisting of Zn, Ni, Pd, Pt, Co, Fe, and Cu; M3 + is trivalent Al, or a combination of trivalent Al and at least one trivalent member selected from the group consisting of Fe and Cr; x is 0.66 to 0.1; M 'is (i) one or more divalent members selected from the group consisting of Pd, Pt, Rh, Ca, and Cu; or (ii) one or more trivalent members selected from the group consisting of Fe, Cr, Au, Ir, and Ru;

or (iii) a mixture of one or more of said divalent members with one or more of said trivalent members; A 'is the anion of ethylenediaminetetraacetic acid; n 'is the absolute value of the sum of the oxidation state of M' (i.e. +2 if M 'is one or more divalent members or +3 if M' is one or more trivalent members) and of the oxidation state of the anion of ethylenediaminetetraacetic acid (-4) (for example, for M'A 'in which M' is Pd2 + with an oxidation state of +2, n 'is +2); with the proviso that if M 'is said mixture, then n' is calculated according to the following equation:

n '= absolute value of [Xo (2) + Xo (-4) + X, (3) + X, {- 4) I,

wherein XD = sum of the number of moles of all divalent members divided by (sum of the number of moles of all divalent members + sum of the number of moles of all trivalent members), and Xr = sum of the number of moles of all trivalent members divided by (sum of the number of moles of all divalent members + sum of the number of moles of all trivalent members); An-es col with n = 2 or OH with n = 1; a is from 0.001 to; e y is from O to 4.

In one aspect of Catalyst B, M2 + is divalent Mg; M3 + is Al trivalent; M 'is Ca or Cu; to 2

it is from 0.01 to 0.44; and An. is C03 -u OH.

The catalysts described in US Pat. No. 822 are derived from a hydrotalcite of the formula defined above by a process comprising heating the hydrotalcite for a time and at a temperature sufficient to cause a decrease in the intensities of the peaks of the X-ray powder diffraction pattern of the hydrotalcite between angles 28 of t O degrees and 70 degrees using CuKa radiation.

In some other aspects of Catalyst B of the present invention, the metal oxide is obtained from the total or partial thermal decomposition of a hydrotalcite, the catalyst having the formula [M1 1- (xy) M2yM3x (OHh] [Am. ( x'yl / m.nH20) With respect to this aspect, it is understood that hydrotalcite means the structural family of laminar mixed hydroxides with the formula described above.M1 is at least one divalent metal (i.e., it has a 2+ charge ) selected from the list comprising Mg, Zn, Cu, Co, Mn, Fe, Ni and Ca; M2 is trivalent Ga; M3 is as described above; A is at least one anion selected from the list comprising hydroxide, chloride, fluoride, bromide, iodide, nitrate, perchlorate, chlorate, bicarbonate, acetate, benzoate, methanesulfonate, ptoluenesulfonate, phenoxide, alkoxide, carbonate, sulfate, terephthalate, phosphate, hexacyanoferrate

(111) and hexacyanoferrate (11); x is a value between O and 0.5; x is a value of 0.1 to 0.5 or 0.1 to 0.4; and is a value of 0.00001 to 0.49, 0.00005 to 0.45 or 0.0001 to 0.4; m is an integer from 1 to 4; and n is greater than 0, such as from O to 100 or from ° to 20; and "n" indicates the number of crystallization water molecules and is dependent on the composition of the hydrotalcite cations.

In some aspects of Catalyst B of the present disclosure, hydrotalcite is obtained by coprecipitation of at least one compound of M1 and at least one compound of a trivalent metal selected from the list comprising M2 and M3. In some other aspects, hydrotalcite is obtained by coprecipitation of compounds of M1, M2 and M3.

In any of the various aspects of the present disclosure, the butanol reactor system and the octanol reactor system can use the same catalyst, or a different catalyst. In aspects of the present invention in which the butanol reactor system and / or the octanol reactor system comprise more than one reactor, each reactor can use the same catalyst or a different catalyst.

As depicted in Figures 4 to 11, the reaction for butanol takes place in the butanol reactor system 40 and the reaction for octanol takes place in the octanol reactor system 230. The butanol reactor system 40 and the reactor system Octanol 230 may each comprise an individual reactor or more than one reactor, such as 2, 3 or 4 reactors. Multiple reactor designs can be suitably configured in a sequential or parallel reactor arrangement, or a combination thereof. In some aspects of the present disclosure, the reaction for butanol (butanol reactor system 40) can be carried out in at least two sequential gas phase reactors, or at least three sequential gas phase reactors. In some other aspects of the present disclosure, the reaction for butanol can be carried out in two or more parallel reactors. In other aspects, the reaction for butanol can be carried out in two or more parallel reactors and one or more reactors in sequential arrangement therewith. In some aspects of the present disclosure, the reaction for hexanol (octanol reactor system 230) can be carried out in at least one gas phase reactor. In other aspects of the disclosure, the reaction for hexanol can be carried out in at least two gas phase reactors arranged in parallel or sequentially.

The selection of suitable reactors is within the scope of those skilled in the art. Suitable reactor designs for the practice of the present disclosure include, for example and without limitation, discontinuous reactors, continuous stirred tank reactors, continuous fixed bed reactors, continuous fluid bed reactors, and semi-continuous reactors. Gas phase reactors having a fixed bed of catalyst are generally preferred. The reactors may suitably have a fluid bed or turbulent flow design. The reaction conditions can be adiabatic or isothermal, or temperature gradient between the reactors can be used in multi-reactor systems. In some aspects of the present disclosure, the reactor system comprises one or more fluid bed reactors in which there is a fixed catalyst bed. In some other aspects of the present disclosure, the reactor system may comprise

at least one fluid bed reactor and at least one truculent flow reactor. The Guerbet reaction is exothermic and in some aspects of the present disclosure the reactors may have intermediate cooling to allow temperature control. Oil can be used as the reactor coolant, and the heat of the reactor coolant heated in a heat exchanger can be recovered and used elsewhere in the process. In some aspects of multiple reactors of the present disclosure, the recovered heat can be used to heat the feed stream to the first reactor.

In some aspects of the present disclosure, the reaction conditions and concentrations of some of the various components in the butanol reactor system 40 and the octanol reactor system 230, and combinations of components of the reaction mixture can be controlled with the in order to maximize the conversion and selectivity in alcohol for the reaction products of Guerbet alcohols n-butanol, n-octanol and n-decane !.

In some aspects of the present disclosure, the reaction mixture 37 for the butanol reactor system 40 comprises ethanol, hydrogen and water and the mole ratio of hydrogen to ethanol can be controlled from 0.01: 1 to 10: 1, from 0.1: 1 to 5: 1, from 0.1: 1 to 3: 1, from 0.1: 1 to 1.5: 1, from 0.1: 1 to 0.8: 1, from 0 , 1: 1 to 0.6: 10 from 0.1: 1 to 0.4: 1, such as 0.1: 1, 0.2: 1, 0.4: 1, 0.6: 1, 0 , 8: 1, 1: 1, 1.5: 1, 2: 1 03: 1.

In some aspects of the present disclosure the reaction mixture 37 (feed stream) further comprises acetaldehyde and the mole ratio of acetaldehyde with respect to the starting alcohol can be controlled from 0.0001: 1 to 0.1: 1. In some other aspects of the present disclosure, the mole ratio of acetaldehyde to alcohol in the reactor feed stream is controlled from 0.0001: 1 to 0.005: 1 or 0.0001: 1 to 0.003: 1. In other aspects of the present disclosure, the mole ratio of acetaldehyde to alcohol in the reactor feed stream is controlled from 0.005: 1 to 0.05: 1, from 0.01: 1 to 0.05: 1, from 0.01: 1 to 0.04: 1, or from 0.02: 1 to 0.04: 1, such as 0.001: 1, 0.002: 1, 0.003: 1, 0.004: 1, 0.005: 1 , 0.01: 1, 0.02: 1, 0.03: 1, 0.04: 1 00.05: 1.

In some aspects of the present disclosure, the mole ratio of water to the starting alcohol in the reaction mixture 37 for the butanol reactor system 40 can be controlled in less than 0.005: 1, less than 0.05: 1 , less than 0.025: 1, 0.001: 1 to 0.05: 1, 0.005: 1 to 0.05: 1, or 0.01: 1 to 0.03: 1, such as 0.001: 1, 0.005 : 1, 0.01: 1, 0.02: 1 00.03: 1.

In some aspects of the present disclosure, reaction mixture 37 (feed stream) further comprises carbon monoxide and the mole ratio of carbon monoxide relative to the starting alcohol can be controlled in less than 0.02: 1, less than 0.01: 1, less than 0.005: 1, or less than 0.003: 1, 0.0005: 1 to 0.005: 1, 0.001: 1 to 0.005: 1, or 0.002: 1 to 0.004: 1 , such as 0.005: 1, 0.003: 1.0.002: 1, or O, OOt: 1.

In other aspects of the present disclosure, the reaction mixture 37 (feed stream) further comprises ethyl acetate and the mole ratio of ethyl acetate with respect to the starting alcohol can be controlled in less than 0.005: 1, less than 0.002: 1, or less than 0.001: t, of O, OOOt: ta 0.003: t, of 0.0005: ta 0.0015: 1, or 0.0005: ta 0.001: 1, such as 0, 0005: 1,0,001: 1,0,003: 1 00,005: 1.

In some particular aspects of the present disclosure, the reaction mixture 37 for the butanol reactor system 40 comprises from 70 mol% to 90 mol%, 75 mol% to 85 mol% or a 78 mol% to 82 mol% ethanol; from 5 mol% to 25 mol%, from 10 mol% to 20 mol% or from approximately 12 mol% to 18 mol% hydrogen; and from 0.5 mol% to 5 mol%, from 1 mol% to 3 mol% or from 2 mol% to 2.5 mol% water.

In some aspects of the present disclosure, the reaction mixture for the octanol 230 reactor system comprises ethanol, n-hexanol, hydrogen and water and the mole ratio of hydrogen to the starting alcohol (predominantly ethanol and nhexanol) can be controlled. from 0.01: 1 to 10: 1, from 0.1: 1 to 5: 1, from 0.1: 1 to 3: 1, from 0.1: 1 to 1.5: 1, from 0.1 : ta 1: 1, from 0.1: 1 to 0.8: 1, from 0.1: 1 to 0.6: 1, from O, t: ta 0.5: t ode 0.1: ta O , 4: t, such as 0.1: 1, 0.3: 1.0.5: 1.0.7: 1, 1: 1, 1.5: 1, 2: 1 03: 1.

In some aspects of the present disclosure, the mole ratio of water to the starting alcohol in the reaction mixture for the octanol 230 reactor system can be controlled in less than 0.005: 1, less than 0.05: 1, less than 0.025: 1, 0.00t: 1 to 0.05: 1, 0.005: 1 to 0.05: 1, or 0.01: ta 0.03: t, such as O, OOt: t , 0.005: 1, 0.01: 1, 0.02: 1 00.03: 1.

In some aspects of the present disclosure, the octanol reaction mixture for the octanol reactor system 230 further comprises carbon monoxide and the mole ratio of carbon monoxide with respect to the starting alcohol can be controlled in

less than 0.05: 1, less than 0.01: 1, or less than 0.005: 1, 0.005: 1 to 0.05: 1, 0.001: 1 to 0.01: 1, or 0.005: 1 to 0.01: 1.

In some aspects of the present disclosure, the mole ratio of ethanol to n-hexanol in the reaction mixture for the octanol 230 reactor system can be controlled to provide an excess of moles of ethanol; a ratio of 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 2: 1, 2.5: 1, 3: 1, 4: 1 or 5: 1, and intervals thereof, such as 1.1: 1 a

5: 1, from 1.1: 1 to 2: 1, or from 1.1: 1 to 1.5: 1.

In some optional aspects of the present disclosure, the octanol reaction mixture for the octanol 230 reactor system further comprises at least one aldehyde and the mole ratio of aldehyde with respect to the starting alcohol can be controlled from 0.001: 1 to 0 ,eleven. In some aspects of the disclosure, the aldehyde is supplied to the octanol reactor system by the second header condensate stream 54 comprising recovered acetaldehyde. Examples of aldehydes within the scope of the present disclosure include ethanal (acetaldehyde), ethylhexanal, propionaldehyde, butanal (butyraldehyde), hexanal (hexanaldehyde) or octane! In some other aspects of the disclosure, the aldehyde is hexanal which is recovered from the condensed header current 116 of the isobutanol column 110 (comprising 30 to 50 mol% hexanal) and / or from the header current 106 of the hexanol 100 column (comprising 5 to 15 mol% hexanal). In some other aspects of the present disclosure, the mole ratio of aldehyde to alcohol in the reactor feed stream is controlled from 0.001: 1 to 0.005: 1 or 0.001: 1 to 0.003: 1. In other aspects of the present disclosure, the mole ratio of aldehyde to alcohol in the reactor feed stream is controlled from 0.005: 1 to 0.05: 1, from 0.01: 1 to 0.05: 1, from 0.01: 1 to 0.04: 1, or from 0.02: 1 to 0.04: 1, such as 0.001: 1.0.002: 1.0.003: 1.0.004: 1.0.005: 1 , 0.01: 1, 0.02: 1.0.03: 1.0.04: 1 00.05: 1.

In some particular aspects of the present disclosure, the reaction mixture for the octanol 230 reactor system comprises from 35 mol% to 50 mol%, 40 mol% to 45 mol% or 41 mol% to 44 mol% ethanol; from 25 mol% to 40 mol%, from 27 mol% to 37 mol% or from 29 mol% to 35 mol% of n-hexanol; from 15 mol% to 30 mol%, 17 mol% to 27 mol% or 18 mol% to 26 mol% hydrogen; and from 0.5 mol% to 3 mol%, from 0.8 mol% to 2 mol% or from 1 mol% to 1.5 mol% water.

The feed rate of the reaction mixture for each of the butanol reactor system 40 and the octanol reactor system 232 is controlled, by a flow control, preferably to provide a liquid hourly space velocity (LHSV) of 0.5 to

5 5, from 0.5 to 2, from 0.75 to 1.5 or from 0.9 to 1.1, such as 0.75, 0.9, 1, t, 1, 1.25, t, 5, 2 or 3.

Various combinations of the process variables described above can be selected to achieve high yield and selectivity of n-butanol, rr octanol and n-decane! For example, the following Table A lists some possible combinations of variables of the butanol reactor system 40 (indicated by "X") that can be controlled to achieve the objectives of the present disclosure, where "AL" refers to aldehyde, " co "refers to carbon monoxide," EA "refers to ethyl acetate," Ale "refers to the total alcohol content in the reactor feed stream and" EtOH: HexOH "refers to the mole ratio of ethanol with respect to n-hexanol in the

15 reactor feed current.

Table A

Combination

H,: EtOH AL: EtOH H, O: EtOH CO: EtOH EA: EtOH LHSV

one

X

2

X

3

X X

4

X X

5

X X

6

X X X

7

X X

8

X X

9

X X X

10

X X

eleven

X X

12

X X X

13

X X

Combination 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

H,: EtOH AL: EtOH X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X H, ü: EtOH X X X X X X X X X X X X X X X X X X CO: EtOH X X X X X X X X X X X X X X X EA: EtOH X X X X X X X X X X X X X X X LHSV X X X X X X X X X X X X X X

Table B lists some possible combinations of 230 octanol reactor system variables (indicated by "X") that can be controlled to achieve the objectives of the

present disclosure, where "AL" refers to acetaldehyde, "CO" refers to carbon monoxide, "EA" refers to ethyl acetate, "Ale" refers to the total alcohol content in the reactor feed stream and "EtOH: HexOH" refers to the mole ratio of ethanol to n-hexanol in the reactor feed stream.

Table B

Comb EtOH: HexOH 1 X 2 X 3 X 4 X 5 X 6 X 7 X 8 9

H,: Alc X X X X X X X H, O: Alc X X CO: Alc X X AL: Alc X X X X X X

In some aspects of the present disclosure, a reactor system design can be used

10 of butanol 40 and / or an octanol 230 reactor system design that uses multiple feed points along the length of the reactor to maintain a predominantly constant aldehyde concentration in the reaction mixture in the reagent feed section of the reactor in order to optimize the performance of n-butanol, noctanol and n-decane!

The n-butanol and n-octanol are produced from ethanol and hexanol, respectively, by a two-stage Guerbet reaction in which, in the first reaction, ethanol or hexanol is dehydrogenated to form the corresponding aldehyde and hydrogen . In the second reaction, ethanol and acetaldehyde or ethanol and hexanal are condensed and hydrogenated

20 to form n-butanol or n-octanol. The n-decanol is generated by a similar mechanism. The dehydrogenation reaction is slightly endothermic, the condensation / hydrogenation reaction is slightly exothermic, and the global Guerbet reaction is slightly exothermic. It has been discovered that, compared to the formation of

aldehyde, the aldehyde rapidly condenses with ethanol to form butanol or octane! In the case of acetaldehyde, based on a simulation that is reflected in the following Table e, it is believed that basically all acetaldehyde present in a reaction mixture is condensed with ethanol in the first third of the reactor length. The simulation was carried out using a kinetic model developed to represent the behavior of the catalyst in different operating conditions that involve combining acetaldehyde with the ethanol and hydrogen reactor stream. The kinetic model was developed using very wide operating conditions of temperature, pressure, hydrogen ratio with respect to ethanol and LHSV. Experimental results for the reaction of a

10 feed stream comprising ethanol, hydrogen and acetaldehyde corresponded to, and validated, the results predicted by the kinetic model. Thus, it is believed that the dehydration of ethanol to acetaldehyde is the speed limiting stage in the Guerbet condensation reaction. It is further believed that a kinetic model similar to the reaction of hexanal with ethanol to form n-octanol is applicable.

15 Table e

Reactor length

1st simulation (molar fraction of acetaldehyde) 2nd simulation (molar fraction of acetaldehyde)

Ocm

0.018 0.037

1.1 cm

0.006 0.015

2.2 cm

0.004 0.006

3.3 cm

0.003 0.004

4.4 cm

0.003 0.003

5.5 cm

0.003 0.003

Based on the experimental evidence to date, it has been discovered that the

The reaction of a feed stream comprising up to 0.05 moles of acetaldehyde per mole of ethanol increases the yield and selectivity of n-butane! It is further believed that a feed stream comprising up to 0.05 moles of hexanal per mole of ethanol can increase the yield and selectivity of n-octanol. Without the desire to be bound by any particular theory, it is believed that the introduction of an aldehyde into the

25 reaction mixture exceeds the limiting stage of the dehydrogenation rate

thereby allowing higher concentrations of aldehyde in the reaction mixture and favoring selectivity in n-butanol and n-octane! It has also been found that the reaction of a feed stream comprising an excess of 0.05 moles of aldehyde per mole of ethanol (for example, 5 mole percent acetaldehyde or hexanal) reduces selectivity in n-butanol and n -octanol and results in an increase in the amounts of higher alcohols compared to feed streams comprising less than 0.05 moles of aldehyde with respect to ethanol. It is believed, without the desire to be bound by any particular theory, that the reduction in selectivity results from at least two factors, and the combination thereof. First, at higher concentrations of aldehyde, the rate of condensation of aldehyde and ethanol may be insufficient to consume basically all of the aldehyde, thereby resulting in a concentration of aldehyde in the reaction mixture too high to allow higher condensation rates. with butanol OR higher alcohols according to the following reaction schemes by way of example:

Butanol + Acetaldehyde + H2 -7 Hexanol + H20

Hexanol + Acetaldehyde + H2 -7 Octanol + H20

Octanol + Acetaldehyde + H2 -7 Decanol + H20

Ethanol + Hexanal + H2 -7 Octanol + H20

Second, it has been found that aldehyde concentrations in the feed stream with an excess of 5 or 10 mol% cause temperature peaks, in which higher reaction temperatures increase the formation of secondary products.

In accordance with the present disclosure, it has been found that a feed stream of the butanol or octanol reactor comprising aldehyde at multiple points along the length of the reactor can be fed in order to maintain a generally constant concentration of aldehyde in at least a part of the reactor and thereby improve the selectivity and yield of n-butanol and n-hexanol. For example, in addition to the inlet port, the reactor feed stream can be supplied at one or more injection points along the length of a part of the reactor, called the reactor feed section. In some aspects of the disclosure, the reactor feed section comprises at least a first reaction mixture addition site and a last reaction mixture addition site located along a length of the reactor, the feed section being from the reactor the reactor section from the first reaction mixture addition site to the last reaction mixture addition site. In some other aspects, the reactor feed section comprises at least one intermediate reaction mixture addition site located between the first reaction mixture addition site and the last reaction mixture addition site. In other aspects, the first reaction mixture addition site is located at the reactor inlet port. In any of the various aspects, two or more injection points can be located at intervals in the first two thirds, the first half, or the first third of the reactor length. In some aspects of the present disclosure, the feed rate of the aldehyde / ethanol stream to the reactor may be based on the aldehyde concentration and / or the measured reaction temperature. The determination and selection of the location and profile of the injection points of the reactor feed stream, the rate of addition of the associated reactor feed stream, and the control strategies designed to achieve an aldehyde concentration in The reactor feed section is within the scope of the person skilled in the art.

Aldehydes can be isolated from any of the various process streams. For example, acetaldehyde can be isolated from the separating column header stream 51, from the ethyl header column header purge stream 64, from the second separator column gas stream 55 or can being present in the header current of the second separating column 54. The condensed header current 116 of the isobutanol column 110 comprises 30 to 50 mol% hexanal and the header current 106 of the hexanol column 100 comprises 5 to 15 mol% hexanal that can be isolated and recycled in the octane reactor! Insulation techniques are known in the art and include distillation.

In any of the various aspects of the multiple feed point to the reactor of the present disclosure, the mole ratio of aldehyde with respect to ethanol in the reactor feed section of the butanol reactor system 40 or the mole ratio of aldehyde with respect to The total ethanol and n-hexanol in the reactor feed section of the octanol 230 reactor system can be controlled by an average of

0.005: 1, 0.01: 1, 0.015: 1, 0.02: 1, 0.025: 1, 0.03: 1, 0.035: 1, 0.04: 1, 0.045: 1 or 0.05: 1, and the

intelValos thereof, such as 0.005: 1 to 0.05: 1, 0.01: 1 to 0.05: 1, 0.01: 1 a

0.04: 1 or 0.02: 1 to 0.04: 1. In some aspects of this disclosure, you can

use a second reactor feed current comprising a proportion in

moles of aldehyde with respect to ethanol or ethanol and n-hexanol in an excess of 0.05: 1, such as between 0.05: 1 and 0.2: 1 at one or more injection points in combination with a first stream of reactor feed comprising a molar fraction of aldehyde with respect to ethanol of less than 0.05: 1. In any of the various aspects of the disclosure, the mole ratio of aldehyde with respect to ethanol or ethanol and n-hexanol in any region of the reactor feed section does not differ by more than 50%, 40%, 30 %, 20% or 10% of the average mole ratio of aldehyde with respect to ethanol or ethanol and n-hexanol in the reactor feed section. In general, the temperature profile in the reactor feed section is such that the temperature in any region of the reactor feed section does not differ by more than 15 Qe, 10 Qe or 5 Qe from the average temperature along the length of the reactor feed section.

In any of the various aspects of the present disclosure, in addition to the process variables described above and combinations thereof, the reaction pressure in the one or more reactors in each of the butanol reactor system 40 and the reactor system of octanol 230 is from 10 bara to 200 bara, from 20 bara to 200 bara, from 20 bara to 150 bara, from 20 bara to 100 bara, from 20 bara to 80 bara, or from 25 bara to 60 bara, such as 25 bara , 30 bara, 35 bara, 40 bara, 45 bara, 50 bara, 55 bara, 60 bara, 65 bara, 70 bara or 75 bara, and their intervals. In addition, the reaction temperature in the one or more reactors is 50 'C to 450' C, 100 'C to 450' C, 150 'C to 450' C, 150 'C to 400' C, of 150 'C to 350' C, 175 'C to 400' C, 175 'C to 300' C, 200 'C to 350' C, or 200 'C to 300' C, such as 200 'C , 210 'C, 220' C, 230 'C, 240' C, 250 'C, 260' C, 270 'C, 280' C, 290 'C, 300' C, 310 'C, 320' C, 330 'C, 340' C, 350 'C, 360' C, 370 'C, 380' C, 390 pe or 400 pe, and their intervals. In some aspects of the present disclosure, the reaction temperature of butanol is 150 pe to 350 pe, 175 pe to 300 pe or 200 'C to 300' C and the octanol reaction temperature is 200 'C to 400 'C or 250' C at

350 pe. In aspects of the present disclosure in which two or more reactors are used in series, temperature and pressure gradients from the first to the last reactor can be used. For example, the temperature for each reactor in series can be 5 pe, 10 pe, 15 pe, 20 pe, 25 oc, 30 oc or 35 oc higher than the temperature in the preceding reactor and the pressure can be 5 bara, 10 bara , 15 bara or 20 bara greater than the pressure in the preceding reactor. In some aspects of the present disclosure, since the catalyst is deactivated towards the end of a production process, the conversion can be maintained by increasing

gradually the inlet temperature. For example, the inlet temperature can be increased 10 'C, 20' C, 30 'C, 40' C, 50 'C, 60' C, 70 'C, 80' C, 90 'C or 100' C from the beginning of a production process until the end of the production process. In general, the reaction temperature can be controlled so that the outlet temperature of the reactor system increases by the same amount. In some aspects of the present disclosure, the outlet temperature of the reactor system reaches 250 pe, 260 2e, 270 pe, 280 pe, 290 2e, 300 2e, 320 2e or 340 pe at the end of the production process. In preferred aspects of the disclosure, the current feeds of the butanol and octanol reactor are each a gas or a vapor and the reaction is a phase reaction.

soda.

In any of the various aspects of the butanol reaction system of the present disclosure, an ethanol conversion of 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50 is achieved %, 55% or 60%, such as 15% to 40%, 20% to 40%, 25% to 40% or 25% to 35%. An ethanol-based n-butanol yield of 10%, 15%, 20%, 25%, 30% or 35%, such as 10% to 35%, 10% to 30%, is achieved , from 15% to 30%, from 20% to 30%. A n-butanol selectivity of 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% is achieved, such as 65% to 95%, from 65% to 90%, from 70% to 90%, from 75% to 85%, or from 80% to 85%. In some aspects of the present disclosure, the yield of ethanol-based n-butanol is 15% to 25% and the selectivity in n-butanol is 70% to 85%, the yield of n-butanol based in ethanol it is 10% to 15% and in the selectivity in n-butanol it is 85% to 95%, or the yield of n-butanol based on ethanol is 30% to 40% and the Selectivity in n-butanol is 65% to 70%.

In any of the various aspects of the octanol reaction system of the present disclosure, an ethanol conversion of 20%, 30%, 40%, 50%, 60%, 70% OR 75 is achieved %, such as 20% to 80%, 20% to 60%, or 20% to 40%. A conversion of n-hexanol is achieved by 10%, 15%, 20%, 25% or 30%, such as from 10% to 30%, from 10% to 25%, of a 15% to 25% or 15% to 20%. The selectivity in n-octanol is at least 20%, at least 30%, at least 40%, 20%, 25%, 30%, 35%, 40%, 45% or a 50%, such as 20% to 50%, 25% to 45%, or 35% to 45%. A n-butanol selectivity of at least 10%, at least 15%, at least 20% or at least 25%, 10%, 15%, 20%, 25%, a 30%, 35% or 40%, such as 10% to 40%, 15% to 40%, or 15 '' to 25%.

As used herein, the selectivity of the reactant compounds in the product compounds is expressed according to the following equation:

(F;, ou'-F;,; n) {nc, / M;) X 100 L [(F ~; "-F ~ ou,) {n" k / Mk) l

k

where: Si (%) = selectivity of compound i; F. en = flow rate of compound i (kg / h) in the feed stream; F. out = flow rate of compound i (kg / h) in the product stream; Mi = molecular weight of compound i (kg / kmol); nc, i = number of carbon atoms in a molecule of compound i; and the summation index k refers to all reactant compounds for which Fk, in is greater than Fk. out-

The product stream of the n-butanol reactor generally comprises 7 to 15 mol%, 8 to 13 mol% or 9 to 12 mol% of n-butanol, such as 7, 8, 9, 10, 11, 12, 13, 14 or 15 mol%; 35 to 60 mol% or 40 to 50 mol% ethanol, such as 42, 44, 46, 48 or 50 mol%; from 0.3 to 1.5 or 0.5 to 1.2 mol% acetaldehyde, such as 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 or 1.2 mol%; 5 to 20 mol% of water, such as 10, 15 or 20 mol%; from 15 to 30 mol% of H2, such as 15, 20 or 25 mol%; from 0.05 to 0.2 mol% ethyl acetate, such as 0.1 or 0.15 mol%; and 0.5 to 6.5 mol% or 1 to 6 mol% of alcohols other than ethanol and nbutanol, including 0.5 to 2.5 mol% or 1 at 2 mol% of nhexanol, 0.1 to 0.5 mol% or 0.1 to 0.3 mol% of n-octanol, and 0.2 to 0 , 6 mol% or 0.3 to 0.5 mol% of -butane!

The product stream of the n-octanol reactor generally comprises 2 to 5 mol%, 2 to 4 mol% or 2 to 3 mol% of n-octanol, such as 2, 3, 4 or 5 mol%; 0.1 to 0.6 mol%, 0.15 to 0.5 mol%, or 0.2 to 0.5 mol% of n-decanol, such as a 0.1, 0.2, 0.3, 0.4, 0.5 or 0.6 mol%; 1 to 6 mol%, 1.5 to 4 mol%, or 2 to 3 mol% of n-butanol, such as 1,2,3,4,5 or 6 mol%; 25 to 40 mol% or 25 to 35 mol% ethanol, such as 25, 30, 35 or 40 mol%; 20 to 35 mol% or 20 to 30 mol% of n-hexanol, such as 20, 25, 30 or 35 mol%; and 20 to 35 mol% or 20-30 mol% hydrogen, such as 20, 25, 30 or 35 mol%.

The n-octanol reactor product stream, at standard temperature and pressure (not containing volatile components such as hydrogen), generally comprises a 0.01 to 0.08 molar fraction of n-octanol, a molar fraction of 0.02 to 0.07 of n-octanol, a molar fraction of 0.025 to 0.06 of n-octanol, a molar fraction of 0.01 to 0.05 of noctanol, or a molar fraction of 0.03 to 0 , 05 of n-octanol, such as a molar fraction of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06 or 0.08; a molar fraction of 0.001 to 0.006 of n-decanol, a molar fraction of 0.002 to 0.006 of n-decanol, or a molar fraction of 0.003 to 0.005 of n-decanol, such as a molar fraction of 0.001, 0.002, 0.003, 0.004 , 0.005 or 0.006; a molar fraction of 0.01 to 0.08 of n-butanol, a molar fraction of 0.02 to 0.07 of n-butanol, a molar fraction of 0.025 to 0.06 of n-butanol, a molar fraction of 0.01 to 0.05 of nbutanol, or a molar fraction of 0.03 to 0.05 of n-butanol, such as a molar fraction of 0.01, 0.02, 0.03, 0.04, 0 , 05, 0.06 or 0.08; a molar fraction of 0.3 to 0.5 of ethanol or a molar fraction of 0.35 to 0.45 of ethanol, such as a molar fraction of 0.3, 0.35, 0.4, 0.45 or 0.5; and a molar fraction of 0.25 to 0.45 of n-hexanol or a molar fraction of 0.3 to 0.4 of nhexanol, such as a molar fraction of 0.25, 0.3, 0.35, 0 , 4 or 0.45. The mole ratio of n-octanol to n-butanol is 0.5: 1 to 1.5: 1, 0.8: 1 to 1.2: 1, or 0.9: 1 to 1 , 1: 1. The mole ratio of n-octanol to n-decanol is 5: 1 to 15:10 of

8: 1 to 12: 1.

In some aspects of the present disclosure that are represented in Figures 1 to 9, a separating fractionation (distillation) column or a preflash fractionation (distillation) column receives and fractionizes the reactor product streams of the butanol reactor system 40 and of the octanol 230 reactor system comprising n-butanol, noctanol and n-decane! In general, the separating column divides the reactor product stream to form a column bottom stream enriched in relatively high boiling compounds that include, but are not limited to, n-butanol, bubutanol, n-hexanol , n-octanol and n-decanol compared to the reactor product stream and a separating column header stream enriched in relatively high condensable and non-condensable gaseous compounds of boiling point including, but not limited to, ethanol, acetaldehyde, ethyl acetate, hydrogen, carbon dioxide, carbon monoxide, methane, ethane and propane compared to the product stream of the reactor. In general, the preflash column divides the reactor product stream to form a preflash column bottom stream enriched in high boiling compounds that include, but are not limited to, n-butanol, bubutanol, n-hexanol, n-octanol and n-decanol compared to the reactor product stream, an intermediate cut-off current of the preflash column enriched in compounds that include, but are not limited to, ethanol, water, acetaldehyde and ethyl acetate compared to the reactor product stream, and a preflash column header stream enriched in non-condensable gaseous compounds that include, but are not limited to, hydrogen, carbon dioxide, carbon monoxide, methane, ethane and propane compared to the stream of reactor product.

Any column design capable of fractionating the various input streams of the present disclosure, such as, for example, the reactor product stream comprising n-butanol, wet ethanol streams, aqueous streams containing organic compounds, n-butanol / hexanol / octanol / decanol streams, to form the various fractionation streams described herein, is suitable for the practice of the present disclosure, and the selection of suitable fractionation columns is within the scope of experts in the field. Generally, fractionation (distillation) columns within the scope of the present disclosure include, for example, columns of filling plate, valve plate, perforated plate, bubble plate, packaging, and moistened wall (drop film). The columns may also comprise conventional components such as, for example, reflux drums, condensers, evaporators and any combination thereof. The columns of the present disclosure are equipped with one, two or more header condensers and one, two or more header accumulation tanks and / or separators that have gas and liquid outlets (condensate) and reflux capacity. In some aspects of the present disclosure, the distillation column has internal trays and / or cartridges in each of the disposal section and the enrichment section. The term "internal" used in the present disclosure means the part of the distillation column where the gas and liquid actually come into contact with each other. Examples of trays include a bubble level tray, a sieve tray, a corrugated perforated tray, a ballast tray, a valve tray, a counter current tray, a Unifrax tray, a Superfrac tray, a Maxfrac tray, a tray dual flow, a grid plate tray, a turbo plate dish tray, a Kittel tray, or the like. Examples of cartridges include random cartridges such as a Raschig ring, a Lessing ring, a Pall ring, a Serl chair, an Intalox chair, a Dixon cartridge, a McMahon or Heli-Pak cartridge, or structured cartridges such as Mellapak, Gempak, Techno -pack, Flexipac, a Sulzer cartridge, a Goodroll cartridge,

Glitschgrid or similar. A multi-stage distillation column that has both a part of trays and a part packaged with cartridges can also be used.

In some aspects of the separator column of the present disclosure, the bottom of the separator column, which contains the reactor product stream comprising nbutanol, n-hexanol, n-octanol and n-decanol is heated to a temperature of 200 2e at 300 2e,

or from 220 2e to 260 pe by means of the separator column evaporator. In some aspects of the present disclosure, hot oil is used as a means of heating the evaporator. The temperature of the upper fraction of gas that passes to the header condenser is 100 2e to 180 2e, or 120 2e to 160 2e. The column pressure is maintained from 10 bara to 30 bara, or from 15 bara to 25 bara. In some aspects of the present disclosure, the cooling temperature of the header condenser is used to control the pressure of the separator column. The separator column generates a header stream enriched in relatively low boiling condensable compounds and non-condensable gaseous compounds that include, but are not limited to, ethanol, acetaldehyde, ethyl acetate, hydrogen, carbon dioxide, carbon monoxide, methane, ethane and propane compared to the product stream of the reactor. The header stream is characterized by the basic absence of high boiling compounds such as n-butanol, n-propanol, ¡-butanol, n-hexanol, n-octanol and n-decanol. In some aspects of the present disclosure, the header stream comprises 55 to 85 mol% or 75 to 80 mol% of ethanol; 0.2 to 2 mol% or 0.5 to 1.5 mol% acetaldehyde; 0.05 to 0.5 mol% or 0.1 to 0.2 mol% ethyl acetate; 1 to 15 mol%, 2 to 8 mol% or 3 to 8 mol% hydrogen; 0.02 to 0.1 mol% or 0.05 to 0.1 mol% carbon dioxide; and 0.1 to 1 mol% or 0.3 to 0.8 mol% carbon monoxide. The separating column generates a background stream enriched in high boiling compounds compared to the product stream of the reactor. In some aspects of the present disclosure, the bottom stream comprises 50 to 95 mol% or 85 to 90 mol% of n-butanol; 0.02 to 0.5 mol% or 0.2 to 0.5 mol% of -butanol; 4 to 15 mol% or 6 to 8 mol% of n-hexanol; from 0.2 to 0.2 mol% of n-octanol.

The header current of the separator column, generated from the reactor product stream comprising n-butanol, is passed through a condenser to form a first condensate stream of header column separator and a second stream of gas column separator. In such aspects of the present disclosure, the first (condensed) stream generally comprises 65 to 95 mol% or 80 to 90 mol% ethanol; 5 to 30 mol%, 5 to 20 mol% or 10 to 15 mol% water; 0.1 to 1.5 mol% or 0.5 to 1 mol% acetaldehyde; and from 0.05 to 0.5 mol% or 0.1 to 0.3 mol% ethyl acetate. In some aspects of the present disclosure at least a portion of the first stream can be refluxed in the separator column and at least a portion is fed into an ethyl acetate column for the generation of an ethyl acetate stream and a stream of wet ethanol The selection of a suitable reflux ratio for the feed is within the scope of the person skilled in the art and varies with, among other factors, the composition of the reactor product stream and the desired compositional profile of the first stream. The header gas stream of the separator column generally comprises, among other components, 30 to 70 mol% or 40 to 60 mol% hydrogen; 25 to 45 mol% or 30 to 40 mol% ethanol; 2 to 10 mol% or 3 to 8 mol% water; 0.5 to 2 mol% or 0.8 to 1.5 mol% acetaldehyde; trace amounts (less than 0.15 mol%) of ethyl acetate; 1 to 8 mol% or 2 to 6 mol% carbon monoxide; and less than 1, 0.5 or 0.3 mol% of total alcohols other than ethanol.

In some aspects of the preflash column of the present disclosure, the column bottom, which comprises the reactor product stream comprising n-butanol, nhexanol, n-octanol and n-decanol is heated to a temperature of 110 2C to 250 2C, from 130 2C to 220 2C, or from 160 2C to 200 2C by means of the evaporator of the preflash column. In some aspects of the present disclosure, hot oil is used as a means of heating the evaporator. The temperature of the upper fraction of gas that passes to the header condenser is 90 2C to 125 2C, 95 2C to 120 2C, or 100 2C to 110 2e, such as 105 2C. The temperature of the average cutting current fed to the separating column is 130 'ca 170' c, 135 'ca 165' c, or 140 'ca 160' c, tat as 150 'C. The column pressure is it keeps from 10 bara to 30 bara, or from 15 bara to 25 bara. In some aspects of the present disclosure, the cooling temperature of the header condenser is used for pressure control of the separator column. The header current of the preflash column is passed through a capacitor to form a first header stream and a second stream of preflash column header gas. Compared to the gas stream of the preflash column, the condensate stream is enriched in ethanol and water. The condensate stream is generally refluxed in the preflash column. In some aspects of the present disclosure, the condensate stream is fully refluxed in the preflash column. In some aspects of the present disclosure at least a part of the first stream can be refluxed in the separator column and at least a part is fed into a separator column, an ethyl acetate column, extractive distillation or molecular sieves for the recovery of non-ethanol components and / or recovery of dry ethanol. The selection of a suitable condenser temperature and the reflux for the feed rate is within the scope of a person skilled in the art and varies with, among other factors, the composition of the reactor product stream, the desired compositional profile of the condensate and gas streams, and the desired operating pressure of the preflash column. The gas stream of the preflash column generally comprises, among other components, 30 to 70 mol% or 40 to 60 mol% hydrogen; 25 to 45 mol% or 30 to 40 mol% ethanol; 2 to 10 mol% or 3 to 8 mol% water; 0.5 to 5 mol% or 1 to 3 mol% acetaldehyde; from 0.03 to 0.15 mol% or 0.05 to 0.1 mol% ethyl acetate; 1 to 8 mol% or 2 to 6 mol% carbon monoxide; and less than 1, 0.5 or 0.3 mol% of total alcohols other than ethanol.

The average cutting current of the preflash column, enriched with compounds that include, but are not limited to, ethanol, water, acetaldehyde and ethyl acetate compared to the product stream of the reactor comprising n-butanol, is fed into a fractionation section of the separator column. The bottom stream of the preflash column, enriched in high boiling compounds that include, but are not limited to, n-butanol, ¡-butanol, n-hexanol, n-octanol and n-decanol compared to the current of product from the reactor, it is also fed to a separating column in a fractionation section located between the evaporator and the inlet port of the medium cutting current. In such aspects of the present disclosure, the separator column evaporator heats the bottom to a temperature of 220!: Le 260!: Le or 230!: Le 250!: Le, such as 240!: Le. The temperature of the upper fraction of gas that passes to the header condenser is 110!: Le at 130!: Le or 115!: Le at 125!: Le, just like 115!: Le. The average cut-off current temperature is 150!: Le to 190!: Le or 160!: IC to 180!: IC, such as 170!: Le. The column pressure is maintained from 10 bara to 30 bara, or from 15 bara to 25 bara. The header current of the separator column, generated from the feed of the preflash column, is passed through a condenser to form a first header condensate stream and a header column separator gas stream. Compositionally, the header, the first condensate stream and the gas streams are similar to the corresponding streams formed from the reactor product stream described above. The gas stream of the separator column can be combined with the gas stream of the pref / ash column. The condensate stream can be refluxed in the separator column, the preflash column,

or a combination thereof.

In some aspects of the present disclosure, the gas stream of the separator column or a combination of the gas streams of the preflash column and the separator column can be passed through a second condenser to form a header condensate stream of a second separating column or preflash and a stream of header gas of a second separating column or preflash. Such second streams of header condensate are characterized in that they generally comprise, among other components, 75 to 95 mol% or 80 to 90 mol% ethanol; 5 to 20 mol% or 10 to 15 mol% water; 1 to 10 mol%, 2 to 8 mol%, or 3 to 5 mol% acetaldehyde; and from 0.05 to 0.5 mol% or 0.1 to 0.3 mol% ethyl acetate. Such second gas streams are characterized in that they generally comprise, among other components, 80 to 95 mol% or 80 to 90 mol% hydrogen; 1 to 10 mol% or 4 to 8 mol% carbon monoxide; 1 to 15 mol% or 2 to 10 mol% of the total methane, ethane and propane; less than 0.2 mol% or less than 0.1 mol% acetaldehyde; and only trace amounts of ethyl acetate.

In some aspects of the present disclosure, represented in Figures 2, 4 to 6 and 9, at least a part of the header condensate stream of the separator column is fed into an ethyl acetate column for the generation of a stream of ethyl acetate and a stream of wet ethanol. Any column design capable of splitting a feed stream to form a bottom stream enriched in water and ethanol compared to the feed stream and a header stream enriched in acetaldehyde and ethyl acetate compared to the feed stream is suitable. for the practice of this disclosure. The selection of the ethyl acetate fractionation columns is within the scope of those skilled in the art, with the appropriate columns described above with respect to the separator column.

In any of the various aspects of the present disclosure, the bottom of the ethyl acetate column (comprising the feed stream) is heated to a temperature of 70!: Le to 100!: Le, or 75 Qe a 95 Qe, by one or more evaporators of the ethyl acetate column. In some aspects of the present disclosure, the isobutanol column header is used as a heating medium in a first evaporator and the header of the separator column is used as a heating medium in a second evaporator. The temperature of the upper fraction of gas that passes to the header condenser is 30 QC at 50 µL, or 35 QC at 45 pe. The column pressure is operated at atmospheric pressure, or at a slightly positive pressure such as 1 bara to 1.5 bara, or 1 bara to 1.2 bara.

The ethyl acetate column generates a header stream enriched in acetaldehyde and ethyl acetate compared to the feed stream of the ethyl acetate column. In some aspects of the present disclosure, the header current comprises 25 to 60 mol% or 30 to 50 mol% acetaldehyde; 1 to 40 mol% or 15 to 30 mol% ethyl acetate; and 5 to 35 mol% or 20 to 25 mol% ethanol. The header stream is passed through a condenser to form a condensate stream that generally corresponds compositionally with the header stream and a gas stream comprising 30 to 60 mol% acetaldehyde; from 1 to 10 mol% of ethyl acetate; and less than 5 mol% ethanol. In any of the various aspects of the present disclosure, at least a portion of the header condensate stream and the gas stream are purged from the process. In some other aspects of the present disclosure, the header condensate stream can be purified to form an ethyl acetate basic product.

The ethyl acetate column generates a bottom stream enriched in ethanol and water compared to the product stream of the reactor comprising n-butanol. The background stream generally comprises 65 to 95 mol% or 80 to 90 mol% ethanol; 10 to 30 mol% of water; and no more than trace amounts of acetaldehyde and ethyl acetate.

In some aspects of the present disclosure, represented in Figures 2-5, 7 and 9, various streams of wet ethanol can be processed, including the bottom stream of the ethyl acetate column, the header stream of the separator column generated from the middle and bottom cutting currents of the preflash column, the ethanol stream of soda, and the header current of the regeneration column, by means of a molecular sieve to generate a feed stream of dry ethanol for the butane conversion! Molecular sieves that are capable of adsorbing water and optionally other impurities of a mixture thereof with an alcohol are well known. In one aspect, the molecular sieve material is selected to remove water. In other aspects, the molecular sieve material is selected to remove addition impurities such as acetic acid and / or ethyl acetate from the third distillate to form the anhydrous ethanol composition. Selection criteria may include, for example, pore size and volume characteristics. In general, such molecular sieves are crystalline, although the particular sieve used is not critical. However, such sieves should be able to adsorb at least 2 w / w, 2 to 30% w / w, or 5 to 25% w / w under adsorption conditions. Suitable molecular sieves include a zeolitic molecular sieve having an average pore diameter of 3 Angstroms. Typical examples of such molecular sieves are type A zeolites, such as 3A, 4A and 5A. Other suitable molecular sieves include inorganic adsorbents such as lithium chloride, silica gel, activated alumina, and / or biologically based adsorbents such as corn powder. Molecular sieves can be configured in a molecular sieve bed and multiple molecular sieve beds can be used sequentially or in a countercurrent arrangement.

In any of the various aspects of the molecular sieve of the present disclosure, one or more wet ethanol feed streams described herein are purified by the molecular sieve to generate a stream of dry ethanol for conversion into n-butanol , n-hexanol, n-octanol and n-decanol, and a wet ethanol stream from the molecular sieve containing the removed water that can be processed for ethanol recovery, such as by a regeneration column. Wet ethanol streams include the bottom stream of the ethyl acetate column, the average cutoff stream of the separator column, the feed stream of soda ethanol, and the header stream of the regeneration column. The dry ethanol stream is characterized by comprising 88 to 99.9 mol%, 98 to 99.9 mol% or 99 to 99.8 mol% ethanol; less than 5 mol%, 0.05 to 5 mol%, 0.1 to 1 mol% or 0.1 to 0.3 mol% of water; less than 0.5 mol% or less than 0.3 mol% of alcohols other than ethanol; and only trace amounts (i.e. less than 0.05 mol%) of acetaldehyde and ethyl acetate. The wet ethanol stream of the molecular sieve generally comprises 35 to 50 mol% or 40 to 45 mol% of ethanol; from 50 to a

65 mol% or 55 to 60 mol% of water; and trace amounts (less than 0.05 mol% each) of other compounds.

The wet ethanol stream of the molecular sieve can be processed in a regeneration column to fractionate the feed stream into head streams of recovered alcohol, medium-cut isoamyl alcohol and bottom of residual water. Any column design described above capable of fractionating the wet ethanol stream of the molecular sieve of the present disclosure is suitable for the practice of the present disclosure. The bottom of the regeneration column (which comprises the wet ethanol feed stream of the molecular sieves) is heated to a temperature of 110 pe to 150 pe, or 120 pe to 140 pe, by a regeneration column evaporator . In some aspects of the present disclosure, the header of the separator column is used as a heating medium. The temperature of the upper fraction of gas that passes to the header condenser is 90 pe to 110 pe, or 95 pe to 105 pe. The pressure of the column is operated at a pressure of 1.5 bara at 4 bara, or from 2 bara to 3 bara. In some aspects of the present disclosure, the column pressure is controlled by the header condenser. In some additional aspects of the present disclosure, soda ethanol is introduced into the regeneration column as reflux.

The regeneration column generates a header current that basically consists of 75 to 85 mol% of ethanol and 15 to 25 mol% of water with only trace amounts of other components. The header stream is recycled in the molecular sieves or processed by extractive distillation to remove water and generate a stream of dry ethanol for conversion into n-butanol, n-hexanol, n-octanol and n-decanol. The regeneration column also generates a lateral withdrawal purge stream comprising from 1 to 20 mol% or from 5 to 15 mol% isoamyl alcohol (3-methyl-1-butanol), from 80 to 99 Mole% water and minor amounts of nbutanol and ethanol. The regeneration column generates a bottom stream that basically consists of water that is discharged from the process in the treatment of wastewater.

In any of the various aspects of the present disclosure, the soda ethanol stream can be processed by molecular sieves, by a combination of the regeneration column and molecular sieves, as described above, by extractive distillation as described in the present document, by means of a fusel column, or by the combination of a fusel column and molecular sieves to generate a feed stream of dry compensation ethanol for conversion into n-butanol, n-hexanol, n-octanol and n-decane ! Various sources of soda ethanol are within the scope of the present disclosure including bioethanol generated in fermentation processes, ethanol generated by ethylene hydration, and ethanol generated in catalytic cracking operations. Ethanol produced from biologically based renewable raw materials (such as from crop energy sources

or cellulosic) may contain a variety of impurities such as fusel oil (amyl alcohol isomers such as 3-methyl-1-butanol and n-amyl alcohol), such / Di! which contains rosin esters and acids (cyclic carboxylic acids), alkali metals, phosphorus, fatty acids, ions (inorganic and organic), and surfactants.

The ethanol feed of soda can optionally be passed through a purification bed before dehydration and / or the fusel column in order to remove and thereby reduce the concentration of various contaminants including ionic contaminants such as salts organic, inorganic salts, anions and cations. Any purification medium capable of removing contaminants from soda ethanol is within the scope of the present disclosure. In some aspects of the present disclosure, ion exchange resin can be used for purification of soda ethanol. The ion exchange resin can be properly placed in a column

or a packed bed. The resins are in the form of cation exchange or anion exchange, or a combination of the two. In principle, cation exchange resins remove cations such as sodium, potassium, nitrogen-containing compounds, or metal ions (eg, nickel, iron and chromium), and anion exchange resins remove anions such as sulfate, chloride, acetate and phosphines. In some optional aspects of the present disclosure, before or after the purification treatment, the soda ethanol can be treated in a treatment zone with a bleaching earth (for example, bentonite clay) and / or activated carbon. In addition, soda ethanol can optionally be filtered before or after purification by methods known to those skilled in the art.

In some aspects of the present disclosure, such as or, for example, those represented in Figure 2, the soda ethanol feed comprising fusel oil impurities, such as ethanol that comes from renewable bio-based raw materials, can be split into a fusel column to generate a header stream comprising purified ethanol for conversion into higher alcohols and a bottom stream comprising fusel oil and water. Suitable fusel columns are those that have been

previously described. The selection of the fractionation conditions necessary for the separation of water and fusel oil (comprising a mixture of amyl alcohol isomers having a boiling point ranging from 113 2e to 140 2e) of the ethanol required to achieve the desired purity is within the scope of an expert in the field.

In some optional aspects of the present disclosure, purified soda ethanol can be added to the process directly in the reactor feed stream instead of being dehydrated and initially purified by a molecular sieve, by a regeneration column, by an oil column fusel, as described above, and by extractive distillation as described herein.

In any of the various aspects of the present disclosure, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least one 96%, at least 97%, at least 98% or at least 99%, such as 50% to 99%, or 90% to 99% of the ethanol present in the reaction mixtures of Butanol and hexanol are recovered from the reactor product streams and recycled into the butanol reactor system and the octane reactor system!

In some aspects of the present disclosure, represented in Figures 6, 8, 10 and 11, the various streams of wet ethanol, including the bottom stream of the ethyl acetate column, the header stream of the column can be processed separator generated from the middle and bottom cut streams of the preflash column, the ethanol feed of soda, and the header current of the regeneration column, by extractive distillation to generate a feed stream of dry ethanol for conversion into n-butanol, n-hexanol, n-octanol and n-decane! As is known in the art, extractive distillation is a method of separating compounds with near boiling points or azeotropes by performing distillation on a multi-plate rectification column in the presence of an added extractive agent (solvent) or a mixture. of solvents, in which the liquid or liquids have a boiling point greater than the compounds to be separated. When the compounds to be separated normally form an azeotrope, the extractive distillation agent will cause the compounds to boil separately during the extractive distillation and thereby make possible a separation in a rectification column that cannot be performed in any way when the agent does not It is present. The extractive agent should boil at a temperature higher than any of the nearby boiling liquids that are to be separated and not form a minimum boiling point azeotrope with them. For example, the additional solvent preferably used for extractive distillation may have a boiling point at the pressure at which the fractionation takes place which is at least 10 Ile, at least 20 µle or at least 30 Ile greater than the point of boiling the component with the highest boiling point of the mixture to be separated. In general, the extractive agent is introduced near the top of the column and flows down until it reaches the evaporator. Their presence in each plate of the rectification column alters the relative volatility of the compounds of nearby boiling points in one direction to make the separation in each plate greater and thus requires a smaller amount of plates to effect the same separation or It makes possible a greater degree of separation with the same number of plates. Typically, the extractive agent is introduced to a few plates from the top of the column to ensure that no amount of the extractive agent is entrained with the lower boiling component. At the bottom of a continuous column, the less volatile components of the mixtures of nearby boiling points and the extractive agent are continuously removed from the column.

Examples of suitable extractive agents include glycerin, propylene glycol, N, N-dimethylformamide, dimethyl sulfoxide, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Examples of mixtures of extractive agents include two, three or four extractive agents selected from phenal, m-pcresol, o-sec-butylphenol, o-tert-butylphenol, catechol, hydroquinone, resorcinol, 1-naphthol, 2-naphthol, acetophenone, ethyl acetoacetate, glycerin phthalate, dibutyl phthalate, dioctito phthalate, diisooctyl phthalate, diisodecyl phthalate, ethylene glycol phenyl ether, 1,5-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, hexylene glycol, diethylene glycol ethyl ether, butoxypropanol, dipropylene glycol methyl ether, Propylene Glycol and Dipropylene Glycol, Dimethylsulfoxide, Dimethylformamide, 1,3-Butanediol, 1,4-Butanediol, 1,6-Hexanediol, Polyethylene Glycol 300, Diisobutyl Phthalate! 2-propanediol. In some aspects of the present disclosure, the extractive agent is glycerin or ethylene glycol.

The selection of the bottom temperature (evaporator), the gas temperature and the column pressure of the extractive distillation depend on, among other factors, the extractive agent, the feed rate of the column, and the degree of purity desired. . In the case of glycerin, the bottom of the column (which includes the feed stream and the extractive agent) is heated to a temperature of 150!: Le to 250!: Le, or 180!: Le to 200!: Le , by one or more evaporators, and the temperature of the upper fraction of gas passing to the header condenser is 90 'C to 110' C, or 95 'C to 105' C. The column pressure is operated at atmospheric pressure, at a slightly positive pressure, or at a pressure of 1 bara at 5 bara, or 2 bara at 4 bara. The header stream is passed through a condenser to form a stream of dry ethanol with a composition as described above. At least a part of the non-condensed gases, which include ethyl acetate and acetaldehyde, can be purged from the process. The dry ethanol condensate stream is a source of ethanol for conversion into n-butanol, n-hexanol, noctanol and n-decane! At least a part of the condensed ethanol can be refluxed in the extractive distillation column.

The bottom stream of extractive distillation comprises extractive agent (solvent), water and various impurities removed. The bottom stream is purified on a regeneration column to generate a bottom stream of purified solvent that is recycled into the extractive distillation column. The header current of the regeneration column is passed through a condenser, and the condensate (comprising ethanol, water and organic impurities) is fed into a water eliminating column. At least a part of the header condensate stream can be refluxed to the extractive distillation column. Losses of extractive solvent can be compensated with soda extractive agent. In the case of the glycerin extractive agent, the bottom of the extractive distillation column (comprising contaminated glycerin) is heated to a temperature of 120 2C to 220 2C, or 150 2C to 190 2C, by one or more column evaporators of regeneration, and the temperature of the upper fraction of gas that passes to the header condenser is 50 2C to 100 2C, or 55 2C to 80 2C. The regeneration pressure is operated with a partial vacuum of 0.1 bara to 0.5 bara.

In some other aspects of the present disclosure, represented in Figures 10 and 11, one or more extractive distillation columns can be used to fractionate the reactor product stream comprising n-butanol to form a header stream comprising organic compounds low boiling point including ethanol, acetaldehyde, and ethyl acetate and a bottom stream comprising water and higher boiling organic compounds that include n-butanol, bubutanol, n-hexanol, noctanol and n-decane !

In some aspects of the present disclosure, two series extractive distillation columns are used in which the first column is operated at a pressure greater than the second column and in which the bottom stream of the first column is further purified in the second column. In such aspects, prior to extractive distillation, the reactor product stream comprising n-butanol and higher alcohols is passed through one or more condensers to generate gas and condensate streams. Generally, the gas stream predominantly comprises non-condensed gases that include 80 to 95 mol% or 80 to 90 mol% hydrogen, and 1 to 10 mol% or a 4 to 8 mol% carbon monoxide. The gas stream also comprises other gases such as 1 to 15 mol% or 2 to 10 mol% of the total methane, ethane and propane; acetaldehyde; And only trace amounts of ethyl acetate. The condensate stream is fed to the first extractive distillation column for the generation of the header and bottom streams. In the case of the glycerin extractive agent, in the first extractive distillation column, the bottom (reactor product stream and glycerin) is heated to a temperature of 150 µl to 250 µl, or 180 µl to 220 µl , by means of one or more evaporators, and the temperature of the upper fraction of gas that passes to the header condenser is 30 µl to 80 µl, or 40 µl to 60 µl. The column is operated at a pressure of 3 bara at 7 bara, or from 4 bara to 6 bara. The header current is condensed in a condenser or two or more sequential condensers to form a dry ethanol condensate stream characterized in that it comprises from 98 to 99.9% by mole or from 99 to 99.8% by moles of ethanol; 0.05 to 0.5 mol% or 0.1 to 0.3 mol% water; less than 0.5 mol% or less than 0.3 mol% of alcohols other than ethanol; and only trace amounts (i.e. less than 0.05 mol%) of acetaldehyde and ethyl acetate. One or more gas streams comprising ethyl acetate and / or acetaldehyde can be purged from the process in the first extractive distillation header system.

In such embodiments of the present disclosure, the bottom stream of the first extractive distillation column comprising extractive agent, n-butanol, -butanol, Ir hexanol, n-octanol, Irdecanol, water, and a certain reduced amount of ethanol is It undergoes a second extractive distillation. In some aspects of the present disclosure, the same extractive agent is used in the first and second extractive distillation columns. In the case of glycerin, in the second extractive distillation column, the bottom (comprising contaminated extractive agent) is heated to a temperature of 120 oC to 220 oC, or 150 oC to 190 oC, by means of one or more evaporators, and the temperature of the upper fraction of gas that passes to the header condenser is 30 oC to 80 "C, or 40 oC to 60 oC. The column is operated at a pressure of 1 bara to 3 bara, or 1, 5 bara at 2.5 bara.The header current is passed through a condenser and refluxes to the first extractive distillation column.The bottom stream, which predominantly comprises extractive agent, n-butanol, ¡-butanol, n -hexanol, n-octanol, n-decanol and water is processed in a regeneration column as described above to generate a bottom stream comprising basically pure extractive agent that is recycled in the first and second extractive distillation columns. header current of the regenerate column tion, which predominantly comprises n-butanol, butanol, n-hexanol, n-octanol, n-decanol and water, condenses and feeds into a column of butane! The bottom of the regeneration column (comprising contaminated extractive agent) is heated to a temperature of 180 2e to 250 2e, or 200 2e to 240 2e, by one or more evaporators, and the temperature of the upper fraction of gas that The header capacitor is 25 2e to 40 2e, or 30 2e to 30 2e. The column is operated with a partial vacuum at a pressure of 0.03 bara at 0.1 bara, or from 0.05 bara to 0.08 bara. In such aspects of the present disclosure, soda ethanol can be introduced into the process in the first or second extractive distillation column.

In some aspects of the disclosure, the reactor product stream 45 can optionally be processed in a secondary reactor to convert the residual aldehyde (acetaldehyde) into ethanol and thereby increase the yield. Such an optional aldehyde reactor is represented as reactor 170 in Figure 11. Such an aldehyde reactor may optionally be included in any of the various aspects of the present disclosure, such as the process depicted in Figures 4 to 10. The reagents of Suitable aldehyde and the operation thereof are as described above with respect to the butanol reactor system 40.

In some other aspects of the present disclosure, an extractive distillation column is used. In such aspects, prior to extractive distillation, the product stream of the reactor can be optionally passed through an aldehyde reactor to convert the residual aldehyde (for example, acetaldehyde) into alcohol (for example, n-butanol) and forming a stream having a reduced aldehyde content compared to the reactor product stream comprising n-butanol. In such aspects, prior to extractive distillation, the reactor product stream is passed through a first condenser to form gas and condensate streams in which the gas stream is passed through the aldehyde reactor. In any aspect, the resulting gas and condensate streams are combined and passed through a condenser, or two or more sequential condensers, to generate a gas comprising recyclable hydrogen and a condensate stream to process by extractive distillation. The composition of the gas stream is as described above. The condensate stream is fed to the extractive distillation column for the generation of the header and bottom streams. In the case of the glycerin extractive agent, the column is operated at a pressure of 10 bara at 30 bara, or 15 bara at 25 bara and the corresponding temperatures. The header stream is condensed in a capacitor or two or more sequential capacitors to form a stream of dry ethanol condensate. The composition of the dry ethanol condensate stream is as described above. One or more gas streams comprising ethyl acetate and / or acetaldehyde in the extractive distillation header system can be purged from the process.

The bottom stream of the extractive distillation column comprising extractive agent, n-butanol, butanol, n-hexanol, n-octanol, n-decanol and water, and a certain reduced amount of ethanol is processed in a regeneration column as It has been described above to generate a bottom stream comprising basically pure extractive agent that is recycled in the first and second extractive distillation columns. A column header stream, predominantly comprising butanol, -butanol, n-hexanol, n-octanol, n-decanol and water, is condensed and fed into a butane column! The selection of suitable extractive distillation pressure and temperature ranges is within the scope of those skilled in the art based on the extractive agent. In such aspects of the present disclosure, soda ethanol can be introduced into the process in the extractive distillation column.

In any of the various aspects of the present disclosure, a dry ethanol source is generated in the process for use in the formation of the reaction mixture, comprising the recovered ethanol recovered ethanol and soda ethanol characterized in that it comprises less than 0.005 moles of acetaldehyde per mole of alcohol, less than 0.001 moles of each acetaldehyde and ethyl acetate with respect to alcohol, less than 0.01 total moles of alcohols other than ethanol with respect to ethanol, and the absence of hydrogen and carbon monoxide.

In aspects of the present disclosure in which a second header condensate stream of the preflash column or the separator column and a second gas stream are formed, as depicted in Figures 2 and 4 to 9, the second stream of Bedside condensate is characterized by comprising 80 to 90 mol% of ethanol, 2 to 8 mol% of acetaldehyde, 0.05 to 0.5 mol% of ethyl acetate, and the absence of hydrogen and carbon monoxide, and the second gas stream is characterized in that it comprises from 80 to 95 mol% of hydrogen, from 1 to 10 mol% of carbon monoxide, less than one 0.2 mol% acetaldehyde, and no more than trace amounts of ethyl acetate, water and alcohols other than ethanol.

In aspects of the present disclosure in which a second header condensate stream of the preflash column or the separator column and a second gas stream are formed, as depicted in Figures 2 and 4 to 9, the concentration of acetaldehyde in the reaction mixture it can be optionally controlled by combining the dry ethanol stream with the second header condensate stream of the preflash column or the separator column. In such aspects of the present disclosure, the isolation of acetaldehyde and its reintroduction into the process allows an predetermined concentration of acetaldehyde to be effectively achieved in the reaction mixture by controlling the mixing ratio. In addition, the removal of acetaldehyde allows

(i) the recovery and recycling of acetaldehyde, (ii) the purging of the acetaldehyde process and

(iii) a second stream of hydrogen-containing gas that can be further purified before recycling in the process. In some aspects of the acetaldehyde concentration control of the present disclosure, as described above, the second header condensate stream 54 comprising recovered acetaldehyde can be partially or totally refluxed optionally to the ethyl acetate column 60 (Figures 4 to 6 or 9) or to the separator column 50 (Figures 7 and 8). The non-refluxed acetaldehyde can be fed to the Guerbet reaction in reactor feed streams 36 and 37. The reflux rate to be fed can be controlled to achieve a pre-selected acetaldehyde concentration in feed streams 36 and 37 of the reactor system of butanol 40.

In aspects of the present disclosure in which a second header condensate stream of the preflash column or the separator column and a second gas stream are formed, as depicted in Figures 2 and 4 to 9, the basic absence ( that is, no more than trace amounts) of ethyl acetate, water and non-ethanol alcohols in the reaction mixture can be achieved by generating a stream of dry ethanol and a second stream of header condensate from the preflash column or the separation column containing only trace amounts of the compounds.

In aspects of the present disclosure in which a second header condensate stream of the preflash column or the separator column and a second gas stream are formed, as depicted in Figures 2 and 4 to 9, the hydrogen concentration and carbon monoxide in the reaction mixture can be achieved by combining (i) the dry ethanol stream and (ii) the second header condensate stream of the preflash column or the separator column with (jii) at least a portion of the second header gas stream of the preflash column or the separator column.

In some aspects of the present disclosure, the second stream of header gas can be incorporated directly into the reaction mixture. Such process options are depicted in Figures 2, 4, and 6 to 11 (second separator column gas stream 21) and Figure 5 (second separator column gas stream 55). In some other aspects of the present disclosure, the second stream of header gas 21 can be purified (such as by pressure change adsorption) to generate a stream consisting basically of hydrogen which is then incorporated into the reaction mixture. Examples of such process options are represented in Figures 2, 4 and 6 a

11. In some other aspects of the present disclosure, a mixture of purified and unpurified second stream of gas can be incorporated into the reaction mixture. In some other aspects of the present disclosure represented in Figures 1 to 3, and within the scope of any of the various aspects of the present disclosure, at least a portion of the hydrogen present in the reaction mixture is provided by a source of hydrogen of soda such as hydrogen generated. Those skilled in the art know such hydrogen generators. In other aspects of the present disclosure, the Guerbet reaction can be carried out in the presence of recycled hydrogen only without the use of hydrogen compensation supplied from a source of generated hydrogen.

In some aspects of the present disclosure, the second stream of header gas is purified by pressure change adsorption ("PSA"). Pressure change adsorption processes (PSA) are known in the art and are used for the purification of hydrogen gas. In PSA processes, the hydrogen gas included with impurity gases is fed to an adsorption tower filled with an adsorbent. Hydrogen gas passes through the high pressure adsorbent, while impurity gases, for example, N:?, CH4, CO and CO :? they are adsorbed by the high pressure adsorbent and purged from the process.

In any of the various aspects of elimination column and evaporation column

Snapshot of the present disclosure, 100%, 50% to 100%, 50% to 80% or 60 to 75%, such as 65% or 70%, of hydrogen is recovered present in the second gas stream and recycled in the reaction mixture. The concentration of hydrogen in the reaction mixture is controlled based on the recovery rate of hydrogen and the recycling rate. For example, in some aspects of the present disclosure, in one example, 0.1 mol of hydrogen is recovered and recycled for each mole of ethanol in the Guerbet reaction mixture.

In any aspect of the present disclosure to process the reactor product stream by extractive distillation, as depicted in Figures 10 and 11, the condensed regeneration column header is fed to an isobutanol column for fractionation and removal of water from it. The header stream comprises a water-butanol azeotrope. The current is passed through a capacitor and fed to a separation tank. The butanol phase is refluxed to the butanol column and the water phase is fed to a water eliminating column. The bottom stream of the butanol column, comprising dry n-butanol, is fed to a hexanol column. The selection of suitable isobutanol column pressure and temperature ranges is within the scope of those skilled in the art. The header stream, which comprises water and minor amounts of n-butanol, is passed through a condenser. A part of condensate is recycled in the elimination column and a part of the condensate is fed as reflux to the first or second extractive distillation column. The selection of the appropriate pressure and temperature ranges of the elimination column is within the scope of those skilled in the art.

In such aspects of extractive distillation of the present disclosure, the bottom (comprising n-butanol bottom stream of the butanol column) is heated in the hexanol column at a temperature of 180 pcs to 200 pcs, or 170 pcs at 190 pcs, using one or more evaporators, and the temperature of the upper fraction of gas that passes to the header condenser is 110 pcs at 150 pcs, or 120 pcs at 140!: IC. The column is operated at a pressure of 1.1 bara at 3 bara, or 1.3 bara at 2 bara. In an optional aspect of the present disclosure, the hexaneol bottom is heated to a temperature of 150 pcs at 190 oC, or from 160 oC to 180 oC, by one or more evaporators, and the temperature of the upper fraction of gas passing The header condenser is 80 oC to 105 oC, or 85 oC to 100 oC. The hexanol column is operated with a partial vacuum of an approximate pressure of 0.2 to 0.6 bara, or 0.3 bara to 0.5 bara.

In some aspects of the present disclosure, represented in Figures 1 to 8, any of the various raw eliminator column bottom streams comprising n-butanol, n-hexanol, n-octanol and n-decanol can be processed in a Hexanol column for generating a header stream predominantly comprising n-butanol and -butanol and a bottom stream comprising nhexanol, n-octanol and n-decane! Suitable hexanol columns are as described elsewhere herein with respect to distillation columns. In the hexanol column, the bottom is heated to a temperature of 130 2C to 190 2e, or 160!: To 180 2e, by one or more evaporators, and the temperature of the upper fraction of gas that passes to the condenser of Header is 35 2C to 130 2C, or 85 2C to 100 2C. In some aspects of the disclosure, the hexanol column is operated with a partial vacuum of an approximate pressure of 0.1 to 0.6 bara, or 0.3 bara to 0.5 bara. In some other aspects of the disclosure, the hexanol column is operated at atmospheric pressure. The header current of the hexanol column comprising n-butanol and -butanol is passed through a condenser and is directed to a -butanol column for the separation of n-butanol from the; -butane !. In some aspects of the present disclosure, a gas stream comprising oxygen, nitrogen and gaseous water can be vented from the process. At least a part of the condensate is refluxed to the hexanol column and the rest is fed to the column of -butane! The bottom stream of the hexanol column generally comprises 70 mol%, 75 mol%, 80 mol% or 85 mol% of n-hexanol, and the intervals thereof, such as 70 to 85 mol%, or 75 to 85 mol%; 5 mol%, 7 mol%, 9 mol%, 11 mol%, 13 mol% or 15 mol% of n-octanol, and the intervals thereof, such as 5 to 15 mol%, or 7 to 11 mol%; 3 mol%, 4 mol%, 5 mol%, 6 mol%, or 7 mol% of 2-ethyl-1-butanol, and the intervals thereof, such as a 3 to 7 mol%, or 4 to 6 mol%; 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, or 2.5 mol% of 2-ethyl-n-hexanol, and the intervals of themselves, such as 0.5 to 2.5 mol%, or 1 to 2 mol%; and 0.3 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, or 2 mol% of n-decanol, and the intervals thereof, such about 0.3 to 2 mol%, or 0.5 to 1.5 mol%.

The header condensate of the crude hexanol column comprising predominantly n-butanol and i-butanol is directed to the isobutanol column for

division. In some aspects of the disclosure, the column is operated with a vacuum of 0.5 psia, 1 psia, 1.5 psia, 02 psia (from 0.03 to 0.15 bara), and the intervals thereof, such as 0.5 to 2 psia, or 0.5 to 1 psia. In such aspects, the header current rich in ¡-butanol is condensed at 10 2C. In other aspects of the disclosure, the bottom of 5 column is heated to a temperature of 70 2C to 140 "e, or from 110 2C to 130 µl, by one or more evaporators, and the temperature of the upper gas fraction which passes to the header condenser is 80 2C to 110 pe, or 95 2C to 105 2 C. In such aspects, the isobutanol column is operated at a pressure of 1 to 2 bara, or 1.1 bara to 1, 5. The header current is passed through a condenser and optionally recycled in the ethyl acetate column, the separating column or the extractive distillation column as reflux and / or purged from the process. In various aspects, the header current of the ¡-butanol column predominantly comprises ethanol, npropanol, ¡-butanol and 2-butanol, and only trace amounts of n-butanol.The bottom stream of the butanol column consists of n- finished butanol comprising more than 99%

15 mol, more than 99.5 mol%, such as 99 to 99.9 or 99.5 to 99.9 mol% of n-butanol with trace amounts of ¡-butan 01 , 3-methyl-1-butanol and 2-butanol.

In an option of the process depicted in Figure 9, but applicable to any of the various aspects of the present disclosure, any of the various n20 butanol streams of raw scavenger bottom can be processed in an isobutanol column to generate a stream background comprising predominantly n-butanol, nhexanol, n-octanol and n-decanol, and a header stream predominantly comprising ¡-butanol. The bottom stream of the isobutanol column is fed to a butanol column to generate a bottom stream comprising

Predominantly n-hexanol, n-octanol and n-decanol and a header current which basically comprises pure n-butanol product.

The bottom stream of the hexanol column is directed to a hexanol purification column to fractionate and recover n-hexanol from the column header for use as a raw material for the octanol reactor system and generates a bottom stream that it comprises n-octanol, n-decanol, 2-ethyl-butanol and 2-ethyl-hexanol. In some aspects of the disclosure, the spine is generally operated at 15 psia, 16 psia, at atmospheric pressure, 18 psia, 19 psia, 20 psia, 21 psia, 22 psia, or 25 psia. The header current generally comprises 90 mol%, 91 mol%, 92 mol%, 93 mol%, 3594 mol%, 95 mol%, or 96% mol moles of n-hexanol; 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, or 9 mol% of 2-ethyl-l-butanol ; 0.1 mol%, 0.2 mol%, 0.3 mol%, 0.4 mol%, or 0.5 mol% of n-butanol; and trace amounts of other compounds. The background stream generally comprises 50 mol%, 55 mol%, 60 mol%, 65 mol%, or 70 mol% of n-octanol; 5% in 5 moles, 10% in moles, or 15% in moles of 2-ethyl-n-hexanol; 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, or 12 mol% of n -decanol; and 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, or 8 mol% of 2-butyl-n-octanol. In any of the various aspects of the disclosure, at least 95% in moles, at least 96% in moles, at least 97% in moles, at least 98% in moles, at least 99% in moles, at least 99.5 mol% or at least 99.8 mol% of the n-hexanol contained in the bottom stream of the hexanol column is recovered and recycled in the octanol reactor system. In some other aspects of the disclosure, at least 95 mol%, at least 96 mol%, at least 97% in

15 moles, at least 98 mol%, at least 99 mol% of the n-hexanol contained in the reaction mixture of the hexanol reaction system is recovered and recycled in the octanol reactor system.

The header current of the hexaneol purification column is directed to a column

20 of 2-ethyl-butanol to fractionate 2-ethyl-butanol as the header stream and form purified nhexanol as the bottom stream and for use as n-hexanol feed to the octanol reactor system for condensation with ethanol. The background stream generally comprises 96 mol%, 97 mol%, or 98 mol% of nhexanol; 2 mol%, 3 mol% or 4 mol% of 2-ethyl-1-butanol; Y

25 trace amounts of other compounds. The header stream generally comprises 90 mol% of 2-ethyl-1-butanol, 7 mol% of n-butanol and 2 mol% of n-hexanol. In some aspects of the disclosure,

The bottom stream of the hexanol purification column can be fractionated to recover n-octanol and n-decanol in alternative process schemes.

In a first such process scheme generally represented in FIG. 2, the hexaneol purification column bottom stream 225 is directed to an octanol column 240 and fractionated to form a bottom stream 242 comprising n35 decanol, 2-ethyl-n-octanol (i-decanol), and high boiling compounds and a header stream 241 comprising n-octanol and 2-ethyl-hexanol. Header current

It generally comprises from 80 mol% to 90 mol% of n-octanol and 10 mol% to 20 mol% of 2-ethyl-n-hexanol. The bottom stream generally comprises from 20 mol% to 40 mol% of n-decanol; from 2 mol% to 6 mol% of 2-ethyl-n-octanol (i-decanol); from 1 mol% to 3 mol% of 2-ethyln-decanol; from 15 mol% to 25 mol% of 2-butyl-n-octanol; and from 40 mol% to 60 mol% of a mixture of high boiling compounds, such as ¡-decanol and hexa-decanol.

In the first scheme, the header stream of the octanol column is directed to a purification column of n-octanol 250 and fractionated to form a header stream 251 predominantly comprising 2-ethyl-hexanol and a bottom stream 252 which generally comprises at least 98 mol% or at least 99 mol% of n-octane! The n-octanol stream is directed to storage and the 2-ethyl-hexanol stream can optionally be sold as merchandise (optionally with additional purification) or incinerated for energy recovery.

In the first scheme, the bottom stream of the octanol column is directed to the column of ¡-decanol 260 and fractionated to form a header stream 261 predominantly comprising 2-ethyl-n-octanol (i-decanol) and a bottom stream 262 comprising n-decanol and high boiling compounds. The header stream generally comprises 35 mol%, 40 mol%, 45 mol%, 50 mol% or 55 mol% of 2-ethyl-n-octanol; 10 mol%, 15 mol%, or 20 mol% of hexoxyhexane; and 1 mol%, 2 mol%, 3 mol% or 4 mol% of n-decanol. The background stream generally comprises 20 mol%, 25 mol% or 30 mol% of n-decanol; 10 mol%, 15 mol%, or 20 mol% of 2-butyl-n-octanol; 35 mol%, 40 mol%, 45 mol%, 50 mol% or 55 mol% of high boiling compounds; and smaller amounts of other components. The header current can optionally be incinerated for energy recovery.

In the first scheme, the bottom stream of the ¡-decanol column is directed to an n-decanol column 270 to form a header stream 271 predominantly comprising n-decanol and a bottom stream 272 predominantly comprising compounds of high boiling point The header stream generally comprises at least 90 mol%, at least 95 mol%, at least 98 mol% or at least 99 mol% of n-decanol. The current of n

Decanol is directed to storage and the background current can be optionally incinerated for energy recovery.

In a second of such process schemes generally represented in FIG. 3, the hexaneol purification column bottom stream 225 is fed into a 2-ethyl-hexanol column 245 and fractionated to form a header stream 247 predominantly comprising 2-ethyl-hexanol and a bottom stream 246 which It predominantly comprises n-octanol, n-decanol, 2-ethyl-n-octanol U-decanol) and high boiling compounds. The 2-ethyl-hexanol column is usually operated under vacuum, such as 1 psia, 2 psia, 3 psia or 4 psia (0.07 to 0.3 bara). The header stream generally comprises at least 95 mol%, at least 96 mol%, at least 97 mol% or at least 98 mol% of 2-ethyl-hexanol. The 2-ethyl-hexanol stream can optionally be sold as merchandise (optionally with additional purification) or incinerated for energy recovery. The background stream generally comprises 55 mol%, 60 mol%, 65 mol%, 70 mol%, or 75 mol% of n-octanol; 10 mol%, 15 mol%, or 20 mol% of heavy compounds; 5 mol%, 10 mol%, or 15 mol% of ndecanol; 2 mol%, 5 mol%, or 8 mol% of 2-butyl-n-octanol; 1 mol%, 2 mol% or 3 mol% hexyl hexanoate; and trace amounts of other compounds.

In the second scheme, the bottom stream 246 is fed to a noctanol column 290 and fractionated to form a header stream 291 predominantly comprising n-octanol and a bottom stream 292 predominantly comprising n-decanol and high compounds boiling point such as hexadecanol. The n-octanol column is usually operated with slight pressure, such as 15 psia, 17 psia, 19 psia, 21 psia, 023 psia, 025 psia (1 to 1.5 bara). The header current generally comprises at least 98 mol% or at least 98 mol% of n-octane! The n-octanol stream is sent to storage. The background stream generally comprises 1 mol%, 2 mol%, 3 mol%, or 4 mol% of n-octanol; 20 mol%, 25 mol%, or 30 mol% of ndecanol; 10 mol%, 15 mol%, or 20 mol% of 2-butyl-n-octanol; 2 mol%, 5 mol%, or 8 mol% hexyl hexanoate; 30 mol%, 35 mol% or 40 mol% of high boiling compounds; and trace amounts of other compounds.

In the second scheme, not shown in FIG. 2, the bottom stream 292 is directed to a decanol topping column and fractionated to form a header stream that predominantly comprises 2-ethyl-n-octanol (i-decanol) and a bottom stream that comprises n-decanol and high boiling compounds. The column usually operates under vacuum at a pressure of 1 psia, 2 psia, 3 psia or 4 psia, or 5 psia (from 0.07 to 0.35 bara). The header stream generally comprises 35 mol%, 40 mol%, 45 mol%, 50 mol% or 55 mol% of 2-ethyl-n-octanol; 10 mol%, 15 mol%, or 20 mol% of hexoxyhexane; and 1% in moles, 2% in moles, 3% in moles or 4% in moles of n-dean !. The bottom stream generally comprises 20 mol%, 25 mol% or 30 mol% of ndecanol; 10 mol%, 15 mol%, or 20 mol% of 2-butyl-n-octanol; 35 mol%, 40 mol%, 45 mol%, 50 mol% or 55 mol% of high boiling compounds; and smaller amounts of other components. The header current can optionally be incinerated for energy recovery. The bottom stream of the decanol topping column is fed into an n-decanol column 270 and fractionated to form a header stream 271 predominantly comprising n-decaneol and a bottom stream 272 comprising predominantly high point compounds boiling (for example, hexa-decanol). The column usually operates with a slight vacuum pressure at a pressure of 15 psia, 16 psia, 17 psia 0 18 psia, 19 psia, 20 psia, 21 psia, 22 psia, or 23 psia (from 1 bara to 0, 07 to 1.5 bara). The header current generally comprises at least 98 mol% or at least 99 mol% of n-decanol. The n-decanol stream is directed to storage and the bottom stream can optionally be incinerated for energy recovery.

The present written description uses examples, which include the best mode, and also allow any person skilled in the art to practice the invention, including manufacturing and using any device or system and carrying out any incorporated method. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. It is intended that such other examples be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

It is understood that all the values indicated in this description, even if they are not complemented by the term "approximately" or similar, encompass the explicitly indicated value and the intervals immediately below and immediately above the same characteristic of the tolerance necessary to execute the invention that the person skilled in the art knows or can establish without an excessive burden based on general knowledge in the sector and in view of the teachings of this document.

Examples

Example 1

Various catalysts were prepared as follows.

The HT -1 catalyst was prepared by means of a conventional caption process using two solutions. The first solution contained 17.79 9 of Mg (N03h.6H20 and 26.05 9 of AI (N03b "9H20, dissolved in 48.72 9 of Milli-O water, with a molar concentration of Al

+

1.5 mg. The second solution contained 13.95 9 of NaOH and 9.86 9 of Na, CO, in 68.85 9 of Milli-O water, and was used to produce adequate precipitation of Al and Mg, Y species to adjust the pH of the total mixture at approximately 13. Both solutions were added, with a total flow rate of 20 ml / h for approximately 4 hours to a vessel with vigorous stirring at room temperature. A gel was formed that was allowed to age at room temperature for 1 to 2 hours after which it was filtered and washed with distilled water until no carbonate was detected in the filtered liquid (at pH approximately 7). Subsequently, the solid was dried in an oven at 60 12C for 18 h. The hydrotalcite obtained was calcined in air at 450 I2C and a mixed oxide was obtained, called HT -1, which had a molar ratio of Mg: AI of approximately 1.54 and a surface area (BET method) of 310.37 m2 / g. The BET method refers to the Brunauer-Emmett-Teller isotherm method.

The HT-3 catalyst was prepared by means of a conventional caption process using two solutions. The first solution contained 27.99 9 of Mg (N03h "6H20 and 13.65 9 of AI (N03b" 9H20, dissolved in 55.31 9 of Milli-O water, with a molar concentration of Al

+

1.5 mg. The second solution contained 13.13 g of NaOH and 10.23 9 of Na2C03 in 73.61 9 of Milli-O water, and was used to produce adequate precipitation of Al and Mg, Y species to adjust the pH of the total mixture at approximately 13. Both solutions were added with a total flow rate of 20 ml / h for approximately 4 hours at a

Vessel with vigorous stirring at room temperature. A gel was formed that was allowed to age at room temperature for 12 hours after which it was filtered and washed with distilled water until no carbonate was detected in the filtered liquid (at pH approximately 7). Subsequently, the solid was dried in an oven at 60 (for 18 hours. The hydrotalcite obtained was calcined in air at 450 2C and a mixed oxide, called HT-3, was obtained which had a molar ratio of Mg: AI of approximately 3.10 And a supertieial area (BET method) of 254.03 m '/ g.

The HT-4 catalyst was prepared by means of a conventional coprecipitation process using two solutions. The first solution contained 36.45 9 of Mg (N03) z-6H20 and 13.60 g of AI (N03h "9H20, dissolved in 67.79 g of Milli-Q water, with a molar concentration of Al

+ Mg of 1.5. The second solution contained 12.53 g of NaOH and 16.16 g of Na2C03 in 89.63 g of Milli-Q water and was used to produce adequate precipitation of the Al and Mg Y species to adjust the pH of the total mixture at approximately 13. Both solutions were added, with a total flow rate of 20 ml / h for approximately 4 hours to a vessel with vigorous stirring at room temperature. A gel was formed that was allowed to age at room temperature for 1-2 hours after which it was filtered and washed with distilled water until no carbonate was detected in the filtered liquid (at pH approximately 7). Subsequently, the solid was dried in an oven at 60 2e for 18 hours, calcined in air at 450 2e to produce a mixed oxide, called HT-4, which had a molar ratio of Mg: AI of about 3.80 and a surface area (BET method) of 257 m '/ g.

Catalyst O, 70% Pd / HT -1 was prepared by impregnating the HT-1 catalyst described above with Pd (1.0% by weight, theoretical). The impregnation was carried out by means of the impregnating moisture impregnation method using 0.0360 g of Pd (NH3) 4eI206H20 dissolved in 2 ml of Milli-Q water to impregnate 1.4086 g of HT-1. Once impregnated, the solid obtained was dried in an oven at 100 2e for 12 hours after which it was calcined in air at 450 2e for 6 hours and then reduced to 450 2e in an H2 atmosphere for 3 hours. The resulting Pd / HT-1 material contained approximately 0.70% by weight of Pd as characterized by chemical analysis and ICP-MS.

The 0.78% Pd / HT-3 catalyst was prepared by impregnating the HT-3 catalyst described above with Pd (1.0% by weight, theoretical). The impregnation was carried out by means of the incipient moisture impregnation method using 0.0308 g of Pd (NH3) 4eI206H20 dissolved in 2 ml of Milli-Q water to impregnate 1.4030 9 of HT-3. Once impregnated, the solid obtained was dried in an oven at 100 2e for 12 hours after which it was calcined in air at 450!: Le for 6 hours and then reduced to 450 2e in an H2 atmosphere for 3 hours. The resulting Pd / HT-3 material contained approximately 0.78% by weight of Pd as characterized by chemical analysis and ICP-MS.

Catalyst O, 77% Pd / HT -4 was prepared by impregnating the HT -4 catalyst described above with Pd (1.0% by weight, theoretical). The impregnation was performed by means of the incipient moisture impregnation method using 0.030 9 of Pd (NH3) 4CI206H20 dissolved in 2 ml of Milli-Q water to impregnate 1,014 g of HT-4. Once impregnated, the solid obtained was dried in an oven at 100 pcs for 14-16 hours after which it was calcined in air at 450 µl for 3-4 hours and then reduced to 350 µl in an H2 atmosphere during 3 hours. The resulting Pd / HT-4 material contained approximately 0.77% by weight of Pd as characterized by chemical analysis and ICP-MS.

The 0.77% Pd / 0.2% V / HT-1 catalyst was prepared by impregnating the HT-1 catalyst described above with Pd (1.0% by theoretical weight) and V (0.2% by theoretical weight) . The impregnation was carried out by means of the impregnation method of incipient moisture in two successive stages. In the first stage, 0.0353 g of Pd (NH3) 4CboSH20 dissolved in 2 ml of Milli-Q water was used to impregnate 1.4037 g of HT-1. Once impregnated, the solid obtained was dried in an oven at 100 [deg.] C. for 12 hours. In the second stage, the dry solid was impregnated with 0.0098 g of NH4V03 dissolved in 1 ml of MiIIi-Q water and 1 ml of 0.2 M oxalic acid. Once impregnated, the solid obtained was dried in an oven at 100 [mu] l for 12 hours after which it was calcined in air at 450 pcs for 6 hours and then reduced to 350 pcs in an H2 atmosphere for 3 hours. The resulting Pd / V / HT-1 material contained approximately 0.77% by weight of Pd and approximately 0.2% by weight of V as characterized by chemical analysis and ICP-MS.

The 0.75% Pd / 0.24% V / HT-3 catalyst was prepared by impregnating the HT-3 catalyst described above with Pd (1.0% by weight, theoretical) and V (0.2% by weight, theoretical). The impregnation was carried out by means of the impregnation method of incipient moisture in two successive stages. In the first stage, 0.03 g of Pd (NH3) 4CI2oSH20 dissolved in 2 ml of Milli-Q water was used to impregnate 1.2094 g of HT-3. Once impregnated, the solid obtained was dried in an oven at 100 µl for 12 hours. In the second stage, the dry solid was impregnated with 0.0084 9 of NH, VO, dissolved in 0.5 ml of Milli-Q water and 1 ml of 0.2 M oxalic acid. Once impregnated, the solid obtained was dried in an oven at 100

l / e for 12 hours after which it was calcined in air at 450! le for 6 hours and then reduced to 450 !! C in an H2 atmosphere for 3 hours. The resulting PdN / HT-3 material contained approximately 0.75% by weight of Pd and approximately 0.24% by weight of V as characterized by chemical analysis and ICP-MS.

Catalyst O, 97% Pd / 1% V / HT-4 was prepared by impregnating the HT-4 catalyst described above with Pd (1.0% by theoretical weight) and V (2.0% by weight, theoretical). The impregnation was carried out by means of the impregnation method of incipient moisture in two successive stages. In the first stage, 0.0270 9 of Pd (NH3), CI2.6H20 dissolved in 2 ml of Milli-Q water were used to impregnate 1.0 g of HT-4. In the second stage, V (2.0%, theoretical) was impregnated in the solid with 0.0460 g of NHN03 dissolved in 2 ml of Milli-Q water. Once impregnated, the solid obtained was dried in an oven at 100 2C for 14-16 hours after which it was calcined in air at 450 2C for 6 h and then reduced to 350 2C in an H2 atmosphere for 3 hours . The resulting Pd / V / HT-4 material contained approximately 0.97% by weight of Pd and approximately 1.0% by weight of V as characterized by chemical analysis and ICP-MS.

The 0.29% Ga / HT-4 catalyst was prepared by a conventional coprecipitation process using two solutions. The first solution contained 29.89 9 of Mg (N03) 2'6H20, 10.90 9 of AI (N03h'9H20 and 0.06 9 of Ga (N03h'9H20 dissolved in 55.2 ml of Milli-Q water, with a molar concentration of (Al + Mg + Ga) of 1.5 The second solution contained 12.52 g of NaOH and 10.52 g of Na2C03 in 72.6 ml of Milli-Q water, and was used to produce adequate precipitation of the Mg, Al and Ga species, and to adjust the pH of the total mixture to approximately 13. Both solutions were added, with a total flow rate of 30 ml / h for approximately 4 hours to a container with vigorous stirring at room temperature A gel was formed that was allowed to age at room temperature for 1-2 hours after which it was filtered and washed with distilled water until no carbonate was detected in the filtered liquid (at pH approximately 7) The solid obtained was dried in an oven at 60 ° C for 14-16 hours The hydrotalcite (Ga-HT-4) obtained was calcined in air at 450 ° C for 3-4 hours to obtain having a mixed oxide having a molar ratio of Mg: AI of about 3.8, a Ga content of 0.29% by weight (measured by chemical analysis and ICP-MS), and a surface area (BET method ) of 262 m '/ g.

Catalyst O, 87% Pd / O, 29% Ga / HT -4 was prepared by the process described above with respect to catalyst O, 29% GalHT-4 in which the incorporation of Pd (1.0% by weight, theoretical) in the Ga-HT-4 material was carried out by means of the impregnation method of incipient moisture with 0.03 9 of Pd (NH3), CI, '6H, O dissolved in 1.7 ml of Milli-Q water, to impregnate 1.1 9 of O, 29% Ga-HT -4. The solid obtained was dried in an oven at 100 µl for 14-16 hours after which it was calcined in air at 450 µl for 3-4 hours and then reduced to 350 pe in an H2 atmosphere for 3 hours. The resulting Pd / O, 29% Ga-HT-4 material contained approximately 0.87% by weight of Pd as characterized by chemical analysis and ICP-MS.

The 0.97% Pd / O catalyst, 29% V / O, 29% GalHT-4 was prepared by the process described above with respect to the 0.29% Ga / HT -4 catalyst in which the incorporation of Pd (1.0% by weight, theoretical) and V (0.2% by weight, theoretical) in the Ga-HT-4 material was carried out by means of the impregnating method of incipient moisture in two successive stages. In the first stage, 0.0355 9 of Pd (NH3), CI, 6H, O dissolved in 2 ml of Milli-O water was used to impregnate 1.4072 g of O, 29% Ga-HT-4. The solid obtained was dried in an oven at 100 2C for 14-16 hours after which V (0.2%, theoretical) was impregnated in the solid with 0.0096 g of NH4 V0 3 dissolved in 1 ml of MiIIi water -Q and 1 ml of 0.2 M oxalic acid. The solid was dried in an oven at 100 2C for 12 hours after which it was calcined in air at 450 2C for 6 hours and then reduced to 350 QC in an atmosphere of H2 for 3 hours. The resulting Pd / V / 0.29% Ga-HT-4 material contained approximately 0.97% by weight Pd and approximately 0.29% V as characterized by chemical analysis and ICP-MS.

The catalyst 4.9% Cu / HT -4 was prepared by means of a conventional coprecipitation process using two solutions. The first solution contained 30.08 9 of Mg (NO,), '6H, O, 10.44 9 of AI (NO'), '9H, O and 1.17 9 of Cu (NO,),' 3H, Or dissolved in 57.62 ml of Milli-Q water, with a molar concentration of (Al + Mg + Cu) of 1.5. The second solution contained 13.05 g of NaOH and 10.52 g of Na2C03 in 74.71 ml of Milli-O water, and was used to produce adequate precipitation of the Mg, Al YCu species, and to adjust the pH of the total mixture at approximately 13. Both solutions were added (total flow rate = 30 ml / h for approximately 4 hours) to a vessel with vigorous stirring at room temperature. A gel was formed that was allowed to age at room temperature for 1 to 2 hours after which it was filtered and washed with distilled water until no carbonate was detected in the filtered liquid (at pH approximately 7). The solid was dried in an oven at 60 'C for 18 hours and the hydrotalcium (Cu-HT-4) obtained was calcined in air at 450 2e for 3-4 hours to obtain a mixed oxide with a molar ratio of Mg: AI of approximately 3.8, a Cu content of 4.9% by weight (characterized by chemical analysis and ICP-MS) and a surface area (BET method) of 190.08 m2 / g.

Catalyst O, 98% Pd / O, 2% V / 4.9% Cu / HT-4 was generally prepared according to the method for preparing the catalyst 4.9% Cu / HT-4 described above. in which the incorporation of Pd (1.0% by weight, theoretical) and V (0.2% by weight, theoretical) in the 4.9% Cu-HT-4 material (Mg + Cu / AI == 4) was carried out by means of the impregnating method of incipient moisture in two successive stages. In the first stage, 0.035 g of Pd (NH3) 4CI2 · 6H20 dissolved in 2 ml of Milli-Q water was used to impregnate 1.4 g of 4.9% Cu-HT-4. The solid obtained was dried in an oven at 100 QC for 12 hours. The solid was impregnated with V (0.2%, theoretical) with 0.009 g of NH4V03 dissolved in 1 ml of Milli-Q water and 1 ml of 0.2 M oxalic acid. The impregnated solid was dried in an oven at 100 QC for 12 hours after which it was calcined in air at 450 QC for 6 hours and then reduced to 350 QC in an H2 atmosphere for 3 hours. The resulting 0.98% Pd / 0.2% V / 4.9% Cu / HT-4 material contained approximately 0.98% by weight of Pd and 0.20% V as characterized by chemical analysis. and ICP-MS.

Example 2

The catalytic activity for the conversion of ethanol into n-butanol and ethanol and n-hexanol into noctanol by condensation of Guerbet was evaluated for the various catalysts described above. In each of the experiments, 1750 mg (38 mmol) of ethanol, 1790 mg (17.5 mmol) of n-hexanol and 350 mg of one of the catalytic materials described above were introduced into a stainless steel autoclave reactor of 12 ml stirred with PEEK (polyether ethyl ketone). The reactor was hermetically sealed, and the system contained a first connector to a pressure gauge (pressure gauge), a second connector for gas charging and a sampling outlet port. The reactor was initially pressurized with 24 bar of N2, and heated to 250 QC to form a gas with continuous stirring, until the total system pressure reached approx. 35-40 bar (reaction time = O). Liquid samples of about 50 to 100 111 were taken after 5 hours of reaction time. The samples were filtered and diluted to 2% by weight of chlorobenzene in a standard acetonitrile solution, and analyzed by gas chromatography on a GC-3900 Varian equipped with an FID detector and

a capillary column 60-m TRB-624.

5 1O

The results are reported in the following Table 1 in which the conversion is calculated by: «starting moles - final moles) / (starting moles)) * 100; and the yield is calculated by: "moles of product) / (moles of all products)) * (conversion of ethanol / 100). In Table 1, "Exp." Refers to the experiment number, "Conv. EtOH" refers to the conversion of ethanol, "Conv. Hex" refers to the conversion of n-hexanol, "Yield of BuOH" refers to the yield of n-butanol, "OcO H yield" refers to the yield of n-octanol, and "Yield of C4 + OH" refers to the total yield of linear alcohols having 4 or more carbon atoms (including n-butanol and noctanol) in the that "A" refers to linear and "Ramif" refers to branched.

Table 1

Exp

Catalyst Conv EtOH Conv. HeO H Performance of BuOH OcOH performance C •• OH performance

A.

Ramif

one

HT-1 11, 4 3.3 0.25 0.18 0.4 °

2

HT-3 11.2 2.8 1.50 1.08 2.5 °

3

HT-4 22.3 3.4 10.56 3.95 14, 9 0.4

4

0.70% Pd / HT-1 36.6 10.3 14.50 6.20 21, 7 0.9

5

0.78% Pd / HT-3 34.7 8.7 9.44 4.24 14, 4 1.3

6

0.77% Pd / HT-4 34.5 8.6 13.21 6.42 21, 3 1.0

7

0.77% Pd / 0.20% V / HT-1 61.6 23.2 11, 61 7.82 25, 4 1.4

8

0.75% Pd / 0.24% V / HT-3 76.2 18.0 17.57 19.55 42, 2 2.4

9

0.97% Pd / l, 0% V / HT-4 37.4 11, 1 15.46 8.55 23rd 1.0

10

0.29% GalHT-4 26.4 4.6 8.77 3.78 12, 6 0.4

eleven

0.87% Pd / 0.29% GalHT -4 42.6 21, 3 16.52 5.69 19 ° 1.1

12

O, 97% Pd / O, 29% V / O, 29% Ga / H T-4 40.9 10.7 14.93 8.3 25, 6 1.1

13

4.9% Cu / HT-4 22.4 8, 0 4.03 4.99 9.6 0.8

14

0.98% Pd / 0.2% V / 4.9% Cu / HT4 36.1 7.9 7.28 3.87 13, 1 0.4

The results show that the incorporation of vanadium in catalysts derived from hydrotalcite with different proportions of Mg / AI in its structure get higher

5 yields of both n-butanol and n-octanol, and in general, higher yield of C4 + alcohols and improved catalytic activity (conversion of ethanol and n-hexanol) compared to analog catalysts that do not contain vanadium.

Comparison of the results of experiments 3, 6 and 9 to 12 shows that the

The incorporation of vanadium in the hydrotalcite-derived catalysts comprising Ga in the structure provides higher yields of n-octanol, and in general, higher yield of C4 + alcohols than analog catalysts without vanadium. This effect occurs even with concentrations of V less than 0.3%, as can be seen in Figure 4. This indicates the greater stability of the catalysts under the conditions of

15 reaction

The comparison of the results of the experiments 6, 8, 9, 11, 13 and 14 shows that the incorporation of vanadium in the catalysts derived from hydrotalcite with different proportions of Mg / AI provides higher yields of n-octanol, and in general, higher

20 yield of C4 + alcohols than analog catalysts without vanadium. However, the production of C4 + OH decreases considerably when the catalyst comprises Cu in its structure, even in the presence of Pd and V. This indicates the greater stability of the catalysts under the reaction conditions.

Example 3

Catalytic activity for catalysts O, 77% Pd / HT-4, O, 97% Pd / l, O% V / HT-4 and

5 O, 87% Pd / O, 29% Ga / HT-4 was evaluated for a reaction mixture comprising ethanol without n-hexanol. In each of the experiments, 3,500 mg (76 mmol) of ethanol and 200 mg catalyst were introduced into a 12 ml stainless steel autoclave reactor coated with PEEK. The reactor was tightly closed, and the system contained a first connector to a pressure gauge (pressure gauge), a second connector for gas charging and

10 an output port for sampling. The reactor was initially pressurized with 24 bar of N2, and heated to 200 0 e to form a gas with continuous stirring, reaching full system pressure at approximately 30 bar (reaction time = O). Liquid samples of approximately 50 to 100 ~ I were taken after 5 hours of

reaction. The samples were filtered and diluted in a standard solution of chlorobenzene 15 2% by weight in acetonitrile, and analyzed by gas chromatography on a Varian 3900 GC-FID equipped with a capillary column and TRB-624. The percentage conversion in

moles of ethanol ("Conv. EtOH") was calculated by: (initial moles of ethanol -moles

end of ethanol) I (initial moles of ethanol) * 100. The results are presented in the following Table 2 where "Lin." refers to linear and "Ramif." refers to branched. The

20 values in square brackets refers to the molar yield in% of the products.

Table 2

Ex.

Catalyst Conv. Seleet Seleet Seleet Seleet

EtOH

nBuOH nHeOH nOelOH

C4 + alcohols

Lin.

Rami!

one

0.77% Pd / HT-4 15.5 76.9 12.3 2.6 [0.4] 93.9 1.2

[11, 9]

[1, 9] [14.6] [0.2]

2

0.97% Pd / I, 0% V / HT-4 14.0 66, S 13.0 1.6 [0.2] S3.1 0.5

[9, 4]

[I, S] [11, 6] [0.11

3

0, S7% Pd / O, 29% Ga-HT-4 15, S 76.5 12.0 1.9 [0, 3] 1.4 1.6

[12.1]

[1, 9] [14.4] [0.3]

Other reaction products included aldehydes (ethanal, butanal, hexanal), ethyl acetate and diethoxyethane.

These results show that the catalysts derived from hydrotalcite and containing Pd, and the combinations of Pd / Ga and PdN in the structure provided higher yields of n-butanol and 1-hexanol, while the yields of n-octanol and especially C4 alcohols + are considerably reduced thereby maximizing the yield of n-butanol.

Example 4

Catalytic activity for catalysts O, 77% Pd / HT-4, O, 97% Pd / 1, O% V / HT-4, 0.87% Pd / O, 29% GalHT-4 and 0.97% Pd / O, 29% V / O, 29% Ga / HT-4 was evaluated for a reaction mixture comprising n-butanol and no ethanol or n-hexanol. In each of the experiments, 35,000 mg (47 mmol) of n-butanol, 1790 mg and 200 mg catalyst were introduced into a 12 ml stainless steel autoclave reactor coated with PEEK. The reactor was hermetically sealed, and the system contained a first connector to a pressure gauge (pressure gauge), a second connector for gas charging and a sampling outlet port. The reactor was initially pressurized with 24 bar of N2, and heated to 250 or e to form a gas with continuous stirring, reaching full system pressure at approximately 35-40 bar (reaction time = O). Liquid samples of approximately 50 to 1 00 ~ I were taken after 5 hours of reaction time. The samples were filtered and diluted in a standard solution of 2% by weight chlorine benzene in acetonitrile, and analyzed by gas chromatography on a Varian 3900 GC-FID equipped with a capillary column and TRB-624. Conversion and selectivity were calculated as previously. The yield was calculated according to: {[(moles of praducta) / (total evils of all praducta)] "(canon of EtOH)) / 100. The results are presented in the following Table 3 where" Lin. "Refers to linear and "Ramif." refers to branched. Bracketed values refers to the molar yield in% of products.

Table 3

Ex

Catalyst Conv. n-BuOH Select n-butanal Select Other Ald. Select n-DctOH Performance Alcohols C4 +

1 2 3 4

0.77% Pd / HT-4 0.97% Pd / 1.0% V / HT-4 0.87% Pd / O, 29% Ga / HT-4 O, 97% Pd / O, 29% V / O, 29% G a / HT-4 17.1 35.5 32.9 25.9 16.9 3.5 [0.6) [2.9] 3.9 [1, 4] 1.6 [0.6] 5.3 [1, 7] 1.8 [0.6] 7, 4 [1, 9] 2.0 [0.5] Lin. Rami L 0.6 [0.1] 37.7 30.9 [6.4] [5.3] 1.7 [0.6] 63.3 18.0 [22.5 [6.4]] 0.6 [0.2] 64.0 20.6 [21, 1 [6.8]] 0.7 [0.2] 57.0 25.2 [14.8 [6.5]]

The results show that the catalyst of the invention with butanol as a reagent does not produce octanol in a high percentage. In addition, the percentage of branched products is 5 higher than when neither hexanol nor ethanol is used in the reaction mixture. Therefore, it is shown that hexanol and ethanol are required to obtain high octane yields!

Example 5

The composition of the feed and product streams of the butanol reactor and the feed and product streams of the octanol reactor were simulated for a process depicted in FIG. 2. The process was simulated with Aspen Plus version 7.1. A two-liquid non-random activity coefficient (NRTL) model was used with the Redlich-Kwong equation of state, defining the non-condensable components by

15 coefficients of Henry's law. The butanol and hexanol reactors were modeled with kinetic reactors and the distillation columns were modeled with Radfrac models. The simulated results are presented in Table 5 in mol%.

Table 5: Simulated compositions of the feed and product streams of the octanol reactor and the butanol reactor.

Butanol IRactor Octanol Reactor Examples 6 to 11

Component

Feeding Product Feeding Product

n-butanol

0.03 10.6 0.015 2.34

2-butanol

0.3 0.38 0.15 0.24

Ethanol

80.2 45.6 42 28.4

Water

2.3 16.2 1.17 9.37

Acetaldehyde

0.009 0.94 0.012 0.49

Butiraldeh Id

0.44 0.57 0.23 0.029

Hexanaldehyde

° ° 0.005 0.47

ethyl acetate

0.066 0.12 0.03 0.14

n-hexanol

° 1.46 32.0 25.4

n-octanol

° 0.2 ° 2.5

n-decanol

° 0.034 ° 0.29

2-ethyl-l -bu tanol

° 0.26 1.05 1.05

2-ethyl-1-hexanol

° 0.056 ° 0.35

2-butyl -1-octanol

° ° ° 0.31

Pentane

° ° 0.015 0.57

Methane

0.096 0.43 0.14 0.30

Ethane

° 0.27 0.09 0.11

Propane

° 0.09 0.025 0.06

hydrogen

16.0 20.3 22.2 25.2

carbon dioxide

0.28 0.85 0.27 0.69

carbon monoxide

0.32 1.65 0.6 1.63

In the following examples 6 to 11, "Exp" refers to the experiment number, "'{;" it means

at the reaction temperature, "Bar" refers to the reaction pressure, "EtOH velocity"

refers to the feed rate of ethanol in moles per hour, "H2IEtOH" refers to

the mole ratio of hydrogen to ethanol, "LHSV" refers to the liquid velocity of the reactor, "x-EtOH" refers to the amount of ethanol conversion, "s-BuOH" refers to the Butanol selectivity, "Yield" refers to butanol yield, "AAlEtOH" refers to the mole ratio of aldehyde with

5 with respect to ethanol and "CO / EtOH" refers to the mole ratio of carbon monoxide with respect to ethanol.

Example 6

In a fluid bed reactor, constructed in a 154 cm long and 2.5 cm diameter stainless steel reactor, a constant flow of gas phase reactants was contacted with 100 9 of an oxide Guerbet catalyst metallic comprising palladium. The reactor was connected to a synthesis loop, which contained a pressure gauge (gauge), a reagent inlet connector and an outlet connector. The pressure of

The reactor operation was controlled by a valve located in the output stream. After the desired operating pressure was reached, the reagents were introduced into the reactor synthesis loop. The composition of the output stream was measured by gas chromatography on a GC-Agilent 7890N equipped with an FID and TCD detector, a 30 m Rt-U PLOT capillary column and two columns packed in series

20 (PORAPPACK OS, 3.6 m long, and CARBOXEN 1000, 4.5 m long).

The results of ethanol conversion, butanol selectivity and butanol yield, measured after it was determined that the composition of the output stream was stable, are reported in the following Table 6A. The proportions of n-butanol with respect to

25 hexanol (BuOH / HexOH), octanol (BuOH / OctOH), -Butanol (BuOH / IBuOH), 2-Butanol (BuOH / 2-BuOH) and 2-ethyl-1-butanol (BuOH / 2-EI-1 -BuOH) in the product range are reported in the following Table 68.

Table 6A Table 6B Example 7

Supply current

Product stream

Exp

' C Pub EtOH speed H, IEtOH LHSV x-EtOH s-BuOH performance

101

220 28 2.84 0.4 1.4 5.76 79.30 4.57

Supply current

Product stream

Exp

' C Pub EtOH speed H, / EtOH LHSV x-EtOH s-BuOH performance

102

240 28 2.84 0.4 1.4 12.08 78.56 9.49

103

250 28 2.84 0.4 1.4 15.70 77.44 12.16

104

250 28 3.49 0.39 1.75 14.48 77.48 11, 22

105

250 40 3.49 0.39 1.75 12.31 77.52 9.54

106

250 fifty 3.49 0.39 1.75 11, 65 78.25 9.12

107

220 30 2.84 0.1 1.4 10.20 76.70 7.82

108

220 28 2.84 0.4 1.4 5.76 79.30 4.57

109

250 28 2.84 0.4 1.4 15.70 77.44 12.16

11 0

250 28 3.49 0.39 1.75 14.48 77.52 11, 23

111

245 Four. Five 3.00 0.5 1.5 10.94 81.30 8.89

11 2

230 30 2.40 0.2 1.2 9.81 79.15 7.76

11 3

230 60 3.58 0.2 1.8 4.92 83.70 4.12

114

230 30 3.58 0.8 1.8 4.71 82.43 3.88

11 5

230 60 2.40 0.8 1.2 4.60 71.07 3.27

11 6

260 30 2.40 0.8 1.2 13.28 78.78 10.46

117

260 60 3.58 0.8 1.8 10.04 83.85 8.42

11 8

245 Four. Five 3.00 0.5 1.5 9.04 82.06 7.42

11 9

260 60 2.40 0.2 1.2 21.24 78.59 16.69

120

260 30 3.58 0.2 1.8 18.63 76.49 14.25

121

260 60 2.40 0.2 1.2 18.53 79.24 14.68

122

230 30 3.58 0.26 1.8 6.71 80.81 5.42

Exp

BuOH / HexOH BuOH / OctOH BuOH / liluOH BuOH / 2-BuOH BuOH / 2-Et-l-BuOH

101

18.44 454.97 323.80 > 1000 99.85

102

14.64 198.17 440.04 240.45 78.81

103

13.72 168.08 436.84 258.30 74.41

104

14.23 182.98 451, 05 250.52 80.92

105

15.51 212.50 442.88 236.81 91, 01

106

15.82 231, 86 621, 89 229.92 94.34

107

10.83 11 2.23 290.73 > 1000 55.33

108

18.44 454.97 323.80 > 1000 99.85

109

13.72 168.08 436.84 258.30 74.41

11 0

14.23 182.98 451, 05 250.52 80.92

111

16.91 266.65 583.66 214.09 94.79

11 2

15.66 240.96 339.75 218.56 87.68

11 3

24.84 633.96 379.03 155.18 146.80

114

33.86 1104.27 378.20 107.06 201, 66

11 5

30.94 1902.63 529.77 105.50 210.25

11 6

24.88 469.54 464.80 127.84 146.85

11 7

29.37 801, 26 547.82 122.70 184.25

11 8

21, 46 399.23 437.18 136.70 140.03

11 9

1130 122.25 726.00 244.37 66.52

120

12.17 134.55 422.38 209.57 78.21

121

12.17 145.28 764.18 230.90 74.47

122

19.60 386.46 311, 29 146.17 132.17

The experiments were carried out following the protocol detailed in Example 6. The results of ethanol conversion, butanol selectivity and butanol yield are reported in the following Table 7A. The proportions of n-butanol with respect to hexanol

(BuOH / HexOH), octanol (BuOH / OctOH),; -Butanol (BuOH / lBuOH), and 2-Butanol (BuOH / 2

BuOH) in the product stream are reported in the following Table 7B.

Table 7A

Supply current

Product stream

Exp

' C Pub EtOH speed H, IEtOH LHSV x-EtOH s-BuOH performance

20 1

245 Four. Five 3.00 0.5 1.5 9.77 82.93 8.10

202

231 60 2.40 0.4 1.2 6.19 85.00 5.26

203

248 57 2.40 0.4 1.2 12.32 82.57 10.17

204

244 63 1.80 0.35 0.9 12.10 82.58 9.99

205

256 75 2.00 0.35 one 15.92 82.01 13.06

206

257 30 2.40 0.42 1.2 18.11 77.39 14.02

207

257 30 3.60 0.43 1.8 14,12 78.76 11, 12

208

260 30 3.60 0.4 1.8 15.67 77.84 12.19

209

265 75 2.40 0.4 1.2 19.11 80.30 15.35

210

263 51 1.80 0.55 0.9 21, 32 79.10 16.87

211

254 49 2.40 0.4 1.2 15.17 80.68 12.24

212

254 40 2.40 0.4 1.2 15.93 79.79 12.71

213

245 Four. Five 3.00 0.5 1.5 9.06 82.06 7.43

214

260 60 3.60 0.4 1.8 14.36 79.84 11.47

215

260 30 3.60 0.4 1.8 15.77 77.28 12.18

216

260 70 3.60 0.4 1.8 15.16 77.51 11, 75

217

245 Four. Five 3.00 0.5 1.5 9.39 82.16 7.71

218

250 fifty 2.40 0.4 1.2 13.11 80.54 10.56

Supply current

Product stream

Exp

' C Pub EtOH speed H, / EtOH LHSV x-EtOH s-BuOH performance

219

250 60 2.40 0.31 1.2 13.90 81.17 11.29

220

250 60 2.40 0.68 1.2 10.40 83.78 8.71

Table 7B

Exp

BuOH / HexOH BuOH / OctOH BuOH / iBuOH BuOH / 2-BuOH BuOH / 2-Et-l-BuOH

20 1

18.34 258.53 584.83 139.31 122.83

202

22.64 477.10 425.24 134.24 142.59

203

16.33 224.38 481, 95 171, 13 118.97

204

15.94 203.06 513.85 164.79 101.71

205

14.59 170.88 530.92 185.85 91, 37

206

12.88 125.37 359.87 171, 93 83.00

207

15.91 192.99 339.29 174.85 106.73

208

14.88 171, 78 335.57 161, 63 98.63

209

13.09 146.68 544.99 201, 47 83.12

210

12.56 129.63 504.05 193.98 77.51

211

14.93 181, 84 436.44 177.83 96.12

212

14.27 168.38 408.94 176.66 91, 67

213

20.96 374.31 466.86 132.67 141.10

214

13.72 146.99 461, 59 178.41 94.02

215

13.41 132.82 359.38 169.79 91, 68

216

14.85 136.60 347.50 159.42 102.17

217

19.22 296.05 421, 94 138.52 131.78

218

14.75 163.69 457.37 173.25 97.45

Exp

BuOH / HexOH BuOH / OctOH BuOH / tBuOH BuOH / 2-BuOH BuOH / 2-Et-l-BuOH

219

13.70 161, 93 485.39 190.26 89.56

220

19.35 298.55 600.06 148.33 131, 60

Example 8

The experiments were carried out following the protocol detailed in Example 6. The results of ethanol conversion, butanol selectivity and butanol yield are reported in the following Table BA. The proportions of n-butanol with respect to hexanol

(BuOH / HexOH), octanol (BuOH / OctOH),; -Butanol (BuOH / tBuOH), and 2-Butanol (BuOH / 2

BuOH) in the product stream are reported in the following Table 8B.

10 Table 8A Table 8B

Supply current

Product stream

Exp

'C Pub EtOH speed H, IEtOH AAlEtOH LHSV x-EtOH s-BuOH performance

301

231 60 2.38 0.4 0.01 1.2 5.66 84.57 4.79

302

254 49 2.38 0.4 0.01 1.2 15.27 81, 73 12.48

303

254 40 2.38 0.4 0.01 1.2 15.80 81.82 12.93

304

256 75 1.98 0.35 0.01 one 15.40 83.32 12.83

305

260 30 3.56 0.4 0.01 1.8 15.42 82.23 12.68

306

263 51 1.78 0.55 0.01 0.9 20.41 81.33 16.60

307

265 75 2.38 0.4 0.01 1.2 18.24 82.52 15.05

308

260 30 3.56 0.2 0.01 1.8 18.43 77.65 14.31

309

260 60 3.56 0.4 0.01 1.8 13.82 82.9 1 11, 45

310

260 30 3.56 0.4 0.01 1.8 15.45 81.18 12.54

311

260 60 3.56 0.8 0.01 1.8 10.65 85.75 9.13

Ex p

BuOH / HexOH BuOH / OctOH BuOH / tBuOH BuOH / 2-BuOH BuOH / 2-Et-t-BuOH

30 1

18.37 303.05 332.98 137.53 104.25

30 2

12.83 137.25 392.29 192.74 78.00

30 3

12.55 121.92 368.71 192.19 78.91

30 4

13.41 150.51 494.32 204.24 81.61

30 5

13.66 142.65 332.52 18 1.08 89.29

30 6

11, 97 114.87 505.93 204.04 73.36

30 7

12.72 133.20 520.59 216.79 78.82

30 8

9.83 72.46 340.54 224.50 63.74

30 9

12.90 133.35 420.50 220.32 84.83

31 OR

13.02 128.38 373.88 192.07 84.48

31 1

17.79 241.92 563.87 155.26 116.68

Example 9

The experiments were carried out following the protocol detailed in Example 6. The

experiment A 101 was processed at 245!: le and all other experiments at 260 2e. The

experiments A211 and A212 contained BuOH in the feed at a rate of 1.16

mol / h (38% by mole of alcohol feed) and 3.92 moVh (51% by mole of alcohol feed), respectively. The results are reported in the following Tables 9A and 98. In Table 98, the results of the product stream are reported in mole% in which PeOH refers to pentanol, 2-Et-1-BuOH refers to 2-ethyl-1-butanol,

5 HexOH refers to hexanol, OctOH refers to octanol, DecOH refers to decanol, DodecOH refers to dodecanol, and TetOH refers to tetradecanol.

Table 9A

Supply current

Product stream

Exp

Pub EIOH speed d H, IEIO H LHS V COI EIO H AA! EIO H H, OI EIO H xEIO H sBuO H Performance

At 1

Four. Five 3.00 0.5 1.6 --- --- --- 11.47 80.38 9.22

To 2

30 3.00 0.5 1.6 --- --- --- 20.67 72.82 15.06

Al to 3

40 3.00 one 1.6 - --- ___or 15.16 78.94 11, 97

A20 1

31 3.00 0.5 1.6 --- --- 0.01 22.77 65.14 14.83

A20 2

41 3.00 one 1.6 --- --- 0.01 17.10 73.69 12.60

A20 3

33 3.30 0.5 1.8 --- --- 0.05 15, 12 64.50 9.75

A20 4

43 3.30 one 1.8 --- --- 0.05 10.46 72.06 7.54

A20 5

33, 1 3.03 0.57 1.7 --- 0.05 ___or 19.64 71.34 14.01

A20 6

Four. Five 3.00 1.14 1.7 --- 0.05 ___or 10.62 79.46 8.44

TO 20

30 2.81 0.5 1.6 --- 0.05 ___or 19.35 71.43 13.82

Supply current

Product stream

Exp

Pub EtOH speed d H, / EtO H LHS V IOC EtO H AN EtO H H, OI EtO H xEtO H sBuO H Performance

7

A20 8

40 2.85 one 1.6 --- 0.05 ___or 15.57 74.33 11, 57

A20 9

30 2.68 0.5 1.6 --- 0.10 --- 28.99 48.36 14.02

A2 1 O

40 2.68 one 1.6 --- 0.10 ___or 19.53 58.61 11, 44

A2 1 1

30 1.87 0.5 2.0 --- --- --- 45.76 33.44 15.30

A2 1 2

40 3.75 0.5 4.0 --- --- --- 15.42 0.00 0.00

A2 1 3

31 3.00 0.5 1.6 0.05 --- --- 7.96 76.03 6.05

A2 1 4

41 3.00 one 1.6 0.05 --- ___or 6.60 76.25 5.03

Table 9B

Exp

BuOH PenOH 2-Et-l -BuOH Hex OctOH DecOH DodecOH TetOH

Al0 1

80.4 0.11 1.2 8.6 0.92 0.14 0.09 0.04

Al02

72.8 0.18 1.75 12.2 2.39 0.69 0.19 0.07

Al03

78.9 0.15 1.17 8.91 1.11 0.17 0.08 0.04

A20 1

65.1 0.34 2.28 13.7 3.89 2.13 1.01 0.38

A202

73.7 0.2 1.74 11.8 2.16 0.6 0.17 0.05

A203

64.5 0.16 2.66 fifteen 3.67 1.25 0.43 0.18

Exp

BuOH PenOH 2-Et-l -BuOH Hex OctOH DecOH DodecOH TetOH

A204

72.1 0.2 2.02 11.6 1.83 0.35 0.11 0.06

A205

71.3 0.19 2.43 14 3.27 1.22 0.47 0.18

A206

79.5 0.15 1.3 9.28 1.18 0.21 0.08 0.04

A207

71.4 0.19 2.1 13.5 3.02 1.05 0.35 0.12

A208

74.3 0.21 1.98 12.2 2.5 0.97 0.34 0.15

A209

48.4 0.23 3.32 fifteen 5.76 4.31 4.48 3.74

A210

58.6 0.18 3.05 14.8 4.95 0.03 2.55 1.38

A211

33.4 0.3 5.33 36.2 7.3 1.95 0.73 0.21

A212

° ° 8.64 61.1 7.56 1.44 0.39 0.09

A213

76 0.2 0.52 4.1 0.31 ° ° °

A214

76.3 ° 0.42 3.11 0.17 0.07 ° 0.05

Experiments A211 and A212 were terminated prematurely due to the heavy components that were generated that blocked the GC input port. The tests of acetaldehyde with a mole ratio of 0.2: 1 with respect to ethanol stopped because the temperature increased by more than 30 pe above the set point.

Example 10

The experiments were carried out following the protocol detailed in Example 6 but in which the reactor was a fixed-bed stainless steel reactor 33 cm long and 0.83 cm in diameter, a constant flow of the reagents and 50 ml / minute of N2 to the reactor, a catalyst charge in the reactor of 3 g was used, and a GCAgilent 6agON apparatus was used. The results of ethanol conversion, butanol selectivity and

The yield of butanol is reported in the following Table 10A. The proportions of n

butanol with respect to hexanol (BuOH / HexOH), octanol (BuOH / OctOH),; -Butanol

(BuOH / 1BOH), and 2-Butanol (BuOH / 2-BuOH) in the product stream are reported in the following Table 10B in which "n.d." Refers to undetected. The analyzes indicated the absence of ¡-Butanol and 2-Butanol.

20 Table 10A

Power supply

Product stream

Exp

'C Pub EtOH speed H, / E10H LHSV AN EtOH x-EtOH x-AA s-BuOH performance

B1 01

220 76 0.079 0.95 1.2 0.01 8.3 74.9 87.04 7.2

B1 02

240 76 0.079 0.68 1.2 0.01 9.5 60.3 84.97 8.0

B103

250 76 0.079 0.68 1.2 0.02 10.9 79.8 83.81 9.1

B104

250 76 0.079 0.95 1.2 0.02 9.0 87.3 84.11 7.6

B105

250 66 0.079 0.95 1.2 0.02 13.4 86.2 84.12 11.2

B1 06

250 76 0.056 1.01 0.93 0.11 9.4 95.2 66.21 6.2

B1 07

220 76 0.056 1.45 0.93 0.11 11.6 96.0 66.48 7.7

Table 10B

Exp

8uOH / HexOH 8uOH / OctOH 8uOH / 2-Et-1-8uOH

8 101

22.54 n.d. 110.81

81 02

16.60 n.d. 92.20

81 03

13.92 n.d. 73.10

81 04

15.79 n.d. 75.92

81 05

16.14 n.d. 78.77

81 06

5.73 36.80 n.d.

81 07

6.12 40.53 n.d.

Example 11

The experiments were carried out following the protocol detailed in Example 6 at a temperature of 260 2e, a pressure of 40 bara and an LHSV of 1.84. The reactor gas stream and reactor product streams comprising n · butanol were produced continuously. The gas stream was recycled into the reactor and the product stream was fractionated to generate recycled ethanol and a product stream comprising nbutanol among other components. A mole ratio of hydrogen to ethanol of 0.4: 1 was used in the reaction. No feed of 5 soda hydrogen was introduced into the reactor. After the starting operation times (i.e., soda catalyst), the gas and the product stream comprising n-butanol were analyzed after 755 hours, 778 hours, 789 hours, 801 hours and 813 hours. The concentrations of ca and CO 2 (in mole%) are reported in the following Table 11 A. The composition of the reactor product stream is also reported in the following Table 10 including (i) the ethanol conversion percentage ("xEtOH % "); (ii) the concentration of ethyl acetate ("EAc"), the concentration of acetaldehyde ("AA"), the concentration of 2butanol ("2-BuOH"), the concentration of n-butanol r n-BuOH "), pentanol concentration

("PentOH"), the concentration of 2-elyl-1-butanol ("2-Et-1 -BuOH"), the concentration of

hexanol ("HexOH"), the concentration of 2-ethylhexanol ("2-Et-HexOH"), the concentration of octanol ("OctOH"), the concentration of 2-ethyl-1-octanol ("2-Et- 1-0ctOH "), the concentration of decanol (" DecOH "), and the concentration of dodecanol (" DodecOH ") are reported in% in

moles and (iii) the yield of bulanol (BuOH%).

Table 11 A

Soda

755 hours 778 hours 789 hours 801 hours 813 hours

CO

° 0.022 0.022 0.051 0.03 1 0.024

CO,

0.014 0.11 6 0.1 0.099 0.108 0.107

xEtOH%

16.9 14.6 15.3 16.1 15.4 15.2

EAc

0.486 0.556 0.554 0.56 0.562 0.579

AA

2.81 2.88 2.95 2.88 3.06 3.22

2-BuOH

1.08 1.02 1.18 1.06 1.08 1.1

n-BuOH

76.89 78.92 77.94 77.55 77.83 77.67

PenlOH

0.165 0.066 0.214 0.174 0.176 0.185

2-EI-l -BuOH

1.46 1.34 1.41 1.46 1.41 1.36

Hex

11, 74 10.8 11, 32 11, 69 11, 53 11, 46

2-EI-HexOH

0.397 0.297 0.326 0.357 0.337 0.336

Soda

755 hours 778 hours 789 hours 801 hours 813 hours

OctOH

2.2 1.77 1.97 2.09 1.96 2.03

DecOH

0.78 0.56 0.64 0.68 0.63 0.63

2-Et-1-0ctOH

0.139 0.1 0.12 0.135 0.121 0.132

DodecOH

0.278 0.21 1 0.231 0.24 1 0.229 0.208

BuOH%

13.02 11, 5 11, 94 12.47 12.02 11, 8

The results of this experiment demonstrate that n-butanol can be prepared with high yield and selectivity in a continuous process using only recycled hydrogen (i.e., in the absence of soda or compensation hydrogen), recycled ethanol, and without purification of the recycled gas.

Claims (20)

1.-Continuous process to prepare n-butanol and n-octanol, the process comprising:

(to)

(1) forming a gaseous phase n-butanol reaction mixture comprising an ethanol source and a hydrogen source, (2) reacting the gaseous phase nbutanol reaction mixture by contact with a Guerbet catalyst in a gas phase nbutanol reactor at a reaction temperature of about 150 pe to 450 pe and a reaction pressure of about 10 to about 200 bara to form a product stream of the n-butanol reactor comprising n-butanol and nhexanol and (3) fractionating the product stream of the n-butanol reactor to form a stream of n-butanol product and a stream of recovered n-hexanol; Y

(b)

(1) forming a gas phase n-octanol reaction mixture comprising a source of n-hexanol comprising at least a portion of the n-hexanol streams recovered from the n-butanol reaction mixture and the mixture Reaction of n-octanol, a source of ethanol and a source of hydrogen, (2) reacting the gas phase n-octanol reaction mixture by contacting a Guerbet catalyst in a gas phase n-octanol reactor at a reaction temperature of about 150 2e to 450 2e and a reaction pressure of about 10 to about 200 bara to form a n-octanol reactor product stream comprising n-octanol, nbutanol and n-hexanol and (3 ) fractionating the product stream of the n-octanol reactor to form a stream of n-octanol product, a stream of recovered n-hexanol and a stream of n-butane product !.

2. The process of claim 1 wherein: (a) (1) the product stream of the n-butanol reactor further comprises ethanol and hydrogen, (2) the process further comprises fractionating the product stream of the n-butanol reactor to form a recovered ethanol stream and a stream of recovered hydrogen and (3) the source of ethanol and the source of hydrogen in the gas phase nbutanol reaction mixture and the source of ethanol and the source of hydrogen in the gas phase n-octanol reaction mixture comprise ( i) at least a part of the recovered ethanol stream formed from the product stream of the n-butanol reactor and (ii) at least a portion of the recovered hydrogen stream formed from the reactor product stream of n-butanol; Y lb) (1) the product stream of the n-octanol reactor further comprises ethanol and hydrogen, (2) the process further comprises fractionating the product stream of the n-octanol reactor to form a recovered ethanol stream and a stream of recovered hydrogen and (3) the source of ethanol and the source of hydrogen in the gas phase nbutanol reaction mixture and the source of ethanol and the source of hydrogen in the gas phase n-octanol reaction mixture comprise (i ) at least a portion of the recovered ethanol stream formed from the n-octanol reactor product stream and (ii) at least a portion of the recovered hydrogen stream formed from the reactor reactor product stream n-octanol. 3.-The process of any preceding claim in which:

(to)

(1) The yield of ethanol-based n-butanol in the reaction of the n-butanol reaction mixture is from about 10% to about 40%, from about 10% to about 30%, from about a 15% to about 30% OR of about 20% to about 30% Y

(2)

The n-butanol selectivity in the reaction of the n-butanol reaction mixture is about 65% to about 95%, about 65% to about 85%, about 65% to about 80 %, or from about 65% to about 75%; Y

(b)

(1) the n-butanol selectivity in the reaction of the n-octanol reaction mixture is from about 10% to about 40%, from about 15% to about 40% or from about 15% at approximately 25%,

(2)

the n-octanol selectivity in the reaction of the n-octanol reaction mixture is from about 20% to about 55%, from about 30% to about 50% or from about 40% to about 50 % Y

(3)

the conversion of ethanol in the reaction of the n-octanol reaction mixture is from about 20% to about 60%, from about 20% to about 40%, about 20%, about 30% or about 40%

4.-The process of any preceding claim wherein the yield of ethanol-based n-butanol in the reaction of the n-butanol reaction mixture is from about 15% to about 25% and the selectivity in n- butanol is from about 70% to about 85%; the yield of ethanol-based n-butanol in the reaction of the n-butanol reaction mixture is about 10% to about 15% and the selectivity in n-butanol is about 85% to about 95% ; or the yield of ethanol-based n-butanol in the reaction of the n-butanol reaction mixture is about 30% to about 40% and the n-butanol selectivity is about 65% to about 70 %. 5. The process of any one of claims 2 to 4 wherein: (a) the source of ethanol for the n-butanol reaction mixture and for the n-octanol reaction mixture each comprises at least one 50 mole percent, at least 60 mole percent, at least 65 mole percent or at least 70 mole percent of recovered ethanol; (b) the source of hydrogen for the n-butanol reaction mixture and for the n-octanol reaction mixture each comprises at least 50 mole percent, at least 60 mole percent, at least one 65 mole percent or at least 70 mole percent of hydrogen recovered; and (c) the source of n-hexanol for the n-octanol reaction mixture comprises at least 50 mole percent, at least 60 mole percent, at least 65 mole percent, at least one 70 mole percent, or consists of recovered n-hexanol. 6. The process of any preceding claim wherein: (a) the mole ratio of ethanol to n-hexanol in the n-octanol reaction mixture is from about 0.3: 1 to about 3: 1 , from about 1.1: 1 to about 2: 1, from about 1.1: 1 to about 1.5: 1, or about 1.3: 1; (b) the mole ratio of hydrogen to ethanol in the n-butanol reactor mixture is about 0.1: 1 to about 5: 1, about 0.1: 1 to about 0.6: 1 , from about 0.1: 1 to about 0.4: 1, from about 0.5: 1 to about 3: 1, or from about 0.75: 1 to about 1.5: 1; and (c) the mole ratio of hydrogen to the sum of ethanol and n-hexanol in the noctanol reaction mixture is about 0.1: 1 to about 5: 1, about 0.1: 1 a about 1: 1, about 0.1: 1 to about 0.5: 1, or about 0.3: 1. 7. The process of any preceding claim wherein: (a) the n-butanol reaction mixture further comprises an acetaldehyde source and the mole ratio of acetaldehyde with respect to ethanol in the n-butanol reaction mixture is from about 0.001: 1 to about 0.1: 1, from about 0.001: 1 to about 0.005: 1, from about 0.001: 1 to about 0.003: 1, from about 0.005: 1 to about 0.1: 1, or from about 0.01: 1 to about 0.04: 1; (b) the n-butanol product stream further comprises acetaldehyde and the n-butanol reactor product stream is fractionated to recover at least a portion of the acetaldehyde and form a recovered acetaldehyde stream; Y (e) at least a portion of the acetaldehyde source in the n-butanol reaction mixture comprises recovered acetaldehyde. 8. The process of any preceding claim wherein: (a) the contact temperature of the n-butanol reactor is from about 150 2C to about 350 2C, from about 175 2C to about 300 2e, or from about 200 2C at about 300 2C; and (b) the contact temperature of the n-octanol reactor is from about 200 2C to about 400 2C or from about 250 2C to about 350 2C. 9.-The process of any preceding claim wherein the Guerbet catalyst is a metal oxide catalyst. 10. The process of any preceding claim wherein the Guerbet catalyst is a metal oxide comprising (a) at least one divalent metal selected from the list comprising Mg, Zn, Cu, Ca, Mn, Fe, Ni and Ca, (b) Trivalent Ga, and (c) a noble metal selected from the list comprising Pd, Pt, Au, Ah and Re, preferably Pd. 11. The process of claim 10 wherein the Guerbet catalyst further comprises an additional trivalent metal selected from the list comprising Al, La, Fe, Cr, Mn, Ca and Ni. 12. The process of any one of claims 1 to 11 wherein the catalyst is a metal oxide comprising: (a) at least one divalent metal, M1, selected from Mg, Zn, Cu, Ca, Mn, Fe , Ni and Ca, (b) at least one trivalent metal, M2, selected from Al, La, Fe, Cr, Mn, Ca, Ni and Ga, (e) at least one noble metal selected from Pd, Pt, Ru, Rh and Re, and. optionally, (d) V, wherein the catalyst comprises V, Ga, or a combination thereof. 13. The process of any one of claims 10 to 12 wherein the noble metal is P.S. 14.-An installation for manufacturing n-butanol and n-octanol from an ethanol source and a n-hexanol source, the installation comprising:

(to)

an n-butanol reactor system comprising at least one gas phase reactor having a fixed catalyst bed, the reactor (1) comprising an inlet port for the input of a feed stream gas from the n- reactor system butanol comprising a source of ethanol and a source of hydrogen, (2) a reaction zone containing a heterogeneous catalyst for contact with the catalyst to form a product stream from the n-butanol reactor, and (3) a port output for the discharge of a product stream from the n-butanol reactor system, the reactor product stream comprising n-butanol ethanol, water, n-hexanol, and hydrogen, in which the n-butanol reactor system It is operational at a reaction temperature of about 150 µL to 450 µL and a reaction pressure of about 10 to about 200 bara;

(b)

an n-octanol reactor system comprising at least one gas phase reactor having a fixed catalyst bed, the reactor (1) comprising an inlet port for the input of a n-octanol reactor feed stream gas comprising a source of ethanol, a source of n-hexanol and a source of hydrogen, (2) a reaction zone containing a heterogeneous catalyst for contact with the reactor feed stream to form a product stream of the reactor noctanol, and (3) an outlet port for the discharge of the product stream from the n-octanol reactor, the reactor product stream comprising n-octanol ethanol, water, nhexanol, n-octanol and hydrogen, in the that the n-octanol reactor system is operational at a reaction temperature of about 150 µL to 450 µL and a reaction pressure of about 10 to about 200 bara;

(C)

a first system for fractionating the product stream of the n-butanol reactor and the product stream of the n-octanol reactor, wherein the first fractionation system comprises a distillation column or an instantaneous evaporation column that forms (1 ) a first fractional stream comprising at least 95 mole percent of each of the water, ethanol and hydrogen contained in the product stream of the n-butanol reactor and the product stream of the n reactor

octanol and (2) a second fractional stream comprising at least 95 mole percent of each of the n-butanol, the n-hexanol and the n-octanol contained in the n-butanol reactor stream and the stream of n-octanol reactor product;

(d)

a second system for fractionating the second fractional stream, wherein the second fractionation system comprises a distillation column that forms (1) a stream enriched in n-butanol comprising at least 95 mole percent of the n-butanol contained in the second fractional stream and (2) a fourth fractional stream comprising at least 95 mole percent of each of the n-hexanol AND the n-octanol contained in the second fractional stream; Y

(and)

a third system for fractionating the fourth fractional stream, wherein the third fractionation system comprises a distillation column that forms (1) a recovered n-hexanol stream comprising at least 95 mole percent of the contained n-hexanol in the fourth fractional stream, in which the recovered n-hexanol stream is interconnected with the n-hexanol source for the noctanol reactor system and at least a portion of the recovered n-hexanol is recycled into the reactor feed stream of n-octanol and (2) a stream of n-octanol comprising at least 95 mole percent of the n-octanol contained in the fourth fractional stream.

15. The installation of claim 14 further comprising a system for fractionating the first fractional stream, wherein the first fractional stream comprises steam and the system for fractionating the first fractional stream comprises a condenser and an ethanol dehydration system in which (a) the first fractional stream is passed through the condenser to form a stream of recovered hydrogen gas and a stream of wet ethanol condensate and (b) the stream of wet ethanol condensate is dehydrated to form a stream of recovered ethanol and a water stream in which the recovered ethanol stream comprises at least 95 mole percent of the ethanol and less than 5 mole percent of the water contained in the first fractionated stream, and in which the recovered ethanol stream and recovered hydrogen stream are interconnected with the ethanol source and the even hydrogen source to the n-butanol reactor system and the n-octanol reactor system and at least a portion of the recovered ethanol and the recovered hydrogen is recycled into each of the n-butanol reactor feed stream and the feed stream of the n-octanol reactor. 16. The installation of claim 14 or claim 15 further comprising:

(to)

flow control for the ethanol source in the n-octanol reactor system and flow control for the n-hexanol source in the n-octanol reactor system in which the mole ratio of ethanol to n- Hexanol in the n-octanol reactor feed stream is controlled by a flow rate of about 0.3: 1 to about 3: 1, about 1.1: 1 to about 2: 1, about 1.1 : 1 to about 1.5: 1, or about 1.3: 1;

(b)

flow control for the hydrogen source in the n-octanol reactor system in which the mole ratio of hydrogen to the sum of ethanol and n-hexanol in the n-octanol reactor feed stream is controlled by a flow rate of about 0.1: 1 to about 5: 1, about 0.1: 1 to about 1: 1, about 0.1: 1 to about 0.5: 1, or about 0.3 :one ; Y

(and)

flow controt for the ethanol source in the n-butanol reactor system and flow control for the hydrogen source in the n-butanol reactor system in which the mole ratio of hydrogen to ethanol is controlled by a flow control from 0.1: 1 to about 5: 1, from about 0.1: 1 to about 0.6: 1, from about 0.1: 1 to about 0.4: 1, from about 0, 5: 1 to about 3: 1, or from about 0.75: 1 to about 1.5: 1.

17.-The installation of any one of claims 14 to 16 wherein:

(to)

at least 50 percent by mole, at least 60 percent by mole, at least 70 percent by mole, at least 80 percent by mole, at least 90 percent by mole, at least 95 percent mole percent, or at least 99 mole percent of the nhexanol present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and recycled into the feed stream of the n-octanol reactor;

(b)

at least 50 percent by mole, at least 60 percent by mole, at least 70 percent by mole, at least 80 percent by mole, at least 90 percent by mole or at least 95 percent mole percent of the ethanol present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and

it is recycled in the n-octanol reactor feed stream and in the n-butanol reactor feed stream; Y (e) at least 50 percent by moles, at least 60 percent by moles, at least 70 percent by moles, at least 80 percent by moles, at least 90 percent by moles or at least 95 mol% of the hydrogen present in the product stream of the n-octanol reactor and in the product stream of the n-butanol reactor is recovered and recycled in the n-octanol reactor feed stream and in the n-butanol reactor feed stream. 18. The installation of any one of claims 14 to 17 in which in addition:

(to)

The n-octanol stream is a raw n-octanol stream that further comprises n-decanol and in which the installation further comprises a distillation column to fractionate the raw n-octanol stream to form (1) a stream of noctanol product comprising at least 95 mole percent of the n-octanol contained in the crude n-octanol stream and (ii) a stream enriched in n-decanol comprising at least 95 mole percent of the n-decanol contained in the crude n-octanol stream;

(b)

The n-butanol enriched stream further comprises ¡-butanol, in which the installation further comprises a distillation column to fractionate the n-butanol enriched stream to form a n-butanol product stream having a purity exceeding 99 mole percent of n-butanol and a stream of impurities comprising i-butanol;

(C)

The installation further comprises a distillation column for purification of the n-octanol product stream, wherein said distillation column fractionats the n-octanol product stream to form a stream of finished n-octanol product having a purity exceeding 99 mole percent of n-octanol; Y

(d)

The installation further comprises a distillation column of the ndecanol stream to fractionate the n-decanol-enriched stream to form (i) a stream of n-decanol product comprising at least 90 mole percent or at least 95 mole percent of the n-decanol contained in the stream enriched in n-channel raw and (ii) a bottom stream of the distillation column of the stream of n

Decanol enriched in compounds that boil at a temperature greater than the boiling point of n-decanol compared to the current enriched in n-decanol. 19. The installation of any one of claims 14 to 18 comprising 5 also flow control for the n-octanol reactor feed streams and flow control for the n-butanol reactor feed streams in which the flow rate of the n-octanol reactor feed streams and the n-butanol reactor feed streams are controlled to provide an LHSV of the n-octanol reactor and an LHSV of the n-butanol reactor of about 0.5 to about 5, of 10 about 0.5 to about 2, about 0.75 to about 1.5 or about 0.9 to about 1.1. 20. The installation of any one of claims 14 to 19 characterized by the absence of a process output current comprising an excess of 0.001, 15.005 or 0.01 mole percent of n-hexanol.