MX354839B

Dehydrogenation of alkanols to increase yield of aromatics.

Abstract

The present invention provides methods, reactor systems, and catalysts for increasing the yield of aromatic hydrocarbons produced while converting alkanols to hydrocarbons. The invention includes methods of using catalysts to increase the yield of benzene, toluene, and mixed xylenes in the hydrocarbon product.

MX354839B, drawing sheet 1 — Sheet 1 of 71

Term

No projected expiry on record.

18 claims: 3 independent, 15 dependent

1
CLAIMS REIVINDICACIONES 1. Un método para convertir alcanoles en hidrocarburos aromáticos, comprendiendo el método:one. A method of converting alkanols to aromatic hydrocarbons, the method comprising: deshidrogenar parcialmente un material de alimentación de alcanol C1-C6 en presencia de un catalizador de la deshidrogenación a una temperatura de deshidrogenación y una presión de deshidrogenación efectivas para producir hidrógeno y una mezcla de componentes oxigenados que comprende (a) alcanol C1-C6 sin reaccionar y . (b) un ácido carboxilico, un aldehido, un éster o cualquier combinación de los mismos;en donde al menos una porción de los componentes oxigenados en la mezcla tienen una relación de hidrógeno a carbono efectiva de menos de 1.6 y en donde el grado de deshidrogenación parcial da como resultado una mezcla de componentes oxigenados que tiene una relación efectiva total de hidrógeno a carbono de 1.0 a 1.5;y exponer la mezcla de componentes oxigenados a un catalizador de conversión oxigenada de zeolita a una temperatura de conversión de compuestos oxigenados y a una presión de conversión de compuestos oxigenados para producir hidrocarburos aromáticos. partially dehydrogenize a C1-C6 alkanol feedstock in the presence of a dehydrogenation catalyst at a dehydrogenation temperature and dehydrogenation pressure effective to produce hydrogen and a mixture of oxygenated components comprising (a) unreacted C1-C6 alkanol and . (b) a carboxylic acid, an aldehyde, an ester, or any combination thereof;wherein at least a portion of the oxygenated components in the mixture have an effective hydrogen to carbon ratio of less than 1.6 and where the degree of partial dehydrogenation results in a mixture of oxygenated components having a total effective ratio of hydrogen to carbon from 1.0 to 1.5;and exposing the mixture of oxygenated components to a zeolite oxygenated conversion catalyst at an oxygenate conversion temperature and an oxygenate conversion pressure to produce aromatic hydrocarbons.
17
21. Un método para convertir etanol en hidrocarburos aromáticos gue comprende:twenty-one. A method of converting ethanol to aromatic hydrocarbons which includes: deshidrogenar parcialmente una alimentación de etanol en presencia de un catalizador de deshidrogenación a una temperatura de deshidrogenación y presión de deshidrogenación efectivas para producir una mezcla de componentes oxigenados que comprende etanol, acetaldehido, ácido acético y acetato de etilo, en donde el grado de deshidrogenación parcial da como resultado la mezcla de componentes oxigenados que tienen una relación efectiva de hidrógeno a carbono total de entre 1.0 y 1.5;partially dehydrogenize an ethanol feed in the presence of a dehydrogenation catalyst at an effective dehydrogenation temperature and dehydrogenation pressure to produce a mixture of oxygenated components comprising ethanol, acetaldehyde, acetic acid and ethyl acetate, where the degree of partial dehydrogenation results in the mixing of oxygenated components that have an effective hydrogen to total carbon ratio of between 1.0 and 1.5;exponer la mezcla de componentes oxigenados a un catalizador de conversión de zeolita oxigenada a una temperatura de conversión de compuestos oxigenados y una presión de conversión de compuestos oxigenados para producir hidrocarburos aromáticos. exposing the mixture of oxygenated components to an oxygenated zeolite conversion catalyst at an oxygenate conversion temperature and an oxygenate conversion pressure to produce aromatic hydrocarbons.
18
22. A method of converting alkanols to aromatic hydrocarbons comprising:22. Un método para convertir alcanoles en hidrocarburos aromáticos que comprende: ΐΝΕτηυτ · .Ί ΐΝΕτηυτ·.Ί DI U. · β.θ! Ί (· ΛΜ> DI U. ·β.θ!Ί(·ΛΜ> INDUSTRIAL Partially dehydrogenating a C1-C6 alkanol feedstock in the presence of a dehydrogenation catalyst at a dehydrogenation temperature and dehydrogenation pressure effective to produce hydrogen and a mixture of oxygenated components comprising (a) unreacted C1-C6 alkanol and (b) a carboxylic acid, an aldehyde, an ester, or any combination thereof;wherein at least a portion of the oxygenated components in the mixture have an effective hydrogen to carbon ratio of less than 1.6 and where the degree of partial dehydrogenation results in a mixture of oxygenated components having a total effective ratio of hydrogen to carbon from 1.0 to 1.5;INDUSTRIAL deshidrogenar parcialmente un material de alimentación de alcanol C1-C6 en presencia de un catalizador de deshidrogenación a una temperatura de deshidrogenación y presión de deshidrogenación efectivas para producir hidrógeno y una mezcla de componentes oxigenados que comprenden (a) alcanol C1-C6 sin reaccionar y (b) un ácido carboxilico, un aldehido, un éster o cualquier combinación de los mismos;en donde al menos una porción de los componentes oxigenados en la mezcla tienen una relación de hidrógeno a carbono efectiva de menos de 1.6 y en donde el grado de deshidrogenación parcial da como resultado una mezcla de componentes oxigenados que tiene una relación efectiva total de hidrógeno a carbono de 1.0 a 1.5;separar la mezcla de componentes oxigenados en una primera corriente de compuestos oxigenados que tiene una relación efectiva total de hidrógeno a carbono de entre 1.0 y 1.5 y una segunda corriente de compuestos oxigenados;separating the mixture of oxygenated components into a first stream of oxygenates having a total effective hydrogen to carbon ratio of between 1.0 and 1.5 and a second stream of oxygenated compounds;exponer la primera corriente de compuestos oxigenados a un catalizador de conversión de zeolita a una temperatura de conversión de compuestos oxigenados y a una presión de conversión de compuestos oxigenados para producir hidrocarburos aromáticos;y exponer la segunda corriente de compuestos oxigenados al catalizador de deshidrogenación a una temperatura de deshidrogenación y presión de deshidrogenación lN.TT»T'»r «.Η,νίο :NU >.%» f.'JAL exposing the first stream of oxygenates to a zeolite conversion catalyst at an oxy compounds conversion temperature and at an oxy compounds conversion pressure to produce aromatic hydrocarbons;and exposing the second stream of oxygenates to the dehydrogenation catalyst at a dehydrogenation temperature and dehydrogenation pressure lN.TT »T '» r «.Η, νίο: NU>.%» f.'JAL - 50 efectivas para producir hidrógeno y una mezcla adicional de componentes oxigenados. - 50 effective to produce hydrogen and an additional mixture of oxygenated components.

Independent claims3

546 paragraphs in 50 sections, as filed

(54) Title: DEHYDROGENATION OF ALCANOLS TO INCREASE THE PRODUCTION OF AROMATIC COMPOUNDS.

(54) Title: DEHYDROGENATION OF ALKANOLS TO INCREASE YIELD OF AROMATICS.

(57) Summary

The present invention provides methods, systems of reactors and catalysts to increase the production of aromatic hydrocarbons produced during the conversion of alkanols to hydrocarbons. The invention includes methods of using the catalysts to increase the production of benzene, toluene and mixed xylenes in the hydrocarbon product.

(57) Abstract

PATENT TITLE No. 354839

Holders): VIRENT, INC.

D micilio:

D nomination:

Classification:

Inventor (s):

3571 Anderson Street, Madison, Wisconsin, 53704, USA

DEHYDROGENATION OF ALCANOLS TO INCREASE THE PRODUCTION OF AROMATIC COMPOUNDS.

CIP:

C07C1 / 2Q7? C (Í7C | l5> ^ 0)) 705/0 ^ C07C15 / 08; C07C45 / 38 coTcl & c ^ otcl / MT ^ c6? Éi / ^ qzevT.

CPC:

PAUL G ^ JBLOMíVIEL; Ll YUAN; CORTRI ^ HT

J

STRAtE | j; Barren lyman; randy d.

The patent of refere

4 '' the

MX / a / 2014/00 & 145

International s^ e2011 : C * '*

I

NUMBER:

13/304.052

Validity: Vejhgí añosr F cha de Vdglligient ^

Date of Ex ^ Xcftción? ^

Pursuant to the as of the date of submission to the Legislation of twenty

expendable, counted to

Industrial.

Who subscribes to this title (Official Gazette of the Federation 25/01/2006, 06/05 / 2009,06 / 01/2010, Regulations of the Mexican Institute articles 1or, 3or, 4or, 5or fraction V subsection 12/27/1999, amended on 10/10/2002, 29/0 Deputy Generals, Coordinator, Departmental Directors and other subordinates of the Institute 08/04/2004 and 09/13/2007).

of Industrial Property £ ¿05/1999, 01/26/2004, 06/16/2005, a), 4or and 12th sections I and III of / 2004, 07/28/2004 and 09/07/2007); or of Industrial Property (shallow DOF that delegates powers to the Directors is, Divisional Deputy Directors, Coordinators 12/1999, amended on 02/04/2000, 07/29/2004,

This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 fraction III, 2 fraction V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

Original string:

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Arenal No. 550. Floor 1, Pueblo Santa Mafia Tepepan, Xochimilco, 16020. Mexico City.

(55) 53340700 www.gob.mx/impi

MX / 2018/24915

Κ ·.

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IMPJ

INsrm, τ <>MSX1CAN.( Η. Dt LA FEOFIIDAD

INOLISTMAL

DEHYDROGENATION OF ALCANOLS TO INCREASE PRODUCTION

OF AROMATIC COMPOUNDS

This request claims the benefit of the Request for

US patent USA

13 / 304,052 filed on November 23, 2011.

TECHNICAL FIELD

The present invention relates to catalysts and methods for increasing the production of aromatic compounds in processes for converting alcandés to hydrocarbons.

BACKGROUND OF THE INVENTION

Aromatic hydrocarbons, especially mixed benzene, toluene, and ortho- and para-xylene) are important industrial commodities that are used, for example, to produce numerous chemicals, fibers, plastics, and polymers, including styrene, phenol, aniline , polyester and nylon.

Mixtures of paraffinic and aromatic hydrocarbons can be produced by converting the alkanols in the presence of a catalyst for the conversion of oxygenates, such as a zeolitic catalyst. For example, methanol can be converted to paraffins, aromatics, and olefins in the gasoline range. Higher alcohols, such as ethanol, n-propanol, isopropanol, n-

d! -J MÍ-.XJCAbL »of the

I.Ol / STíUAL butanol, 2-butanol, isobutanol, 'tert-butyl /' pentanol alcohol and hexanol can also be converted to hydrocarbons using this process.

When oxygenates are converted to hydrocarbons in the presence of a zeolitic catalyst, the effective ratio of hydrogen to carbon (H: C ratioandf) of the reagents affects the H: C ratioandf of the reaction products. H: C ratioandf is calculated as follows:

H — 20

H: CandF = ~, where H represents the number of hydrogen atoms, O represents the number of oxygen atoms and C represents the number of carbon atoms. Water and molecular hydrogen (diatomic hydrogen, H2) are excluded from the calculation. H: C ratioandf applies to both individual components and component mixtures, but is not valid for components that contain atoms other than carbon, hydrogen, and oxygen. For mixtures, the C, H, and O of all components except water and molecular hydrogen are added. The term hydrogen refers to any hydrogen atom, while the term molecular hydrogen is limited to diatomic hydrogen, H2.

For illustrative purposes, the H: C ratioandf of ethanol (and of all alkanols) is 2, as shown in Table 1 below.

INSTITUTO MfcXiCAN ') 0' La í k 'h L tN bUÍTRl AL

Table 1. H: C ratioandf of alcohols

<td>Alcohol (in number of carbon atoms)</td><td>H: Cef</td>

Paraffins generally have an H: C ratioef greater than 2, whereas monoaromatic alkyl compounds generally have an H: C ratioandf 5 between 1 and 2, as shown below in Tables 2 and 3.

Table 2. H: C ratioef of for fine

<td>Paraffins</td><td>H: Cef</td>

Table 3. H: C ratioandf of alkyl substituted monoaromatic compounds

<td>Aromatic compound</td><td>H: Cef</td>

<td>Benzene</td><td> 1.0</td>

<td>Toluene</td><td> 1.14</td>

<td>Xylene</td><td> 1.25</td>

Other species of interest include carbon dioxide (CO2) with an H: C ratio.andf of -4, carbon monoxide 5 (CO) with an H: C ratioandf of -2 and carbon (C) with an H: C ratioandf of 0. Carbonaceous residue or coke that can accumulate on catalysts or other surfaces exhibits a range of H: C ratiosef, depending on the amount of hydrogen and residual oxygen of the coke.

For the conversion of alkanols to hydrocarbons, many

instíT'm hgxíCano

FROM THE FKOPiEDAÍ>

! fi JUSTR1AL

raw materials of interest are essence ± mgTrt'eT'free' - non-C, H and O atoms, which allow characterizing, from a practical point of view, the material fed to a reaction step using the H: C ratioandf and the products of a reaction step using the H: C ratioandF. For example, the alcandés can react through zeolitic catalysts to form a hydrocarbon mixture. Due to the high H: C ratioandf of the alkanes, the conversion of alkanols through zeolitic catalysts generally generates a relatively high proportion of paraffins with respect to aromatic compounds (approximately three moles of paraffins are generated per mole of benzene or alkyl-substituted monoaromatic compounds). This is a desirable blend for some applications, such as gasoline production. However, the low production of aromatic compounds limits the application of this process to the production of high value aromatic chemical compounds such as benzene, toluene and xylenes (BTX).

Zhang and his collaborators have recently studied the impact of the H: C ratioef on the conversion of biomass-derived raw materials to coke, olefins and aromatics using a ZSM-5 catalyst (Zhang et al., Catalytic conversion of biomass-derived feedstocks into olefins and aromatics with ZSM-5: the hydrogen to carbon

, Τ Τ '/ τΑ k I INSTITUTO M.XICAN. > FROM LA RRÚRIEO industrial

effective ratio, Energy Environ. Sci., 2011, 4/22 9 /}. · Εγτ · this study, Zhang reported that biomass-derived raw materials with H: C ratiosandf between 0 and 0.3 produced high levels of coke, which makes the conversion of biomass-derived raw materials into aromatic and chemical compounds unprofitable. Zhang also reported that the production of aromatic compounds + definas increases and the production of coke decreases with increasing H: C ratio.ef of the raw material. However, there is a turning point for an H: C ratio.ef 1.2, in which the production of aromatics + olefin does not increase as rapidly. The ratio of olefins to aromatic compounds also increases with increasing H: C ratio.ef, while CO and CO productions2 are maximized by increasing the H: C ratioandF. Specifically, Zhang reported that productions of aromatics and olefins increased from 12% and 15% to 24% and 56% with increasing H: C ratio.ef, respectively, and that the production of olefins is higher than the production of aromatic compounds for all raw materials, this difference increasing every time the higher the H: C ratio.andF. Again, this low production of aromatic compounds limits the application of this process to the production of high value aromatic chemical compounds such as benzene, toluene and xylenes (BTX).

IMPI ζ MEXICAN INSTITUTE OF INDUSTRIAL ERORIEDAD

There is still a need for a method to increase the production of aromatic hydrocarbons produced during the conversion of alcandés to hydrocarbons.

SUMMARY OF THE INVENTION

The invention provides methods for converting alkanols to aromatic hydrocarbons. The method generally involves: (1) exposing an alkanolic feedstock to a dehydrogenation catalyst at a dehydrogenation temperature and a dehydrogenation pressure to produce hydrogen and an oxygenated component; and (2) exposing the oxygenated component to an oxygenate conversion catalyst at an oxygenate conversion temperature and an oxygenate conversion pressure to produce aromatic hydrocarbons.

One aspect of the invention is that the oxygenated component has a desired effective ratio of hydrogen to carbon (H: C ratioandf). In one embodiment, the oxygenated component has an effective ratio of hydrogen to carbon of less than 2.0, 1.9, 1.8, 1.7, or

1.6. In another embodiment, the oxygenated component has an effective ratio of hydrogen to carbon greater than 1.0, 1.1, 1.2, 1.3 1.4, or 1.5. In yet another embodiment, the oxygenated component has an effective ratio of hydrogen to carbon comprised between

MEXICAN INSTITUTE □ E LA l'KOHEi AL> industrial

1.0 and 1.8, or between 1.2 and 1.7.

Once the dehydrogenation and the conversion of the oxygen component have been completed, part of the carbon in the alkanolic raw material is contained in the aromatic hydrocarbons. In one embodiment, more than 40% of the carbon in the alkanolic feedstock is contained in the aromatic hydrocarbon product. In another embodiment, more than 45% of the carbon in the alkanolic feedstock is contained in the aromatic hydrocarbon product.

Another aspect of the invention is the composition of the alkanolic raw material. In one embodiment, the alkanolic feedstock is derived from material of recent biological origin, so that the age of the compounds or of the fractions containing the compounds is less than 100 years, preferably less than 40 years and more preferably less than 20 years, as calculated from the carbon 14 concentration of the raw material. In other embodiments, the alkanolic raw material comprises a primary alcohol, ethanol, n-butanol, 2-butanol, or isobutanol. In other embodiments, the alkanolic feedstock is derived from a fermentation, Fischer-Tropsch, pyrolysis, aqueous phase reforming, or other catalytic conversion process.

When the alkanolic raw material is exposed to a dehydrogenation catalyst at a dehydrogenation pressure temperature, hydrogen and a

IMPI

M2XICANO INSTITUTE

Say THE iROHEDAD industrial

oxygenated component. In one embodiment, the oxygenated component comprises a carboxylic acid, an aldehyde, and an ester. In other embodiments, the oxygenated component comprises a carboxylic acid and an ester, or the oxygenated component comprises an aldehyde.

The dehydrogenation catalyst is capable of dehydrogenating calendars to form the oxygenated component. In one embodiment, the dehydrogenation catalyst comprises a metal selected from the group consisting of Cu,

Ru, Ag, CuCr, CuZn, Co, alloys thereof and combinations thereof. The dehydrogenation catalyst may further comprise a support. The support may comprise a material selected from the group consisting of alumina, silica, silica-alumina, titania, carbon, zirconia, and mixtures thereof. In one embodiment, the dehydrogenation catalyst comprises Cu on a silica support. In another embodiment, the dehydrogenation catalyst comprises zinc-copper aluminate or Raney copper.

The dehydrogenation reaction is carried out at a temperature and pressure at which the thermodynamic conditions are favorable.

In one embodiment, the dehydrogenation temperature is between about

500 or z-1

C, and atmospheric pressure at approximately 1000 psig.

dehydrogenation varies from below or pressure

- 10 IMPI

INSTITUTO MiXICAN>

OF INDUSTRIAL RETURN

Aromatic hydrocarbons are produced by catalytic reaction of the oxygenated component in the presence of an oxygenate conversion catalyst at an oxygenate conversion temperature and an oxygenate conversion pressure. In one embodiment, the catalyst for the conversion of oxygenates comprises a zeolite. In another embodiment, the catalyst for the conversion of oxygenates is ZSM-

5. The catalyst for the conversion of oxygenates can be modified by a material selected from the group consisting of phosphorus, gallium, zinc, nickel, tungsten, and mixtures thereof. The catalyst for the conversion of oxygenates can also contain a binder selected from the group consisting of alumina, silica, silica-alumina, titania, zirconia, aluminum phosphate and mixtures of these.

The conversion reaction of the oxygenated compounds is carried out at a temperature and pressure at which the thermodynamic conditions are favorable. In one embodiment, the conversion temperature of the oxygenates is between about 250 ° C and 550 ° C, and the conversion pressure of the oxygenates varies from below atmospheric pressure to about 1000 psig.

Another aspect of the invention is a method of producing

Hydrocarbons by catalytic reaction of an alkanolic feedstock with a multifunctional dehydrogenation / oxygenate conversion catalyst at a suitable temperature and pressure to produce hydrocarbons.

Still another aspect of the invention is a method of producing aromatic hydrocarbons comprising the following steps or actions: (1) exposing a raw material comprising a first oxygenated component to a dehydrogenation catalyst at a dehydrogenation temperature and a dehydrogenation pressure to produce hydrogen and a second oxygenated component; and (2) exposing the second oxygenated component to an oxygenate conversion catalyst at an oxygenate conversion temperature and an oxygenate conversion pressure to produce aromatic hydrocarbons.

Another aspect of the invention is a method of converting ethanol to aromatic hydrocarbons, where the method comprises the following steps or actions: (1) exposing an ethanolic raw material to a dehydrogenation catalyst at a dehydrogenation temperature and a dehydrogenation pressure to producing a reaction stream comprising acetaldehyde, acetic acid, and ethyl acetate; and

<td>(2) expose</td><td>the</td><td colspan="2">reaction current to</td><td>a catalyst of</td><td>the</td>

<td>conversion</td><td>of</td><td>compounds</td><td>oxygenated to</td><td>a temperature</td><td>of</td>

<td>conversion</td><td>of</td><td>compounds</td><td>oxygenated</td><td>and a pressure</td><td>of</td>

IMPI MEXICAN INSTITUTE OF! A INDUSTRIAL PROPERTY

conversion of oxygenated compounds to produce aromatic hydrocarbons.

DESCRIPTION OF THE DRAWINGS

Fig. 1 is an illustration of the chemistry involved in one aspect of the present invention using ethanol as the raw material.

Fig. 2 is a graph illustrating the increased production of aromatic compounds in the claimed processes versus traditional methods of converting alcohols to hydrocarbons as a function of the effective ratio of hydrogen to carbon.

Fig. 3 is a graph illustrating the shift in the composition of the liquid product associated with a reduction in the effective ratio of hydrogen to carbon.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to methods, systems of reactors and catalysts for increasing the production of aromatic hydrocarbons produced during the conversion of alkanols to hydrocarbons. The invention includes methods of using the catalysts to increase the production of benzene, toluene and mixed xylenes in the hydrocarbon product.

The term alkanols, as used herein, refers, without limitation, to alcohols

IMP

7 JK MEXICAN INSTITUTE

DS THE PROPERTY

INDUSTRIAL

- 13 aliphatics of general formula CnH2n + 20i. Suitable alkanols for use in the raw materials according to the invention include the Οχ-ϋβ alkanols, which can be primary or secondary alcohols, such as one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol , isobutanol, n-pentanol or n-hexanol. Tertiary alcohols are less preferred as the sole components of an alkanolic feedstock, but can be used if combined with more suitable primary or secondary alcohols.

The alkanols can come from any source, but are preferably derived from biomass. The term biomass, as used herein, refers, without limitation, to organic materials produced by plants (such as leaves, roots, seeds, and stems), and metabolic residues from animals and microbials. Common sources of biomass include: (1) agricultural residues, such as corn stalks, straw, seed husks, offal from sugarcane, bagasse, walnut shells, and manure from cattle, poultry, and pigs; (2) wood material, such as wood or bark, sawdust, wood shavings, and mill waste; (3) municipal waste, such as waste paper and grass clippings; and (4) energy crops, such as poplar, willow, rod grass, alfalfa, blue grass, corn, soybeans, and the like. The term also refers to the fundamental constituent units of the above, namely saccharides, lignin, materials

cellulosics, hemicellulose and starches, among others.

Biomass-derived alkanols can be produced by any known method. Such methods include fermentation technologies that employ enzymes or microorganisms, Fischer-Tropsch reactions to produce alpha C alcohols.2-io and pyrolysis technologies to produce alcohols from oil, among others.

In one embodiment, the alkanols are produced using catalytic reforming technologies such as BioForming® technology developed by Virent Inc.

(Madison, Wisconsin) and described in the Patents of

USA USA N.03 7,767,867, 8,053,615 (Cortright et al.), 8,017,818 (Cortright et al.) And 7,977,517 (Cortright et al.), All of which are incorporated herein by reference. The alkanols can also be derived from natural gas using Fischer-Tropsch-type reactions.

Surprisingly, the inventors increased aromatic hydrocarbon productions by partially dehydrogenating alkanolic raw materials using a dehydrogenation catalyst in the reaction environment described below. Without being bound by any particular theory, the inventors believe that the catalyst can transfer hydrogen atoms, which are available through the

T> -y

MEXICAN JNSTITUTE

OF THE FROI-IEDAD

INDUSTRIAL

conversion of alcandés with a relatively high content of hydrogen in aromatic compounds, to unsaturated components. If hydrogen is transferred to a define, a paraffin is generated. Because olefins are 5 precursors of aromatic compounds, converting an olefin to a paraffin reduces the amount of available material that can be converted to aromatic compounds.

If the hydrogen is transferred to a ketone or an aldehyde, an alkanol is formed. In this way, the carbonyl group of the ketone or aldehyde acts as a hydrogen trap, eliminating the reactive hydrogen and avoiding the conversion of olefins to paraffins, thus reducing the amount of paraffins and increasing the overall production of aromatic compounds. The resulting alkanol is also productive since it serves as additional raw material for hydrocarbon formation reactions.

Oxygenates capable of reacting with hydrogen in this way, as used herein, are called hydrogen acceptors. The 20 carbonyls, carboxylic acids, esters, cyclic ethers, diols, polyols, furans and other oxygenated compounds characterized by having an H: C ratio are believed to beandf <2 can be hydrogen acceptors, either directly or after other reactions (such as dehydration) that have turned the components into hydrogen acceptors. The

The net impact of the transfer of hydrogen to unsaturated oxygenates is the production of fewer paraffins and the increased production of aromatic hydrocarbons.

In one embodiment, the alkanol is ethanol. Oxygenated compounds produced from ethanol generally include acetaldehyde, acetic acid, and ethyl acetate. During the claimed reaction, the primary alkanols produce the corresponding equivalent products with the carbon number of the starting alkanol. Secondary alcohols are not capable of converting to acids or esters and will mainly produce ketones, unless they are used in admixture with other alkanols. The specific products depend on several factors including the composition of the alkanolic raw material, the reaction temperature, the reaction pressure, the concentration of the alkanol, the reactivity of the catalyst and the flow of the alkanolic raw material since this affects the space velocity (the mass / volume of reagent per unit of catalyst per unit of time).

Ethers can also be produced from alkanols.

For example, the conversion of methanol to dimethyl ether can be used to reduce the exotherm of the conversion of oxygenates.

Dialkyl ethers may also be present in the material fed to the catalyst for the conversion of oxygenates such as *

- 17 IMPI

MEXICAN INSTITUTE OF PROPERTY

INDUSTRIAL

product of the dehydrogenation catalyst or as a separately introduced component. Dialkyl ethers, such as diethyl ether, dimethyl ether, etc., have an H: C ratioandf of 2.0 and, as such, affect the ratio of aromatic compounds to paraffin in the product as well as an alkanol.

As indicated above, the H: C ratioandf of the reagents affects the H: C ratioandf of the reaction products. When the hydrogen acceptors are passed as reagents by a catalyst for the conversion of oxygenates, aromatic hydrocarbons production obtained H: C ratioandDehydrogenation f of an improved production is achieved, compared to when the reagents are aldehydes which are alkanadic.

can form the

The por is between zero and 2 as shown below in the Table

Table 4. H: C ratioef of aldehydes and ketones

<td>Carbon number of aldehydes or ketones</td><td>H: Cef</td>

IMPIp ^ a

MRXICAN INSTITUTE ·> »

PROPERTY '& 3

INDUSTRIAL; ί? · Τ *. ^

According to the invention, the process for converting alkanols to hydrocarbons can be a two-step process (in which the catalyst for dehydrogenation and the catalyst for the conversion of oxygenates 5 can be independent catalysts) or a one-step process. step (in which the dehydrogenation catalyst and the conversion catalyst of the oxygenates can be a multifunctional catalyst). When independent catalysts are provided, they may be present in separate containers, in separate beds within a single container, in alternate layers in a single catalyst bed, or physically mixed within the same bed.

The general two-step process is as outlined below. An alkanolic feedstock is first passed into contact with a dehydrogenation catalyst through a reactor at a dehydrogenation temperature and a dehydrogenation pressure, and thereby molecular hydrogen is released and oxygenated compounds are produced.

IMPI

MEXICAN INSTITUTE

PE THE PROPERTY _ 2_9 - IWISTEMI.

illustrated in Figure 1. The alkanolic raw material can be an essentially pure alkanol stream or, alternatively, the alkanolic raw material can be mixed with water to create an aqueous solution in which the alkanol concentration is greater than 1%, or greater than 5%, or greater than 10%, or greater than 20%, or greater than 30%, or greater than 40%, or greater than 50%.

The dehydrogenation catalyst includes one or more basic and / or metallic functional materials capable of catalyzing the conversion of hydroxyl-type elements to carbonyls. Suitable metal components include, without limitation, Cu, Ru, Ag, CuCr, CuZn, Co, Sn, Mo, and combinations thereof. Suitable base-catalyzed dehydrogenation catalysts include Li, Na, K, Cs, Mg, Ca, Ba, Zn, Ce, La, Y, Zr, hydrotalcite, zeolitic aluminosilicate treated with base. Basic catalysts can also include an oxide of Ti, Zr, V, Mo, Cr, Mn, Al, Ga, Co, Ni, Si, Cu, Zn, Sn, Mg, P, Fe, and combinations thereof. Preferred Group IA materials include Li, Na, K, and Cs. Preferred Group HA materials include Mg, Ca, and Ba. A preferred Group IIB material is Zn. Preferred Group IIIB materials include Y and La. Basic resins include resins that exhibit basic functionality, such as Amberlyst A26 and Amberlyst A21. The basic catalyst can

- 20 IMPI

MEXICAN INSTITUTE of industrial eroeity

be self-supporting or adhering to any of the supports described in more detail below, including supports containing carbon, silica, alumina, zirconia, titania, vanadia, ceria, alloys and mixtures thereof.

The basic catalyst may also include zeolites and other microporous supports containing Group IA compounds such as Li, Na, K and Cs. Preferably, the Group IA material is present in an amount greater than that required to neutralize the acidic nature of the support. These materials can be used in any combination and also combined with alumina or silica. A metallic function can also be provided by

<td>the</td><td>addition of metals</td><td>of the</td><td>group VIIIB or Cu,</td><td>r Ga,</td><td>In, Zn, Cr or</td>

<td></td><td>The catalyst of</td><td>the</td><td>dehydrogenation</td><td>this</td><td>self-supporting</td>

<td>or,</td><td>preferably</td><td colspan="2">includes a material</td><td>of</td><td>support. The</td>

support for the metal component may contain any one or more of alumina, silica, silica-alumina, titania, carbon, zirconia and mixtures thereof. Copper on a silica support, Raney copper and zinc-copper aluminate are particularly preferred dehydrogenation catalysts. For the copper catalyst on a silica support, the copper content can generally vary between 0.05% and 40%, preferably between 0.1% and 20%, and even more preferably between 0.2% and 10%.

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In some embodiments, dehydrogenation is between about 80 ° C and 500 ° C, preferably between about 100 ° C and 450 ° C, and even more preferably between about 150 ° C and 400 ° C. The dehydrogenation pressure ranges from below atmospheric pressure to approximately 100 psig, preferably from approximately atmospheric pressure to approximately 700 psig, and even more preferably from approximately 10 psig to approximately 500 psig.

The degree of dehydrogenation of the alkanolic raw material can be measured according to the amount of molecular hydrogen released during dehydrogenation, and can range from 0.05 to 2.0 moles of molecular hydrogen released per mole of alkanolic raw material. Values greater than 1 mol of molecular hydrogen released per mole of raw material can be obtained when carbonyls are subsequently converted to acids, with associated water consumption and molecular hydrogen release. In general, the reaction should be carried out under conditions in which the time of the alkanolic raw material in the catalyst is adequate to generate the desired dehydrogenation products. For example, dwell time can be set to a mass hourly space velocity (WHSV) of between 0.01 and 30, or between 0.05 and 10, or between 0.1 and 5, or between

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1.0 and 4. -----------!----------- Desirable levels of dehydrogenation depend on the composition of the alkanolic raw material. To produce a displacement of the ratio of aromatic compounds to paraffins during the conversion of oxygenates, long chain alcohols must be dehydrogenated to a greater extent than short chain alcohols. For a methanolic feedstock, it is desirable that the dehydrogenation be less than 50% (0.5 moles of molecular hydrogen released per mole of total feedstock fed into the system) and it is preferred that it be less than 37% to prevent the coking rate from being excessive. For an ethanolic feedstock, it is desirable that the dehydrogenation be less than 85% (0.85 moles of molecular hydrogen released per mole of total feedstock fed into the system) and it is preferred that it be less than 75%. For mixed alkanolic raw materials, the overall degree of dehydrogenation must be such that the H: C ratioandglobal f is less than 2.0, 1.9, 1.8, 1.7 or 1.6 and greater than 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5. For example, the overall degree of dehydrogenation should be such that the effective proportion of carbon is between 1.0 and 1.8, and preferably between 1.2 and

1.7. For alcandins containing three or more carbons, any level of up to total dehydrogenation may be desirable. The degree of dehydrogenation can be controlled by varying the catalyst

Higher temperatures higher hydrogen levels than the catalyst dehydrogenation of the

Can be

and operating conditions.

High levels generally lead to dehydrogenation. Reaction can be added to and to avoid dehydrogenation.

limiting the degree of deactivation adding other components, such as additional hydrogen and oxygenates, to the dehydrogenation products. If additional components are added, it may be preferable to dehydrogenize shorter chain alcohols, such as methanol and ethanol, to a greater extent so that the H: C ratioef global is between 1.0 and 1.8, and preferably between 1.2 and 1.7.

The products of dehydrogenation, including unreacted alcohols and hydrogen acceptors, are then passed in whole or in part in contact with a catalyst for the conversion of oxygenated compounds by a reactor under conditions of effective temperature and pressure to convert a portion of the products of dehydrogenation into aromatic hydrocarbons. The catalyst for the conversion of oxygenated compounds has one or more acidic materials capable of catalyzing the conversion of the products of dehydrogenation into the desired aromatic hydrocarbons. The conversion catalyst may include, without limitation, aluminosilicates (zeolites),

INSTITUTO MEXIC / N 'DE Ι.Λ PH; '· £ γ λ I INDUSTRIAL silicoaluminophosphates (SAPO), aluminum phosphates (ALPO), amorphous silica-alumina, zirconia, sulfated zirconia, tungsten zirconia, titania, acidic alumina, phosphate alumina, phosphate silicate, sulfate carbons, phosphate carbons, heteropolyacids and combinations of these.

In one embodiment, the catalyst may also include a modifier such as Ce, Y, Se, La, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The catalyst can also be modified by adding a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr , Mo, W, Sn, Os, alloys and combinations thereof, to provide metallic functionality, and / or oxides of Ti, Zr, V, Nb, Ta,

Fe, Co, Go, Ni, Si, Cu, Zn, these. The catalyst of

Mo, Cr, W, Mn, Re, Al, Ga, In,

Sn, Cd, P and conversion combinations may be self-supporting or adhering to any of the supports described in more detail below, including supports containing carbon, silica, alumina, zirconia, titania, vanadia, ceria, heteropolyacids, alloys and mixtures of these.

Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Se, Y, Ta, and lanthanides can also be exchanged on zeolites to provide a zeolitic catalyst. The term zeolite, as used herein, refers not only to a microporous crystalline aluminosilicate but also to

MEXICAN INSTITUTE r> E la frop.'Eda! INDUSTRIAL aluminosilicate structures containing microporous crystalline metals such as galloaluminosilicates and

<td>galosilicates.</td><td>The</td><td>functionality</td><td>metallic</td><td>can</td><td>to be</td>

<td>provided by</td><td colspan="2"> metals such as</td><td>Cu, Ag, Au,</td><td>Pt, Ni,</td><td>Faith,</td>

Os, alloys and combinations of these.

Examples of suitable zeolitic catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM48. ZSM-5 zeolite and its conventional preparation are described in Pat. from the USA USA N.you 3,702,886; Re. 29,948 (ZSM-5 very siliceous); 4,100,262 and 4,139,600, all of which are incorporated herein by reference. ZSM12 zeolite and its conventional preparation are described in Pat. from the USA USA No. 3,832,449, incorporated herein by reference. ZSM-23 zeolite and its conventional preparation are described in Pat. from the USA USA No. 4,076,842, incorporated herein by reference. ZSM-35 zeolite and its conventional preparation are described in Pat. from the USA USA

No. 4,016,245, incorporated herein by reference.

Another ZSM-35 preparation is described in Pat. from the USA USA

No. 4,107,195, the contents of which are incorporated herein by reference. The ZSM-48 zeolite and its conventional preparation are presented in Pat. from the USA USA No. 4,375,573, incorporated herein by reference. Other examples of zeolitic catalysts are described in US Pat.

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USA 5,019,663 and in US Pat. USA 7,022,888, which are also incorporated herein by reference.

As described in US Pat. USA No. 7,022,888, the acid catalyst may be a bifunctional pentasilic zeolitic catalyst including at least one metal element from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh , Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys or combinations thereof, or a modifier from the group consisting of Ga, In, Zn, Fe, Mo, Au, Ag, Y, Se, Neither,

P, Ta, the lanthanides and combinations of these. Zeolite can be used with reagent streams containing an oxygenated hydrocarbon at a temperature below 600 ° C.

The zeolite may have a crystal structure of the ZSM5, ZSM-8 or ZSM-11 type consisting of a large number of 5-membered oxygen-containing rings, i.e., pentasilic rings. Zeolite with a ZSM-5 type structure is a particularly preferred catalyst.

The catalyst may optionally contain any binder such as alumina, silica, or clay material. The catalyst can be used in the form of pellets, extrudates and particles of different shapes and sizes. In one aspect, the catalysts for the conversion of oxygenates are ZSM-5 and zeolite beta.

In general, the conversion temperature of oxygenated compounds is between approximately

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250 ° C and 550 ° C, preferably between about 300 ° C and 500 ° C, and even more preferably between about 320 ° C and 480 ° C. The conversion pressure of the oxygenates varies between below atmospheric pressure and about 1000 psig, preferably between about atmospheric pressure and about 700 psig, and more preferably between about 10 psig and about 500 psig. In general, the reaction should be carried out under conditions in which the residence time of the dehydrogenation products in the catalyst of the conversion of oxygenates is adequate to generate the desired hydrocarbons. For example, dwell time can be set to a mass hourly space velocity (WHSV) of between 0.01 and 30, or between 0.05 and 10, or between 0.1 and 5, or between 1.0 and 4.

Excluding molecular hydrogen (H2), the H: C ratioandOverall f of the dehydrogenation products is generally less than 2, which produces an increase in the production of aromatic compounds and an improvement compared to traditional methods for the conversion of alcohols to hydrocarbons. When the dehydrogenation and conversion of oxygenates are complete, more than 40%, or 45%, or 50%, or 60%, or 70%, or 75%, of the carbon in the alkanolic raw material is contained in the product aromatic hydrocarbon. Figure 2 shows the improvement in the production of compounds, reduction of the proportion shows the increase in the achieved liquid.

H: Candf below

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aromatic obtained by

H: Candf below 2. Figure 3 content of products by reducing the of 2. It is also possible to proportion aromatics by introducing additional oxygenated components fed into the second reactor.

The present invention can also be practiced in a one-step process in which the dehydrogenation catalyst and the oxygenate conversion catalyst is a multifunctional catalyst.

In this approach, the alkanols are converted to hydrocarbons using a multifunctional catalyst containing one or more materials capable of catalyzing both the dehydrogenation reaction and the conversion of oxygenated compounds. The multifunctional catalyst may include any of the elements suitable for the catalysts for dehydrogenation and conversion of independent oxygenated compounds indicated above. A particularly useful catalyst is silica bonded ZSM-5 supported copper. In this single-step embodiment, the dehydrogenation reaction and the conversion reactions of oxygenates occur in the same reaction vessel under conditions of temperature and pressure as those described above and which are suitable for

Mixica Institute:; ·. '! FROM THE Μ · Ό ··! Η: · ΑΕ> INDUiTillAL

produce both for dehydrogenation and conversion reactions of oxygenates.

In some embodiments, the products of the dehydrogenation step are separated to provide one or more streams that are directed to the conversion reactor and one or more streams that are not directly fed to the conversion reactor. Streams that are not fed directly to the conversion reactor can be removed from the system or recycled to the dehydrogenation reactor for later conversion.

Separation means include, but are not limited to, separation based on volatility differences between components, extraction, membranes, and ion exchange.

In a preferred embodiment, the products of the dehydrogenation step are cooled and a portion of the molecular hydrogen produced in the reaction step is removed as a product to send the remainder of the gas phase components to the conversion reactor. In another preferred embodiment, the dehydrogenation product is distilled off to provide an aldehyde-enriched stream that is recycled to the dehydrogenation reactor to convert the aldehydes to acids and esters. In yet another preferred embodiment, the alkanols are separated from the product stream and recycled to the dehydrogenation reactor to increase the overall conversion of the alkanols.

In other embodiments, oxygenated compounds other than alkanols can be used in addition to or as a supplement to the alkanolic raw material.

The following examples are to be considered illustrative of various aspects of the invention and are not to be construed as limiting the scope of the invention, which is defined in the appended claims.

EXAMPLES

Preparation of ethanol dehydrogenation catalysts

Example 1

Copper modified monoclinic zirconia was prepared by adding an aqueous solution of copper nitrate to monoclinic zirconia (Saint-Gobain Norpro, Ohio) using an incipient moisture impregnation technique to achieve a target copper load of 1, 2 and 5% by weight. The catalyst was dried overnight under vacuum at 110 ° C and calcined at 400 ° C in air flow for 6 hours.

Example 2

Copper nitrate (Acros, Geel, Belgium) was added to a gamma alumina support (Norpro Saint Gobain, Paris, France) using an incipient moisture impregnation technique to achieve a target Cu loading of 5% by weight. The catalyst was dried in an oven with a purge of

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air at 120 ° C, then calcined in the same oven with a gradual increase in temperature from 2 ° C / min to 550 ° C and held at this temperature for 7 hours.

Example 3

A copper modified and calcium doped gamma alumina catalyst was prepared by adding an aqueous solution of copper nitrate to calcium doped gamma alumina (Saint-Gobain Norpro, Ohio) using an incipient moisture impregnation technique to achieve a target copper load of 2% by weight. The catalyst was dried overnight under vacuum at 110 ° C and calcined at 400 ° C in air flow for 6 hours.

Example 4

Copper nitrate (Acros, Geel, Belgium) was added to a silica support (Davisil, grade 635, Sigma Aldrich, St. Louis, Missouri) using an incipient moisture impregnation technique to achieve a target Cu load of 5% in weigh. The catalyst was dried in an oven with an air purge at 120 ° C, then calcined in the same oven with a gradual increase in temperature from 2 ° C / min to 550 ° C and kept at this temperature for 7 hours. .

Example 5

Raney copper (WRGrace) was used directly in the ethanol dehydrogenation test after washing with water and co-feeding H2 to the catalyst overnight.

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OF INDUSTRIAL PROPERTY

Example 6 ~

Zinc-copper aluminate (Sud-Chemie, ShiftMax® 230) with mesh size 18x30 was formed and used directly in the ethanol dehydrogenation test.

Ethanol dehydrogenation

Example 7

The catalyst systems referenced in Examples 1-6 were investigated to determine the dehydrogenation of ethanol. The studies were performed in a stainless steel tube-shaped reactor with a size equivalent to an internal diameter of 8.5 mm. 22 grams of catalyst were introduced into the reactor. In all cases, the catalyst was reduced to 350 ° C with hydrogen flow before use. Next, a raw material consisting of 95% ethanol in water was passed over the catalyst under the conditions shown in Table 5.

The gas, the organic phase (when it was present) and the aqueous phase were collected and analyzed to determine the productions of the products. Table 5 shows the reaction products as a function of the operating conditions for the catalysts described in Examples 1-6. The overall degree of dehydrogenation can be estimated by the production of hydrogen, which varied between 0.18 and 0.84 moles of hydrogen produced per mole of ethanol.

fed.

Various reaction routes are evident from the product profiles, due to the functionality inherent in both the metallic copper function and the supports.

These reaction products were mixtures of oxygenated compounds suitable for further processing into hydrocarbons.

It should be noted that the H: C ratioandf of the mixtures of oxygenated compounds was lower than that of the fed alkanol in all cases.

Table 5. Dehydrogenation of Ethanol on the Catalysts of the Examples

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Dehydrogenation and condensation of ethanol using copper and acid catalysts

The following examples illustrate a process for dehydrogenating an alkanolic feedstock to oxygenated hydrocarbons and then converting oxygenated compounds to hydrocarbons through a condensation catalyst.

In these experiments a support of ZSM-5 joined by A1 was used2OR3 marketed (extruded 1/16, 20% of

AI2O3 as binder, ZSM-5 SAR 30, Zeolyst).

Example 8

Nickel nitrate (Sigma Aldrich, St. Louis,

Missouri) to a ZSM-5 bracket attached by A12OR3 commercialized (extruded 1/16, 20% of A12OR3 as binder, ZSM-5 SAR

30, Zeolyst) using excess water and evaporating the water

<td>by heating to 60 ° C under vacuum and</td><td>with rotation in</td><td>a flask</td><td>of</td>

<td>round bottom to dry until</td><td>Get one</td><td>load of</td><td>Neither</td>

<td>target of 1% by weight.</td><td></td><td></td><td></td>

<td>Example 9</td><td></td><td></td><td></td>

(Comparative example without dehydrogenation)

In an Inconel reactor with an internal diameter of 0.369 inches the depth of the catalyst introduced from the bed of the catalyst of Example 8 was reduced to with a flow of approximately an 18 inch catalyst.

H2 at atmospheric pressure with

800 mL / min and temperature

The one is

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MXÁ1CAKO INSTITUTE OF THE industrial i'KJJlW'Lr

gradually increased from 25 ° C to 370 ° C in 3 hours.

Once this temperature was reached, the reactor was pressurized with H2 up to 100 psig and then a downstream mixture was fed into the reactor at a WHSV of 1.9 g ethanol / g catalyst / hour. Once the conditions were stabilized, an analysis of the reaction products was carried out. The gaseous products were analyzed by means of a gas chromatograph equipped with a flame ionization detector, the products in the aqueous phase were analyzed to determine their total carbon content and the components in the organic phase were analyzed using a gas chromatograph. equipped with a flame ionization detector and a mass spectrometer. The results obtained for this experiment are shown in Table 6.

Example 10

In an Inconel reactor with an internal diameter of 0.87 inches and with an Inconel thermowell with a DE of 0.1875 inches passing through the center of the reactor, the catalysts of the Examples (bottom catalyst, 8.5 inches) were introduced in stacked beds, separated by a thin layer of quartz wool.

The catalyst was reduced with H2 at atmospheric pressure with a flow of approximately 800 mL / min and the temperature gradually increased from 25 ° C to 350

INSTITUTE ΜΕΧΙΟΝΓ ·

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° C in 3 hours. Once this temperature was reached, the reactor was pressurized with H2 up to 125 psig and then a mixture of 70% ethanol (in deionized water) was fed downstream to the reactor at a WHSV of 1.1 g ethanol / g catalyst ZSM-5. Once the conditions were stabilized, an analysis of the reaction products was carried out. The gaseous products were analyzed by means of a gas chromatograph equipped with a flame ionization detector, the products in the aqueous phase were analyzed to determine their total carbon content and the components in the organic phase were analyzed using a gas chromatograph. equipped with a flame ionization detector and a mass spectrometer. The results obtained for this experiment are shown in Table 6.

Example 11

Catalysts from Examples 2 (top catalyst, 9.5 inches) and 8 (bottom catalyst, 9.5 inches), separated by a thin layer of quartz wool, were introduced in a stacked bed into an Inconel reactor with an internal diameter of 0.369 inches. . The catalyst was reduced with H2 at atmospheric pressure with a flow of approximately 800 mL / min and the temperature gradually increased from 25 ° C to 370 ° C in 3 hours. Once this temperature was reached, the reactor was pressurized with H2 up to 100 psig and

a mixture of a-kan oi-a4 -— ferr water DI) was then fed into the reactor downstream to a WHSV of 1.9 g ethanol / g catalyst ZSM-5. Once the conditions were stabilized, an analysis of the reaction products was carried out. The gaseous products were analyzed by means of a gas chromatograph equipped with a flame ionization detector, the products in the aqueous phase were analyzed to determine their total carbon content and the components in the organic phase were analyzed using a chromatograph of gases equipped with a flame ionization detector and a mass spectrometer. The results obtained for this experiment are shown in Table 6.

Table 6. Dehydrogenation and condensation of ethanol using copper and acid catalysts.

<td>Experiment</td><td></td><td>Example 9</td><td>Example 10</td><td>Example eleven</td>

<td>Catalyst</td><td></td><td>None</td><td>5 of</td><td>5% Cu</td>

<td>dehydrogenation</td><td></td><td></td><td>on</td><td>gamma</td>

<td>ethanol</td><td></td><td></td><td>SiO2</td><td>alumina</td>

<td>Catalyst</td><td></td><td>1 of</td><td>1 of</td><td>ZSM-5</td>

<td>condensation</td><td></td><td>Neither</td><td>Neither</td><td>united</td>

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<td></td><td></td><td>united by AI2O3</td><td>united by AI2O3</td><td></td>

<td>Production in the organic phase</td><td>% carbon fed</td><td> 55</td><td> 69</td><td> 59</td>

<td>Production of hydrogen</td><td>Moles of H2 produced / moles of carbon fed</td><td> 0.03</td><td> 0.42</td><td> 0.10</td>

<td>Total production of aromatic compounds</td><td>% carbon fed</td><td> 41</td><td> 57</td><td> 50</td>

<td>Total production of paraffins</td><td>% carbon fed</td><td> 49</td><td> 29</td><td> 42</td>

Control of the degree of dehydrogenation of alkanol bypassing the catalyst of dehydrogenation

In certain cases it may be convenient to feed a portion of the fed alkanol directly to the condensation catalyst without going through the dehydrogenation catalyst. This allows precise control of the average degree of dehydrogenation.

Example 12

In an Inconel reactor with an internal diameter of 0.87 inches and with an Inconel thermowell with a DE of 0.187 5 inches passing through the center of the reactor, a

ÍHl> L '; TIJAL

V, stacked bed configuration using Examples 4 and 8. A thermowell with a DE of 0.1875 inches was placed on the center line of the catalyst bottom bed of Example 4. Said catalyst was introduced to a length of 8.5 inches. The top catalyst, from Example 8, was introduced to a length of 8.5 inches. The two catalyst beds were separated by a thin layer of quartz wool and approximately 2 inches of inert packing material. Two feed lines and two HPLC pumps were installed to supply the raw material to both catalyst beds. A feed line entered through the reactor head and the second line extended along the top catalyst bed to divert the raw material to the conversion catalyst. The entire catalyst bed was reduced to atmospheric pressure with a flow of approximately 800 mL H2 / min and the temperature gradually increased from 25 ° C to 370 ° C in 3 hours. Once this temperature was reached, the reactor was pressurized with H2 up to 100 psig and then a mixture of 70% ethanol (in deionized water) was fed downstream to the reactor at a WHSV of 1 g ethanol / g catalyst ZSM-5 / hour. Once the conditions were stabilized, an analysis of the reaction products was carried out. Ethanol feedstock was divided between upper and lower catalyst

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in proportions of 1: 1, 2: 1 and 1: 2, and an oxidative regeneration was carried out between the weight controls for each proportion of the raw material division. The gaseous products were analyzed by means of a gas chromatograph 5 equipped with a flame ionization detector, the products in the aqueous phase were analyzed to determine their total carbon content and the components in the organic phase were analyzed using a chromatograph of gases equipped with a flame ionization detector and a mass spectrometer. The results obtained for this experiment are shown in Table 7.

Example 13

Example 12 was repeated at 300 psig. All other specific details of the experimental setup and operation remained unchanged. The results obtained for this experiment are shown in Table 7.

Table 7. Dehydrogenation and condensation of ethanol using copper and acid catalysts.

<td>Experiment</td><td></td><td>Example 9</td><td>Example 12</td><td>Example 13</td>

<td>Ethanol dehydrogenation catalyst</td><td></td><td>None</td><td>5% Cu over SiO2</td><td>5% Cu about SiO2</td>

<td>Condensation catalyst</td><td></td><td>1% Ni over ZSM-5 joined by A12OR3</td><td colspan="3">1% Ni over ZSM-5 attached by A12OR3</td><td colspan="3">1% Ni over ZSM-5 bound by A12OR3</td>

<td>Pressure</td><td>Psig</td><td> 100</td><td> 100</td><td></td><td></td><td> 300</td><td></td><td></td>

<td>Raw material division ratio</td><td>Dehydrogenation: Condensation</td><td> 0:1</td><td> 2:1</td><td> 1:1</td><td> 1:2</td><td> 2:1</td><td> 1:1</td><td> 1:2</td>

<td>Production in the organic phase</td><td>% carbon fed</td><td> 55</td><td> 60</td><td> 56</td><td> 57</td><td> 62</td><td> 53</td><td> 58</td>

<td>Production of hydrogen</td><td>Moles of H2 produced / moles of carbon fed</td><td> 0.03</td><td> 0.19</td><td> 0.13</td><td> 0.08</td><td> 0.11</td><td> 0.09</td><td> 0.06</td>

<td>Total production of aromatic compounds</td><td>% carbon fed</td><td> 41</td><td> 57</td><td> 52</td><td> 49</td><td> 51</td><td> 45</td><td> 43</td>

<td>Total production of paraffins</td><td>% carbon fed</td><td> 49</td><td> 39</td><td> 39</td><td> 42</td><td> 38</td><td> 48</td><td> 46</td>

INSTITUI O Μ '.X ICAA'O

P? The Fp.ji'ISrSA »(« CVÍTCI Al

- 44 It is noted that in relation to this date, the best method known by the applicant to put the aforementioned invention into practice, is the one that is clear from the present description of the invention.

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BR112014012108A8	Brazil	A8	2017-06-20
US9873643B2	United States of America	B2	2018-01-23
US9878966B2	United States of America	B2	2018-01-30
MX354839BThis record	Mexico	B	2018-03-22
CA2856531C	Canada	C	2019-03-12
EP2782887B1	European Patent Office (EPO)	B1	2019-04-17
MY170515A	Malaysia	A	2019-08-08
BR112014012108B1	Brazil	B1	2019-10-15
PL2782887T3	Poland	T3	2019-10-31

Abstract

Term

CIP:

CPC:

J

I

NUMBER:

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

MX / 2018/24915

IMPJ

INOLISTMAL

DEHYDROGENATION OF ALCANOLS TO INCREASE PRODUCTION

OF AROMATIC COMPOUNDS

CROSS REFERENCE TO RELATED REQUESTS

TECHNICAL FIELD

BACKGROUND OF THE INVENTION

H — 20

SUMMARY OF THE INVENTION

IMPI

M2XICANO INSTITUTE

- 10 IMPI

OF INDUSTRIAL RETURN

DESCRIPTION OF THE DRAWINGS

DETAILED DESCRIPTION OF THE INVENTION

IMP

7 JK MEXICAN INSTITUTE

DS THE PROPERTY

INDUSTRIAL

MEXICAN JNSTITUTE

OF THE FROI-IEDAD

INDUSTRIAL

- 17 IMPI

MEXICAN INSTITUTE OF PROPERTY

INDUSTRIAL

IMPI

MEXICAN INSTITUTE

- 20 IMPI

INDUSTRIAL

EXAMPLES

MSXICAN INSTITUTE

OF INDUSTRIAL PROPERTY

INDUST1 JAL

I

THE

CO

I

INDUSTRIAL

GAVE

X 2L MEXICAN INSTITUTE EU LA MOHEDAL 'INDUSTRIAL

IMPI

OF THE

Priority claims7

Members33

Events

Numbers

Titles2

Classification