Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
  • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
  • C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
  • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
  • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
  • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation

Definitions

• the present invention relates to a process for preparing a mixture of alcohols.
• the most important alcohols are ethanol, 1-propanol, n-butanol, alcohols for plasticizers having a (C6-C1 1) alkyl chain and fatty alcohols having a (C12-C18) alkyl chain. used as detergents.
• These different alcohols are prepared from fossil resources either by the oxo olefins route or by the Ziegler process (trialkylaluminum oxidation) (Ziegler, K. et al., Justus Liebigs Ann.Chem 629 (1960) 1).
• Alcohols are also used as solvents, paint thinners (mainly light alcohols having (C1-C6) alkyl chain), as intermediates leading to esters, but also as organic compounds, as lubricants or as fuels.
• alcohols having a C6 alkyl chain are synthesized by co-dimerization of butene and propene and then converted to a mixture of aldehydes by hydroformylation, before being hydrogenated, to finally lead to a mixture of alcohols having a C6 alkyl chain.
• butanol has so far been produced largely by the process of hydroformylation of propylene a petroleum derivative (Wilkinson et al., Comprehensive Organometallic Chemistry, The synthesis, Reactions and Structures of Organometallic Compounds, Pergamon Press 1981, 8).
• Butanol can also be obtained by fermentary processes that are up-to-date with the rise in petroleum raw materials.
• Acetobutyl fermentation better known as ABE fermentation, co-produces a mixture of ethanol, acetone and butanol in a weight ratio of about 1/3/6.
• the source bacterium of fermentation belongs to the family of Clostridium acetobutylicum.
• the object of the present invention is to provide a process comprising a simplification of the step of separating the alcohols formed.
• the invention also aims to prepare a mixture of alcohols without incondensable gas.
• Another object of the present invention is to provide a process for obtaining a mixture of alcohols free of aldehyde and in particular of acetaldehyde.
• the object of the invention is to provide a process for stabilizing the reaction medium.
• Another object of the present invention is to provide a process for the preparation of alcohols, in particular butanol, which is easy to implement and leads to a better overall yield of the reaction.
• the subject of the present invention is therefore a process for preparing a mixture (M) comprising at least one alcohol (Aj), said process comprising the following steps:
• mixture (A) a mixture from step i) of oligomerization of at least one alcohol (Ai) gas phase.
• the mixture (A) therefore represents a gaseous mixture at the reaction temperature.
• mixture (A) condensed means a mixture (A) which has undergone a step ii) of condensation at the end of step i).
• the condensed mixture (A) constitutes the mixture subjected to step iii) of hydrogenation in the liquid phase.
• alcohols (Ai) means alcohols whose linear or branched alkyl chain comprises n carbon atoms, with n representing an integer of from 1 to 10. According to the invention, the term “alcohols (Ai)” also includes the term “starting alcohols”.
• the “alcohols (Al)” according to the invention can be for example: methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol or decanol.
• Alcohols (Al) denote the starting alcohols before the oligomerization step.
• alcohols (Aj) means alcohols whose linear or branched alkyl chain comprises m carbon atoms, with m representing an integer from 2 to 20 According to the invention, the The term “alcohols (Aj)” also includes the term “formed alcohols” or "upgraded alcohols”.
• the “alcohols (Aj)” according to the invention may be, for example, ethanol, butanol, hexanol, octanol, decanol, ethyl-2-butanol and ethyl-2-hexanol.
• the alcohols (Aj) are obtained by oligomerization of one or more alcohols (Ai).
• oligomerization of an alcohol means a process for converting a monomeric alcohol into an oligomeric alcohol. According to the invention, the oligomerization may for example be a dimerization.
• the alcohol (Al) is ethanol.
• the oligomerization is a dimerization, preferably a dimerization of ethanol.
• the mixture (M) obtained comprises butanol.
• the present invention relates to a process for preparing a mixture (M) comprising butanol, said process comprising the following steps:
• the oligomerization stage, in particular dimerization, in the gas phase can be carried out using any reactor, generally known to those skilled in the art.
• the alcohol (s) (Ai) used may be anhydrous or aqueous. If the alcohol (s) (Ai) used is (are) aqueous, it (they) may (s) comprise from 0.005 to 20% by weight of water relative to the total weight of alcohol (s) (Ai).
• step i) of oligomerization, in particular of dimerization, of the process can be carried out in the presence of an acid-base solid catalyst.
• the catalyst is alkaline earth phosphate type. More particularly, the catalyst is selected from catalysts of the family of calcium hydroxyapatite (HAP) of the general formula Caio- z (HP0 4) z (P0 4) 6-z (OH) 2 - z with 0 ⁇ z ⁇ 1.
• the molar ratio (Ca + M) / P is between 1, 5 and 2 preferably from 1.5 to 1.8, and preferably from 1.6 to 1.8.
• M may represent a metal or a metal oxide, ranging from 0 to 50 mol% of calcium substitution, in particular from 0 to 20 mol%, and may be chosen from Li, Na, K, Rb, Cs, Se, Y, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Yb.
• step i) of the process may be carried out at a temperature of from 100 ° C. to 500 ° C., preferably from 200 ° C. to 450 ° C., and preferably from 300 ° C. to 450 ° C.
• the temperature is from 350 ° C to 425 ° C, and more particularly from 375 ° C to 425 ° C.
• step i) can be carried out at a pressure of from 0.3 to 6 bar absolute, and preferably from 0.8 to 5 bar absolute.
• step i) of the process of the invention one or more alcohols (Ai), in particular ethanol, can (wind) be fed (s) in the vapor phase.
• the flow rate of alcohol (s) (Ai) of said step i) is from 1 to 10 g of alcohol (Ai), per hour and per g of catalyst, preferably from 1 to 8, preferably from 1 to 6 and even more preferably from 1 to 5.
• the flow rate of alcohol (s) (Ai) is from 2 to 6 g of alcohol (s) (Ai) per hour and per g of catalyst.
• productivity means measuring the efficiency of the process.
• productivity according to the invention corresponds to the amount of an alcohol (Aj), in particular butanol, produced per hour, for one gram of catalyst used in the process.
• yield means the ratio expressed as a percentage, between the quantity of product obtained and the desired theoretical amount.
• step i) in the gas phase (vapor phase), can lead to a mixture (A) comprising especially from 1% to 30% by weight of reducible products, considered as reaction intermediates.
• the term "reducible product” means a compound that can be reduced during the hydrogenation step iii), such as an alkene, an alkyne, an aldehyde or a ketone.
• the reducible products can be, for example, acetaldehyde, the crotonaldéhydes (c / 's and trans), the crotyl alcohol (c /' s and trans), the buten-1-ol, butadiene, butanal, hexenols and hexanal.
• the mixture (A) is subjected at the end of step i) and before step iii), to a condensation step of the mixture (A) (step ii) leading to a gas flow and to a condensed mixture (A) corresponding to a liquid flow.
• This step makes it possible to carry out the hydrogenation reaction in the liquid phase.
• the condensed mixture (A) may be subjected at the end of step ii) and before step iii), to a step of separation of the liquid / gas streams, in order to eliminate the gas flow.
• the additional step of separating the liquid / gas flows can be carried out on the condensed mixture (A), in order to eliminate the gas flow and the non-valorized light constituents.
• This step advantageously makes it possible to overcome incondensable gases.
• incondensable gas means a gas that can not be condensed in a liquid phase at a temperature above 20 ° C at atmospheric pressure.
• the non-condensable gases may be for example carbon monoxide, butene, ethylene, hexene, butane, carbon dioxide, hydrogen and ethane.
• the process according to the invention advantageously makes it possible to obtain a better life of the catalyst of the hydrogenation reaction.
• the process according to the invention comprises a step ii) of the condensation of the reaction mixture (A) at the exit of oligomerization, in particular of dimerization, (at the end of stage i) and of separation of the liquid streams / gas, separates the incondensable gases from the liquid phase to be hydrogenated (step iii).
• these noncondensable gases contain in particular significant amounts of carbon monoxide (CO), up to 130 ppm, which is a poison of hydrogenation catalysts conventionally used industrially as nickel.
• CO carbon monoxide
• This separation also makes it possible to avoid the coking of the hydrogenation catalyst, which is often due to the incondensible carbonaceous species of the ethane, ethylene, hexene, butane or butadiene type. Some of these species tend to polymerize.
• This separation also allows a saving of hydrogen since the unsaturated species, butadiene, ethylene, hexene in particular present in the gas stream are not hydrogenated.
• the mixture (A) obtained at the end of step i) is cooled to a temperature of between 0 ° C. and 100 ° C. in order to condense and separate the various constituents of said mixture (A) . Cooling can be achieved using technology well known to those skilled in the art, such as a tube / shell heat exchanger or a plate heat exchanger.
• a vapor flow (gas flow) and a liquid flow (condensed mixture (A)) are obtained.
• the vapor stream and the condensed mixture (A) can be separated in one or more single vapor liquid separators operating at lower and lower temperatures, including heat exchangers, in a distillation column or in these two types of equipment in series.
• two flows can be obtained, a gas flow preferably containing at least one alcohol (Ai), in particular ethanol, and gases such as hydrogen, ethane, ethanol. ethylene or butene and a liquid stream containing the remainder of alcohol (s) (Ai) unconverted, the water from the reaction and the alcohols (Aj) valued.
• Alcohol in particular ethanol
• gases such as hydrogen, ethane, ethanol.
• ethylene or butene ethylene or butene
• the method may comprise a step of washing the gas stream obtained at the end of the separation step.
• the washing step can be carried out in an absorber in order to recover the alcohol (s) (Ai) contained, in particular ethanol, as well as acetaldehyde entrained in the gas stream resulting from the step of separation.
• this absorption washing step can be carried out in a washing column operating at the minimum possible temperature, comprised between 0 ° C. and 50 ° C., depending on the cold sources available, and at the same pressure as step i) (with the pressure losses close). It can be carried out with alcohol-free water (Al), and in particular free of ethanol, or by using alcohols (Aj) produced later in the process.
• the gas stream from the washing step is advantageously purified so as to recover the hydrogen present in said gas stream for use in the hydrogenation step iii).
• the hydrogen can be purified by a pressure swing adsorption mechanism (known under the PSA technology to denote the expression Pressure Swing Adsorption), by use of a porous membrane, by absorption or by cryogenics.
• the condensed mixture (A), having optionally been subjected to an additional separation step, is subjected to a step iii) of hydrogenation in the liquid phase.
• the alcohol (s) (Ai), used in said step i) of the process according to the invention present in said mixture (A) condensed and unreacted, for example ethanol, are advantageously separated from (es) alcohol (s) (Aj) also present (s) in said mixture (A) condensed by liquid / liquid separation, prior to the implementation of said step iii).
• said condensed mixture (A) is preferably subjected to at least one distillation step so as to obtain at least a first liquid stream comprising, preferably consisting of, the alcohol (s) (Ai) n ' unreacted during the implementation of said step i) of the process according to the invention and a second liquid stream comprising, preferably consisting of (s) alcohol (s) (Aj).
• the alcohol (s) (Ai) extracted (s) from said mixture (A) condensed are advantageously directly valued, for example to be introduced (s) into fuel bases.
• the condensed mixture (A) resulting from stage ii) can be brought to a temperature below 165 ° C. by a technology well known to those skilled in the art, such as a heat exchanger. shell or plate type.
• the hydrogenation step in the liquid phase is carried out at a temperature of less than or equal to 165 ° C.
• the temperature is from 50 ° C to 165 ° C, preferably from 60 ° C to 162 ° C, and preferably from 80 ° C to 160 ° C.
• the condensed mixture (A) is then brought into contact with a hydrogen flow rate sufficient to hydrogenate the reducible products.
• the hydrogen flow rate can be from 0.48 to 240 L / g a
• the hydrogenation step in the liquid phase is carried out at a pressure greater than or equal to 10 bar.
• the pressure is from 10 to 50 bar, preferably from 12 to 45 bar, and preferably from 15 to 40 bar.
• the hydrogen used in said step iii) comes from said purified gas stream according to one of the methods described above and / or from a process for producing hydrogen using a hydrocarbon or an alcohol such as ethanol.
• the liquid phase hydrogenation step may be carried out in the presence of a metal catalyst selected from the group consisting of Fe, Ni, Co, Cu, Cr, W, Mo, Pd, Pt, Rh and Ru, said catalyst being optionally supported.
• a metal catalyst selected from the group consisting of Fe, Ni, Co, Cu, Cr, W, Mo, Pd, Pt, Rh and Ru, said catalyst being optionally supported.
• a support mention may be made of alumina, celite, zirconium dioxide, titanium dioxide or silica.
• the catalyst used is selected from the group consisting of Ni, Co, Cu, Pd, Pt, Rh and Ru, optionally supported.
• the catalyst may be of the Raney nickel type.
• the metals can be used alone or as a mixture.
• the hydrogen phase in the liquid phase can be carried out using any reactor, generally known to those skilled in the art.
• the liquid phase hydrogenation step can be carried out in a tubular or multitubular fixed bed reactor, isothermal or adiabatic, or a catalyst-coated exchanger reactor, or a reactor agitated by a self-aspirating mobile, or a venturi or tubular ejector.
• the catalyst used in step iii) can be immobilized, in the form of grains, extrusions or in the form of metal foam.
• the catalyst used in step iii) may be in the form of fine particles.
• the catalyst can be immobilized in a reactor in the form of grains or extrudates or supported on a metal foam.
• the reactor associated with this type of catalyst is preferably a fixed tubular or multitubular bed, isothermal or adiabatic, or a catalyst-coated exchanger reactor, operated in dripping or flooded mode;
• the reactor preferred for this type of catalyst may be selected from the group of reactors agitated by a self-aspirating mobile or a venturi or tubular ejector. Typically, in this type of equipment, the catalyst must then be separated by a suitable technology type tangential filter or decanter.
• the hydrogenation stage in the liquid phase is carried out in equipment of type a) described above.
• the mixture (M) obtained at the end of the hydrogenation stage is devoid of the intermediate species obtained at the end of stage i), such as alcohologens, such as crotyl alcohols (c). / 's and trans), butanal, buten-1-ol, hexanal or crotonaldéhydes (c /' s and trans), the héxénols which were reduced in the form of products of economic value.
• the hydrogenation step may therefore allow an increase in the yield of the reaction in all the different alcohols (Aj) generated.
• the mixture (M) obtained is devoid of aldehyde species, and in particular free of acetaldehyde, which allows a better stability over time of said mixture (M).
• the mixture (M) may comprise the remainder of unconverted alcohol (s) (Ai), and in particular ethanol, water resulting from the reaction and / or derived from alcohol. (s) (Ai) nine, and alcohols (Aj), especially butanol.
• the mixture (M) obtained according to the process may comprise at least 5% (by weight relative to the total weight of the mixture (M)) of butanol, preferably at least 8%, and preferably at least 10% butanol.
• the alcohol (Ai) new differs from the alcohol (Ai) recycling.
• said mixture (M) preferably comprises several alcohols (Aj) whose linear or branched alkyl chain comprises m carbon atoms, with m representing an integer equal to 2 or comprised from 2 to 20
• the mixture (M) comprises, besides butanol, other alcohols (Aj), the linear or branched alkyl chain of which comprises m carbon atoms, with m representing an integer equal to at 2 or from 2 to 20.
• the mixture (M) may comprise, in addition to butanol, linear alcohols, such as hexanol, octanol or decanol, or branched alcohols such as ethyl-2-butanol or ethyl- 2-hexanol.
• the process may comprise, at the end of step iii), successive distillation steps for separating the different valued alcohols from the mixture (M), as well as stages of alcohol recycling. (s) (Ai), especially ethanol.
• the mixture (M) containing the residue of unconverted alcohol (s) (Ai), especially ethanol, the water resulting from the reaction and / or from alcohol (s) (Ai) nine (s), and the valued alcohols can be separated into a set of distillation columns intended to recover the valuable alcohols, remove the water resulting from the reaction and the water from alcohol (s) (Ai) nine ( s) (in the case where the alcohol (s) (Ai) used for the oligomerization is (are) aqueous) and recycle the unconverted alcohol (s) (Ai) ( s) of the reaction, usually in their azeotropic form.
• the mixture (M) resulting from the hydrogenation under pressure can be expanded to a pressure making it possible to carry out the separation of the azeotrope water / alcohol (s) (Ai) and of the valued alcohols.
• mixture (M) expanded a mixture (M) which was expanded at the end of the hydrogenation step.
• the expanded mixture (M) resulting from the hydrogenation can be directed to a set of two distillation columns designated C1 and C2, nested to obtain three streams:
• F1 the azeotrope water / alcohol (s) (Al), and especially the water / ethanol azeotrope, which is recycled;
• the columns C1 and C2 may be tray columns or packed columns.
• the supply can be performed in column C1, the floor to optimize the performance of the whole.
• a decanter can be installed in the lower part of the column C1, below the supply tray which separates these two liquid phases, or the settling tank can be installed inside or outside the column. C1.
• the organic phase, rich in alcohol (s) (Aj) can be recycled as internal reflux of the column C1 and provides the mixture of alcohols (Aj) at the bottom of this column C1.
• the aqueous phase can exit column C1 and be sent to a column C2 which can be a reflux separation column or a simple stripper.
• This column C2 may be reboiled and may make it possible to obtain at the bottom a flow of water which is free of alcohols (Al) and (Aj), and in particular of ethanol and butanol.
• the distillate of the column C2 may be preferably in vapor form, this column operating at the same pressure as the column C1.
• the vapor phase of this column C2 can be returned to the column C1, preferably to the stage above the stage of the liquid / liquid settler.
• the head of column C1 is conventional and may include a condenser to obtain the reflux required for separation.
• the azeotrope water / alcohol (s) (Al) (F1), and in particular the water / ethanol azeotrope, can then be obtained at the top. It can be obtained in the vapor phase or in the liquid phase. If it is obtained in the vapor phase, it avoids having to vaporize it before feeding the synthesis reaction, which advantageously makes it possible to reduce the energy consumption required.
• the alcohols (Aj) (F3) are obtained at the bottom of the column C1. They can be separated by simple distillation in an additional C3 column to obtain the pure butanol at the head and the other alcohols (Aj) different from butanol at the bottom.
• the different alcohols (Aj) can then be separated by successive distillations to obtain these different alcohols in the order of their boiling points. Distillation of the alcohols by distillation can still be carried out by the so-called partition column distillation technique (known by the English term DWC to designate the expression Dividing Wall Column).
• the alcohol (Ai) new, and in particular new ethanol, pure or containing water as well as the alcohol (Ai) recycling, including recycling ethanol, if is liquid can be vaporized and then overheated to the temperature reaction before entering a reactor where the oligomerization takes place (oligomerization reactor).
• the recycling alcohol (Ai) in particular the recycle ethanol, is in vapor form
• the alcohol (Ai) new, and especially the fresh ethanol may be vaporized and then superheated to the reaction temperature before to enter the oligomerization reactor.
• the method according to the invention advantageously allows an increase in the overall yield of the reaction, a simplification of the separation step of the alcohols (Aj) formed and a stabilization of the reaction medium.
• the hydrogenation step in the liquid phase advantageously allows a better selectivity than a process comprising a step of hydrogenation in the gas phase.
• the gas phase hydrogenation of batches resulting from an oligomerization, and in particular a dimerization, of alcohol (s) (Al), and in particular ethanol, on acid-base catalysts is not complete;
• aldehydes such as acetaldehyde remain, as has been observed in application EP 2206763. This is due to a thermodynamic equilibrium.
• acetaldehyde is not a valuable product and causes separation problems. Indeed, the separation of ethanol and acetaldehyde is difficult because there is an azeotrope.
• the process according to the invention makes it possible to facilitate the separations insofar as the mixture comprises one less species to be separated and that there are fewer acetaldehyde-alcohol binaries.
• the ethanol formed from the acetaldehyde according to the invention can then be reinjected into the process. This has the effect of lowering the conversion of ethanol and thus increasing selectivities and yields of valuable alcohols, especially butanol.
• the hydrogenation stage in the liquid phase makes it possible to improve the efficiency and the overall selectivity of the process.
• the hydrogenation in liquid phase is interesting because it allows to stabilize the mixture over time, due to the absence of aldehyde species.
• the hydrogenation stage in the liquid phase is advantageous for reducing the size of the process.
• a hydrogenation in the liquid phase makes it possible to use smaller amounts of hydrogen and catalyst than for hydrogenation in the gas phase (of which a molar excess of H 2 is necessary), while maintaining a high efficiency.
• the following examples illustrate the invention without limiting it. Examples
• Example 1 Hydrogenation Liquid Phase with Catalyst Ni (HTC) at 130 ° C.
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• the conversion of ethanol is 25.5%.
• the weight percentages of the different products are as follows:
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• the conversion of ethanol is 20%.
• the weight percentages of the different products are as follows:
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• the conversion of ethanol is 30.4%.
• the weight percentages of the different products are as follows:
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• Example 6 Hydrogenation Liquid Phase with Catalyst Ni (HTC) at 160 ° C.
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%
• Example 7 (Comparative Example): hydrogenation gas phase
• This example corresponds to amounts identical to Example 6, but with a different hydrogenation equipment adapted for gaseous phases.
• Acetaldehyde 0.84% (corresponding to 2.54% of selectivity)
• Crotyl alcohol and isomers 0.05%
• Crotonaldehyde 0%
• Example 8 hydrogenation gas phase with another catalyst and a different flow rate
• the conversion of ethanol is 31.6%.
• the weight percentages of the different products are as follows:
• Crotyl alcohol and isomers 0.06%
• Crotonaldehyde 0%
• a liquid phase was recovered after condensation at 10 ° C of the mixture at the reactor outlet.
• a hydrogenation was carried out with 14.4 g of catalyst 13% (by weight) CuO / SiO 2 from the supplier Evonik-Degussa (beads 3 to 5 mm in diameter) immobilized in a glass reactor at 180 ° C with a hydrogen flow rate of 100 ml / min at atmospheric pressure and a liquid flow rate to be hydrogenated of 0.55 ml / min.
• Crotyl alcohol and isomers 0.06%
• Crotonaldehyde 0%
• a selectivity of 0.1% (CO) corresponds to 0.013% (by weight) or 130 ppm of CO in the stream to be hydrogenated. This level is largely sufficient to deactivate a hydrogenation catalyst very rapidly.
• Example 10 (Comparative Example): Cracking During a Gas Phase Hydrogenation
• Crotyl alcohol and isomers 0%
• Crotonaldehyde 0%

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