# Patent

## Title
Method for dehydrating a mixture containing ethanol and n-propanol

## Abstract

The present invention relates to a process for the production of a mixture of ethylene and propylene from a mixture containing ethanol and n-propanol and having a water content comprised between 30 and 75% by weight with respect to the total weight of the mixture.

## Background
The present invention relates to a process for the production of a mixture of ethylene and propylene from an aqueous mixture containing ethanol and n-propanol. The process according to the invention allows in particular the treatment of an aqueous mixture of ethanol and n-propanol which is obtained from renewable sources such as for example biomass.
STATE OF THE ART
The light olefins are important intermediates in the chemical industry and are mainly produced by catalytic cracking or steam cracking of hydrocarbons.
For example propylene is widely used in the chemical industry in the production of acrylonitrile, acrylic acid and above all polypropylene. The same applies to ethylene which is used for the synthesis of a large number of polymers and plastic materials, such as polyvinyl chloride (PVC), polyethylene (PE) and polyester via monoethylene glycol (MEG).
In order to respond to future challenges associated with decreasing oil resources and environmental concerns, much research is currently being carried out in order to develop alternative technologies for the syntheses of these intermediates from renewable resources.
At present one of the most studied routes for the production of olefins is that of the catalytic dehydration of alcohols.
The dehydration reaction of ethanol to ethylene is known and has been presented in detail since the end of the 19th century. It is known that this reaction is very endothermic, balanced and shifted toward ethylene at high temperature. The reference catalyst that is often used is a monofunctional acid catalyst. Gamma-alumina is the most cited catalyst. The article “The Dehydration of Alcohols over Alumina. I: The reaction scheme”, H. Knözinger, R. Köhne, Journal of Catalysis (1966), 5, 264-270 is considered to be the basic publication on the works on the dehydration of alcohols including ethanol.
The zeolites are also used for this application, and in particular ZSMS since the 1980s, as described in “Reactions of ethanol over ZSM-5”, S. N. Chaudhuri & al., Journal of Molecular Catalysis 62:289-295 (1990).
The dehydration route for alcohols corresponds well to the problem of producing olefins in an alternative and “green” manner. In fact, ethanol and its higher homologues can be synthesized by the fermentation of sugars obtained from renewable sources such as starch- or sugar-containing plants (e.g. maize, sugar cane respectively) or from lignocellulosic biomass such as for example wood shavings or culture residues (wheat straw).
Document WO 2004/078336 is known from the state of the art, which discloses a process for the production of α-olefins by dehydration of linear or branched alcohols having 4 to 14 carbon atoms in the presence of a γ alumina comprising:
a pore volume greater than 0.9 mL/g (determined according to the DIN 66133 method);
pores in the mesoporous domain (maximum diameter comprised between 20 and 90 Å);
pores in the macroporous domain (maximum diameter greater than 250 Å).
The subject of application WO 2011/162717 is a process for the production of olefins by dehydration of a mixture of alcohols using a catalyst comprising a zeolite doped with a metallic element chosen from: Mg, Ca, Ba, Sr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ce, Ag, Bi, Ti, V, Zr, Mo, W, Li, La. The use of alcohols obtained by the treatment of biomass is envisaged in this document.
Finally, the patent application FR 2 961 202 describes a process for the production of C4 olefins from a C4 monoalcohol feedstock by a dehydration reaction of said alcohol in the presence of a catalyst based on alumina with controlled porosity.
A purpose of the present invention is to provide a process for the production of a mixture of ethylene and propylene directly from a mixture containing water, ethanol and n-propanol. According to the invention, the process applies in particular to a mixture of ethanol and n-propanol of biological origin obtained from the treatment of biomass.
SUMMARY OF THE INVENTION
Therefore the present invention relates to a process for the production of a mixture of ethylene and propylene from a mixture containing ethanol and n-propanol and having a water content comprised between 30 and 75% by weight with respect to the total weight of the mixture, in which:

    
    
        a) the mixture is brought into contact, in a dehydration unit, with a dehydration catalyst chosen from:
        
            an alumina (A) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 350 m2/g, a mean mesopore diameter comprised between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulphur content of less than 40 ppm by weight; and
            an alumina (B) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 130 and 180 m2/g, a mean mesopore diameter comprised between 14 and 20 nm, a sodium content comprised between 300 and 600 ppm by weight and a sulphur content comprised between 800 and 1300 ppm by weight;
        
        
        the bringing into contact being carried out at a temperature comprised between 350 and 500° C., at a total pressure comprised between 0.2 and 2 MPa and with a weight hourly space velocity (whsv) defined as being the ratio of the mass flow rate of ethanol and n-propanol to the mass of catalyst comprised between 1 and 10 h−1 
        b) an effluent containing ethylene and propylene is drawn off from said dehydration unit.
    
    


The process according to the invention thus makes it possible to respond to the challenges of the energy transition by proposing an alternative process to the petrochemical sector for the production of ethylene and propylene, starting from a mixture of alcohols which can be of biological origin.
Surprisingly, the inventors have found that a catalyst having the characteristics mentioned above has a high dehydration activity, while also being selective for the sought olefins.
The process according to the invention has the advantage that it dispenses with a stage of separating the ethanol from the n-propanol before the dehydration stage. In fact, thanks to the catalysts according to the invention, it is possible, in a single catalytic stage, to dehydrate the mixture of said alcohols and thus produce an effluent comprising ethylene and propylene.
The process is therefore advantageous from an economic and energy point of view when it is envisaged to produce ethylene and propylene for petrochemistry. In fact, thanks to the process it is not necessary to carry out a prior separation of the ethanol and the n-propanol from the aqueous mixture before dehydration. This separation of the two alcohols is particularly costly in terms of investment because in order to be efficient, due to the existence of azeotropic compositions, it is necessary not only to concentrate the mixture of alcohols in such a way as to obtain a concentration of alcohols greater than 50% by weight, but also to utilize a distillation column having a large number of trays. Thus an advantage of the process according to the invention is that it makes it possible to produce ethylene and propylene for petrochemistry involving a smaller number of unit operations which produces a not inconsiderable economic advantage. Thus, after the dehydration stage according to the invention, a flow is obtained containing propylene and ethylene which can, however, be easily separated by distillation.
The process according to the invention makes it possible to dehydrate a mixture containing water, ethanol and n-propanol and to advantageously use the water contained in said mixture as thermal fluid during the dehydration stage. The dehydration reaction is highly endothermic and the fact that the feedstock is diluted with water makes it possible to reduce the endothermic nature of the reaction and thus carry out the reaction with a limited number of reactors. The water also makes it possible, thanks to the feedstock/effluent exchangers, to recover the condensation energy of the reaction products in order to produce the temperature required to dehydrate the feedstock.
Preferably, the alumina (A) has a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 280 m2/g and more preferably comprised between 200 and 230 m2/g.
Preferably the alumina (A) has a mean mesopore diameter comprised between 6 and 12 nm and more preferably comprised between 7 and 11 nm.
Preferably, the alumina (B) has a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 150 and 180 m2/g.
Preferably the alumina (B) has a mean mesopore diameter comprised between 15 and 20 nm.
According to a very preferred embodiment, the catalysts (A) and (B) according to the invention are gamma aluminas. More preferably, the catalysts according to the invention are constituted by gamma alumina.
The aluminas according to the invention can be prepared by any method known to a person skilled in the art. For example they can be obtained from an alumina gel (or gel of alumina) which essentially comprises a precursor of the aluminium oxy(hydroxide) (AlO(OH)) type—also denoted boehmite. The alumina gel (otherwise denoted boehmite gel) is for example synthesized by precipitation of basic and/or acid solutions of aluminium salts induced by changing the pH or any other method known to a person skilled in the art (P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, J. L. Le Loarer, J. P. Jolivet, C. Froidefond, Alumina, in Handbook of Porous Solids, Eds F. Schüth, K. S. W. Sing, J. Weitkamp, Wiley-VCH, Weinheim, Germany, 2002, pp. 1591-1677). The gel obtained is then subjected to one or more heat treatment stages which comprise in particular drying and calcination in order to form an alumina having the required structural characteristics according to the invention. It should be noted that the aluminas according to the invention can also be obtained from other alumina precursors such as for example bauxite, bayerite or by the oxidation of aluminium.
According to a particular embodiment, before stage a), a stage of reducing the water content (drying stage) of the ethanol/n-propanol/water mixture is carried out which comprises bringing the mixture into contact, in a liquid-liquid extraction column, with an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms. The aromatic cut is preferably a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene. Alternatively, the aromatic cut is a heavy reformate cut originating from a separation of the reforming product of a gasoline cut. The bringing into contact of the mixture of alcohols with the aromatic cut in the extraction column is preferably carried out in counter-current and preferably with a contact temperature comprised between 70 and 90° C.
This extraction stage makes it possible to separate an aqueous fraction and an organic fraction containing the aromatic cut, ethanol and n-propanol from the column. The organic fraction is then sent into a distillation column configured in order to separate an effluent containing the aromatic cut and an effluent containing ethanol and n-propanol. Finally, the effluent containing ethanol and n-propanol is sent into the dehydration unit of stage a) with a supply of water.
Alternatively, before stage a), a stage of reducing the water content of the ethanol/n-propanol/water mixture is carried out, which consists of sending the mixture into a distillation column in order to separate an aqueous fraction and an effluent having a reduced water content and containing ethanol and n-propanol. The effluent thus recovered is treated in the dehydration unit according to stage a).
Preferably the mixture containing ethanol, n-propanol originates from an esterification of propanoic acid with ethanol then hydrogenation of the ester (ethyl propanoate). Metabolic routes also exist allowing the conversion of the propanoic acid to the alcohol by enzymatic catalysis. In particular, the propanoic acid is the product of a propionic-type fermentation of a substrate chosen from the sugars, glycerol, lactic acid, malic acid. Preferably, the propanoic acid originates from the fermentation of sugars obtained by the treatment of biomass, for example lignocellulosic biomass. Another possible route is the fermentation of CO, H2, CO2 by anaerobic bacterial route, for example via Clostridium ljungdahlii which produces mixtures of alcohols containing n-propanol. Ethanol is for example the product of the fermentation of sugars obtained from renewable sources such as starch- or sugar-containing plants (e.g. maize, sugar cane respectively) or from lignocellulosic biomass such as for example wood shavings or culture residues (wheat straw).
Preferably, the dehydration process is carried out in two adiabatic reactors in series.
DETAILED DESCRIPTION OF THE INVENTION
The feedstock treated in the process according to the invention is a mixture containing between 30 and 75% by weight of water with respect to the total weight of the mixture of ethanol and n-propanol. The mixture which is treated by dehydration according to the invention can comprise any proportion of ethanol and n-propanol. Preferably, the mixture contains between 1 and 75% by weight of ethanol and between 99 and 25% by weight of n-propanol with respect to the total weight of ethanol and n-propanol.
The ethanol/n-propanol feedstock advantageously originates from renewable resources. Preferably the feedstock is a product originating from the biological treatment of biomass. Preferably, the ethanol/n-propanol feedstock is a feedstock produced by the esterification of propanoic acid with ethanol then hydrogenation of the ester. The propanoic acid is preferably of biological origin. The propanoic acid (also called propionic acid) is obtained by a so-called “propionic” fermentation of various substrates, such as glycerol, lactic acid, malic acid and sugars. Preferably, the propanoic acid originates from the fermentation of sugars which are produced from cultures of sugar-containing plants such as sugar cane, sugar beet, or also starch-containing plants or the treatment of lignocellulosic biomass or hydrolyzed cellulose. Microorganisms of the genus Propionibacterium are known which are capable of converting the substrates mentioned above to propanoic acid.
According to the invention the conversion of ethanol and n-propanol to ethylene and propylene respectively is carried out, for example in a reactor, by bringing the feedstock into contact with a catalyst chosen from:

    
    
        an alumina (A) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 350 m2/g, a mean mesopore diameter comprised between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulphur content of less than 40 ppm by weight; and
        an alumina (B) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 130 and 180 m2/g, a mean mesopore diameter comprised between 14 and 20 nm, a sodium content comprised between 300 and 600 ppm by weight and a sulphur content comprised between 800 and 1300 ppm by weight.
    
    


Determination of the mean mesopore diameter is carried out by mercury porosimetry according to the standard ASTM D 4284-03 with a contact angle of 140°. Analysis by mercury porosimetry corresponds to the intrusion of a volume of mercury characteristic of the existence of mesopores and macropores in said catalyst according to standard ASTM D4284-03, it being assumed that the pores are of cylindrical shape. This technique provides the value of the mesoporous mercury volume, defined as being the volume of mercury adsorbed by all of the pores having a diameter in the mesopore range, namely comprised between 2 and 50 nm. This mean mesopore diameter is obtained from the derived curve dV/d log(D) (V being the volume of mercury adsorbed and D the diameter of the pores) as a function of the diameter of the pores D and corresponds to the ordinate for which the abscissa dV/d log(D) is at its maximum.
The dehydration catalyst used in stage a) of the process according to the invention is advantageously formed in the form of grains of different shapes and sizes. It is advantageously used in the form of cylindrical or multilobed extrudates, such as bilobed, trilobed, multilobed of straight or twisted shape, but can optionally be manufactured and used in the form of crushed powder, pellets, rings, beads, wheels, or spheres. Preferably, said catalyst is in the form of extrudates. Said dehydration catalyst used in stage a) of the process according to the invention is advantageously utilized in at least one reactor, in a fixed bed or in a moving bed.
Within the scope of the invention, the catalyst can include at least at least one matrix of the oxide type, also called binder. Said matrix is advantageously selected from the elements of the group formed by clays (such as for example from the natural clays such as kaolin or bentonite), magnesia, aluminas, silicas, silica-aluminas, aluminates, titanium oxide, boron oxide, zirconia, aluminium phosphates, titanium phosphates, zirconium phosphates, and carbon.
According to a preferred embodiment, the alumina denoted “A” has a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 280 m2/g and preferably between 200 and 230 m2/g. Preferably, the alumina denoted “A” has a mean mesopore diameter comprised between 6 and 12 nm and more preferably comprised between 7 and 11 nm.
According to another embodiment, the alumina denoted “B” has a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 150 and 180 m2/g. Preferably, the alumina denoted “B” has a mean mesopore diameter comprised between 15 and 20 nm.
Preferably, before being utilized, the catalysts according to the invention, are subjected to a calcination stage which has the objective of removing the species optionally adsorbed onto their surface.
The calcination stage consists for example of heating the catalyst to a temperature of at least 500° C. under a flow of air or nitrogen for at least 1 hour.
The dehydration reaction involving the following reactions:

C2H6O→CH2═CH2+H2O

and

C3H8O→CH3—CH═CH2+H2O

is carried out:

    
    
        at a temperature comprised between 350 and 500° C., preferably comprised between 350 and 450° C. and more preferably comprised between 375 and 425° C.;
        at a total pressure comprised between 0.2 and 2 MPa, preferably comprised between 0.2 and 1 MPa and more preferably comprised between 0.2 and 0.7 MPa;
        and with a weight hourly space velocity (whsv), which is defined as being the ratio of the mass flow rate of alcohols (i.e. ethanol and n-propanol) to the mass of catalyst, comprised between 1 and 10 h−1, preferably comprised between 2 and 8 h−1.
    
    


The conversions of ethanol and n-propanol are advantageously greater than 90%, preferably greater than 95% and more preferably greater than 99%.
The conversions are calculated using the following formula:



  
    
      
    
    ⁢
    
      
        Alcohol
        ⁢
        
          
        
        ⁢
        conversion
      
      =
      
        
          (
          
            1
            -
            
              
                mC
                
                  alcohol
                  ⁢
                  
                    
                  
                  ⁢
                  output
                
              
              
                mC
                
                  alcohol
                  ⁢
                  
                    
                  
                  ⁢
                  input
                
              
            
          
          )
        
        *
        100
      
    
  




  
    
      and
      ⁢
      
        
      
      ⁢
      with
      ⁢
      
        
      
      ⁢
      
        mC
        alcohol
      
    
    =
    
      Mass
      ⁢
      
        
      
      ⁢
      of
      ⁢
      
        
      
      ⁢
      alcohol
      *
      
        
          Molar
          ⁢
          
            
          
          ⁢
          mass
          ⁢
          
            
          
          ⁢
          of
          ⁢
          
            
          
          ⁢
          Carbon
        
        
          Molar
          ⁢
          
            
          
          ⁢
          mass
          ⁢
          
            
          
          ⁢
          of
          ⁢
          
            
          
          ⁢
          alcohol
        
      
    
  



It has been found that the catalysts utilized according to the invention also make it possible to achieve selectivities for the sought olefins (ethylene and propylene) greater than 95%, preferably greater than 99%.
The ethylene and propylene selectivities are calculated in carbon mass equivalent and with respect to the corresponding alcohol according to the formulae:



  
    
      Selectivity
      ethylene
    
    =
    
      
        (
        
          
            mC
            
              ethylene
              ⁢
              
                
              
              ⁢
              output
            
          
          
            
              mC
              
                ethanol
                ⁢
                
                  
                
                ⁢
                input
              
            
            -
            
              mC
              
                ethanol
                ⁢
                
                  
                
                ⁢
                output
              
            
          
        
        )
      
      *
      100
    
  




  and




  
    
      Selectivity
      propylene
    
    =
    
      
        (
        
          
            mC
            
              propylene
              ⁢
              
                
              
              ⁢
              output
            
          
          
            
              mC
              
                n
                ⁢
                
                  -
                
                ⁢
                propanol
                ⁢
                
                  
                
                ⁢
                input
              
            
            -
            
              mC
              
                n
                ⁢
                
                  -
                
                ⁢
                propanol
                ⁢
                
                  
                
                ⁢
                output
              
            
          
        
        )
      
      *
      100
    
  



The dehydration reaction is generally carried out in a unit comprising at least one isothermal or adiabatic reactor containing a bed, for example a fixed bed, of dehydration catalyst.
Preferably, the dehydration reaction is implemented in two adiabatic reactors in series, such as described in the document FR 2 978 146.
According to this preferred embodiment, the feedstock comprising the mixture of ethanol and n-propanol is mixed with a portion of the flow of recycled purified water and a portion of the flow of ethanol and n-propanol which have not been converted, originating from a purification zone. The mixture is introduced under pressure into a first gas/liquid exchanger in which said mixture undergoes an exchange of heat with the effluent originating from the last adiabatic reactor. The latent heat or enthalpy of condensation of the effluent originating from the last adiabatic reactor is used in order to vaporize the feedstock of alcohols in a mixture with the flow of recycled purified water and a flow of unconverted (non-dehydrated) ethanol/n-propanol, without the supply of external heat.
The feedstock of alcohols in a mixture with a flow of recycled purified water and a flow of unconverted (non-dehydrated) ethanol/n-propanol is then generally sent into a compressor.
Said vaporized and compressed mixture is then sent into a second single-phase gas-type exchanger, in which said mixture is heated using a heat exchanger with the effluent originating from the last adiabatic reactor. In said exchanger, for example of single-phase gas type, said vaporized and compressed feedstock is superheated and the effluent in the gaseous state, originating from the last adiabatic reactor is “desuperheated” without being condensed.
Said mixture of the feedstock and the two vaporized, compressed and heated flows in the single-phase gas-type exchanger is then heated, for example in a furnace so as to make the inlet temperature in the first adiabatic dehydration reactor compatible with the temperature of the dehydration reaction. The effluent originating from the first reactor is sent into a second heating means before being introduced into the second adiabatic dehydration reactor.
The effluent originating from the second reactor then undergoes the two successive exchanges described previously, in the exchangers.
The effluent after passing through the first exchanger is sent into a gas/liquid separation column where it is separated into an effluent comprising ethylene and propylene and an effluent comprising water. A portion of the effluent comprising water is optionally recycled, after cooling down, into the separation column.
The portion of the effluent comprising non-recycled water in the column is sent to a purification and separation stage. At least one flow of purified water and at least one flow of unconverted ethanol/n-propanol are then separated. A portion of said flow of unreacted ethanol/n-propanol originating from the purification stage is mixed with at least one portion of the flow of recycled purified water. The mixture of these two flows is carried out upstream of the first exchanger, with the aqueous feedstock of alcohols to be dehydrated.
The process according to the invention advantageously makes it possible to treat a mixture containing ethanol and n-propanol which is, by hydrogenation of ethyl propanoate, itself obtained by the esterification of propanoic acid with ethanol. Preferably, the propanoic acid originates from a propionic-type fermentation of a substrate chosen from the sugars, glycerol, lactic acid and malic acid using microorganisms of the genus Propionibacterium. Preferably, the propanoic acid is produced by fermentation of fermentable sugars obtained after pre-treatment of a biomass of lignocellulosic type and enzymatic hydrolysis. Lignocellulosic biomass represents one of the most abundant renewable resources on earth. The substrates considered are very varied, as they involve both the ligneous substrates (leafy and resinous), the by-products of agriculture (straw) or those of the industries that generate lignocellulosic waste (agri-food industries, paper mills). Preferably the ethanol is the product of the fermentation of sugars obtained from renewable sources such as starch- or sugar-containing plants (e.g. maize, sugar cane respectively) or from lignocellulosic biomass such as for example wood shavings or culture residues (wheat straw).
In the specific case where the feedstock treated is an aqueous solution containing ethanol and n-propanol with more than 80% by weight of water with respect to the total weight of the aqueous solution, the process according to the invention comprises before stage a) of dehydrating the ethanol and n-propanol, a stage of separating water from (or drying of) the aqueous solution. This stage can be carried out according to any technique known to a person skilled in the art.
For example according to a first embodiment, this separation consists of distillation in a column.
According to a second embodiment, the separation stage consists of a stage of solvent extraction using an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms. Preferably, the aromatic cut comprises a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene. This extraction is preferably carried out at a temperature comprised between 50 and 120° C. and preferably according to a counter-current extraction method. An aromatic cut containing the mixture of n-propanol and ethanol is extracted from the extraction column, which is then sent into a distillation unit the purpose of which is to separate the extraction solvent from the mixture of alcohols.



BRIEF DESCRIPTION OF DRAWINGS
Other features and advantages of the invention will be better understood and become clearly apparent on reading the description given hereafter with reference to the drawings in which:
FIG. 1 diagrammatically shows a first embodiment of the process according to the invention;
FIG. 2 diagrammatically shows a second embodiment of the process according to the invention;



Generally, similar elements are denoted by identical references in the figures.
With reference to FIG. 1, an aqueous effluent containing a mixture of ethanol and n-propanol, which originates from a unit 1 for dehydrogenation of an ethyl propanoate solution, is sent via the line 2 to a separation unit 3, which is a distillation column in the example of FIG. 1. The objective of this first stage, which can be described as “partial drying”, is to reduce the water content of the effluent.
The flow 2 entering the distillation column 3 can thus comprise up to 98% by weight of water.
With reference to FIG. 1, an aqueous fraction is extracted from the distillation column 3, which is removed at the bottom of the column via the line 5 and a fraction from the top containing an aqueous mixture of alcohols via the line 4. The aqueous mixture of alcohol typically has a content by mass of water with respect to the total weight of the aqueous mixture ranging up to 50% by weight. The distillation column 3 is designed and operated so as to preferably recover 99% by weight of the alcohols at the top of the column.
The mixture comprising water, n-propanol and ethanol is heated and vaporized using a heat exchanger 6 and then compressed using a compressor 7 before being sent to the dehydration stage, in the dehydration unit 8, in order to convert said alcohols to ethylene and propylene.
The dehydration reaction is carried out in a dehydration unit 8 comprising at least one reactor in which the ethanol and n-propanol are brought into contact with a catalyst capable of carrying out dehydration of the ethanol and n-propanol. In the case where the mixture of ethanol and n-propanol has a water content of less than 30% by weight with respect to the total weight of the mixture, the addition of water to said mixture is provided before dehydrating it. To this end it is provided, as indicated in FIG. 1, for a line 9 to be arranged upstream of the dehydration unit 8 allowing the injection of water into the mixture leaving the compressor 7. Preferably, the water is added in the form of vapour to the mixture of ethanol and n-propanol.
According to the invention, this stage of converting ethanol and n-propanol to olefins utilizes an alumina chosen from:

    
    
        an alumina (A) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 350 m2/g, a mean mesopore diameter comprised between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulphur content of less than 40 ppm by weight; and
        an alumina (B) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 130 and 180 m2/g, a mean mesopore diameter comprised between 14 and 20 nm, a sodium content comprised between 300 and 600 ppm by weight and a sulphur content comprised between 800 and 1300 ppm by weight;
    
    


It should be noted that the dehydration reaction in the presence of the catalyst according to the invention does not require thorough drying of the mixture of ethanol/n-propanol to the extent where its water content is comprised between 30 and 75% by weight with respect to the total weight of the mixture. The water contained in the mixture of alcohols is advantageously used in the dehydration process according to the invention as thermal fluid.
The catalytic dehydration reaction is carried out at a temperature comprised between 350 and 500° C., at a total pressure comprised between 0.2 and 2 MPa and with a weight hourly space velocity (whsv) defined as being the ratio of the mass flow rate of the ethanol and n-propanol to the mass of catalyst comprised between 1 and 10 h−1.
The dehydration stage is carried out in a unit which comprises one or more reactors arranged successively. The reactor(s) is (are) provided with the catalyst according to the invention, which is preferably in the form of extrudates and operate(s) either in a fixed bed or in a moving bed, but preferentially in a fixed bed.
The stage of dehydrating the alcohols is preferably implemented according to the process described in the patent application FR 2961202 which involves at least one adiabatic dehydration reactor. The process involves the effluent originating from the last dehydration reactor being sent to the heat exchanger and the feedstock to be dehydrated being introduced in a prior vaporization stage at a pressure less than the pressure of the effluent leaving the last dehydration reactor, so as to maximize the exchange of heat between the feedstock and the effluent originating from the last reactor, i.e. to exchange all of the enthalpy of vaporization of the feedstock and the enthalpy of condensation of said effluent.
At the end of the dehydration stage and after a distillation stage, a gaseous effluent 10 containing a mixture of propylene and ethylene is recovered at the outlet of the dehydration unit 8 and an effluent comprising water via the line 11. This gaseous effluent of propylene and ethylene can subsequently undergo a distillation stage with a view to separating the two olefins, which can then be upcycled as a raw material in petrochemistry, in particular in the polymer industry. As mentioned above the process according to the invention is advantageous from an economic point of view as it allows the production of ethylene and propylene from an aqueous mixture of n-propanol and ethanol by dispensing with a costly stage of separating the alcohols. Thanks to the process according to the invention, the ethanol and n-propanol are converted concomitantly in order to produce a flow of ethylene in a mixture with propylene which are olefins that can be easily separated in particular by distillation.
FIG. 2 represents a second embodiment of the process according to the invention which differs from that of FIG. 1 in that the water separation (drying) unit is a solvent extraction unit comprising a liquid-liquid extraction column preferably completed by a distillation column.
With reference to FIG. 2, the fermentation liquor containing ethanol, n-propanol and water, originating from the fermentation unit 1 is sent via the line 2 into a liquid-liquid extraction column 12 and into which a solvent which is an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms is injected, via the line 13, preferably in counter-current, for example at the bottom of the extraction column 12. The solvent according to the invention has the ability to absorb ethanol and n-propanol and moreover is virtually insoluble in water. For example the solvent is a heavy reformate originating from a catalytic reforming unit for gasolines which treats a naphtha cut from crude oil in order to increase the aromatic compounds content. This stage of catalytic reforming (aromatization of gasoline) makes this gasoline heavier. Also, in order to guarantee a final boiling point of the gasoline in accordance with the commercial specification, it is usual to redistill these gasolines in order to remove the heaviest fraction which is called “heavy reformate”.
By means of the difference in density and thanks to the affinity of the solvent vis-á-vis ethanol and n-propanol, an organic effluent 14 containing the aromatic cut and the sought alcohols are recovered at the top of the extraction column and a flow of water is recovered at the bottom, via the line 5. In order to implement the liquid-liquid extraction, the weight ratio between the feedstock and the solvent is generally comprised between 0.5 and 5. The bringing into contact with the solvent is generally carried out at a temperature comprised between 60 and 120° C. and at a pressure comprised between 0.5 and 5 MPa. As shown in FIG. 2, a line 15 makes it possible to top up with solvent if this is necessary for the operation of the column 30. Thus, an effluent containing at least 99% by weight of the alcohols present in the mixture of alcohols is recovered at the top of the liquid-liquid extraction column.
According to FIG. 2, the organic effluent extracted at the top of the liquid-liquid extraction column 12 is sent into a distillation column 15 configured in order to separate, at the top, the mixture comprising the ethanol and n-propanol from the extraction solvent. Thus the mixture of alcohols is recovered via the line 17 whereas the aromatic cut is drawn off at the bottom of said distillation column 15 via the line 16 and is recycled via the line 13 into the liquid-liquid extraction column 12. This distillation is preferably carried out at reduced pressure, preferably comprised between 0.02 and 0.05 MPa in order to reduce the temperature at the bottom of the column and thus be able to use a “low pressure” vapour as a reboiling fluid. The process according to the embodiment in FIG. 2 has the advantage of consuming less energy with respect to the first embodiment as, unlike a distillation, the utilization of the liquid-liquid extraction column does not require the mixture of alcohols to be vigorously heated in order to dry it.
In the embodiment of FIG. 2, the effluent drawn off via the line 17 which is essentially constituted by ethanol and n-propanol is heated by the exchanger 6 then compressed by the compressor 7 before being sent with water supplied via the line 9 into the dehydration unit 13. The supply of water, via the line 9, makes it possible to regulate the water content of the feedstock of alcohols so as to provide an ethanol/n-propanol/water mixture the water content of which is comprised between 30 and 75% by weight of water with respect to the total weight of the mixture.
EXAMPLES
Different catalysts were tested for the dehydration of a mixture containing 25% by weight of ethanol, 25% by weight of n-propanol and 50% by weight of water with respect to the total weight of the mixture. The catalysts are in the form of trilobed extrudates with a diameter of 1.6 mm.
Table 1 below gives the characteristics of the catalysts tested.












TABLE 1








Specific surface area






Mean
(m2/g) measured
Sodium
Sulphur



Type of
mesopore
according to ASTM D
content (ppm
content (ppm


Catalyst
alumina
diameter (nm)
3663-03
by weight)
by weight)




















C1 (according to
Pseudo-cubic γ
10.3
208
Less than 20
Less than 40


the invention)
alumina


C2 (according to
Cubic γ
8.5
216
28
Less than 40


the invention)
alumina


C3 (according to
Cubic γ
7.4
232
35
Less than 40


the invention)
alumina


C4 (comparative)
Cubic γ
5.7
155
417
Less than 40



alumina and χ



alumina


C5 (comparative)
Cubic γ
8.7
270
394
1262



alumina


C6 (according to
Cubic γ
15.7
175
550
 903


the invention)
alumina


C7 (according to
tetragonal γ
18.3
152
448
1210


the invention)
alumina + θ



alumina


C8 (comparative)
δ alumina and
25.8
154
401
Less than 40



χ alumina


C9 (comparative)
Cubic γ
18.3
143
222
1121



alumina









The catalysts C1, C2 and C3 are consistent with an alumina (A) according to the invention and the catalysts C6 and C7 are consistent with an alumina (B) according to the invention.
Catalyst C4 is not consistent with an alumina (A) according to the invention as its specific surface area and its sodium content are outside the claimed ranges. Moreover, catalyst D is not consistent with an alumina (B) according to the invention as its mean mesopore diameter is outside the range 14-20 nm.
Catalyst C5 which does not conform is distinguished from an alumina (A) according to the invention by the sodium and sulphur contents which are higher than the upper limit of the claimed ranges. Catalyst C5 which also is not consistent with an alumina (B) according to the invention and is distinguished by its mean mesopore diameter and its specific surface area.
Catalyst C8 does not correspond to the definition of an alumina (A) according to the invention as the mean mesopore diameter, the specific surface area and the sodium content are outside the claimed ranges. Moreover, catalyst C8 is not consistent with an alumina (B) according to the invention as it has a mean mesopore diameter greater than the claimed range and a sulphur content of less than 800 ppm by weight
Catalyst C9 is not consistent with an alumina (A) according to the invention because of its mean mesopore diameter, its specific surface area, its sodium and sulphur content. Catalyst I is distinguished from an alumina (B) according to the invention by its sodium content.
Before their utilization in the dehydration test of the mixture of alcohols, all the catalysts have undergone a conditioning phase which comprises the following stages:

    
    
        i) heating the catalyst from ambient temperature to 550° C. under a flow of air at 5 NI/h with a temperature gradient of 20° C. per hour;
        ii) maintaining a temperature of 550° C. under a flow of air for 2 hours;
        iii) cooling the catalyst to the temperature of the test under a flow of nitrogen at 100 NI/h;
        iv) maintaining the catalyst at the temperature of the test under a flow of nitrogen at 100 NI/h for 5 hours.
    
    


The dehydration reaction is carried out in an isothermal reactor containing a fixed bed of dehydration catalyst. All the catalysts were tested under the same operating conditions namely:

    
    
        temperature in the reactor=400° C.;
        relative pressure in the reactor=0.2 MPa;
        weight hourly space velocity (whsv), which is defined as being the ratio of the mass flow of (ethanol+n-propanol) to the mass of catalyst=2 h−1.
    
    


The effluent leaving the dehydration reactor is sent into a high pressure (HP) separator in order to separate a first gaseous flow and a liquid flow. The liquid flow is then transferred into a low pressure (LP) separator where a second gaseous flow and a second liquid flow are separated. The two gaseous flows are mixed before being analyzed.
The liquid and gaseous flows are analyzed by gas chromatography.
Table 2 gives the catalytic performances of the tested aluminas after testing for 72 hours.
The conversions and the selectivities were calculated from the formulae described above.
Finally, the purity of the C2 cut is calculated with respect to the ethylene, ethane and methane whereas the purity of the C3 cut is calculated with respect to the propylene, propane and cyclopropane. Thus, the ethylene purity of the C2 cut and the propylene purity of the C3 cut are expressed as follows:



  
    
      Ethylene
      ⁢
      
        
      
      ⁢
      purity
    
    =
    
      
        (
        
          
            mC
            
              ethylene
              ⁢
              
                
              
              ⁢
              output
            
          
          
            
              mC
              
                ethylene
                ⁢
                
                  
                
                ⁢
                output
              
            
            +
            
              mC
              
                ethane
                ⁢
                
                  
                
                ⁢
                output
              
            
            +
            
              mC
              
                methane
                ⁢
                
                  
                
                ⁢
                output
              
            
          
        
        )
      
      *
      100
    
  




  
    
      Propylene
      ⁢
      
        
      
      ⁢
      purity
    
    =
    
      
        (
        
          
            mC
            
              propylene
              ⁢
              
                
              
              ⁢
              output
            
          
          
            
              mC
              
                propylene
                ⁢
                
                  
                
                ⁢
                output
              
            
            +
            
              mC
              
                propane
                ⁢
                
                  
                
                ⁢
                output
              
            
            +
            
              mC
              
                cyclopropane
                ⁢
                
                  
                
                ⁢
                output
              
            
          
        
        )
      
      *
      100
    
  



















TABLE 2





Catalyst
C1
C2
C3
C4
C5
C6
C7
C8
C9
























Conversion of n-Propanol (%)
99.98
99.99
99.99
98.80
99.50
99.99
99.97
95.76
99.55


Propylene Selectivity
99.96
99.74
99.56
98.84
99.02
99.29
99.44
97.86
97.75


Dipropylether Selectivity
0
0
0
0.05
0
0
0
0.14
0.02


Propane Selectivity
0.06
0.06
0.12
0.18
0.22
0.11
0.08
0.06
1.02


Propanal Selectivity
0.13
0.17
0.16
0.16
0.17
0.25
0.18
0.05
0.55


Ethoxypropane Selectivity
0
0
0
0.12
0.09
0
0
1.35
0.07


Cyclopropane Selectivity
0.14
0.04
0.02
0.65
0.50
0.35
0.30
0.54
0.59


C3 cut composition (% by weight)


Propylene
99.79
99.91
99.86
99.17
99.28
99.54
99.62
99.39
98.38


Propane
0.07
0.03
0.09
0.2
0.21
0.12
0.07
0.07
0.97


Cyclopropane
0.15
0.04
0.02
0.65
0.50
0.35
0.30
0.55
0.59


Ethanol conversion (%)
99.34
99.88
99.56
91.99
95.47
99.70
99.56
65.20
98.20


Methane Selectivity
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00


Ethylene Selectivity
99.57
99.66
99.49
98.14
98.68
99.53
99.58
84.55
96.79


Ethane Selectivity
0.16
0.13
0.19
0.25
0.26
0.18
0.15
0.25
1.20


Diethylether Selectivity
0
0
0
1.00
0.55
0
0
13.17
0.40


EthylPropylEther Selectivity
0
0
0
0.20
0.11
0
0
1.82
0.08


Butane Selectivity
0.13
0.10
0.14
0.17
0.16
0.10
0.09
0.16
0.50


Butene Selectivity
0.11
0.09
0.15
0.21
0.15
0.13
0.13
0.03
0.68


C5+ Selectivity
0.02
0.02
0.02
0.03
0.09
0.05
0.04
0.02
0.35


C2 cut composition (% by weight)


Ethylene
99.84
99.87
99.81
99.75
99.74
99.82
99.85
99.71
98.78


Ethane
0.16
0.13
0.19
0.25
0.26
0.18
0.15
0.29
1.22


Methane
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00









The utilization of the catalysts according to the invention (C1, C2, C3, C6 and C7) makes it possible to obtain excellent n-propanol conversion rates but also ethanol conversion rates which are greater than 99%. On the other hand, it is noted that with the catalysts not according to the invention (D, E, H, I) the ethanol conversion rates are less than 99%.
Moreover it is observed that the purity of the propylene in a C3 cut and that of the ethylene in a C2 cut are better when the catalysts according to the invention are utilized. The C2 and C3 cuts thus produced are of polymer grade and can therefore be used in the petrochemical industry in particular for the manufacture of polymers.

## Claims

1. Process for the production of a mixture of ethylene and propylene from a mixture containing ethanol and n-propanol and having a water content comprised between 30 and 75% by weight with respect to the total weight of the mixture, in which:
a) the mixture is brought into contact, in a dehydration unit, with a dehydration catalyst chosen from:
an alumina (A) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 200 and 280 m2/g, a mean mesopore diameter comprised between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulphur content of less than 40 ppm by weight; and
an alumina (B) having a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 130 and 180 m2/g, a mean mesopore diameter comprised between 14 and 20 nm, a sodium content comprised between 300 and 600 ppm by weight and a sulphur content comprised between 800 and 1300 ppm by weight;


the bringing into contact being carried out at a temperature comprised between 350 and 500° C., at a total pressure comprised between 0.2 and 2 MPa and with a weight hourly space velocity (whsv) defined as being the ratio of the mass flow rate of ethanol and n-propanol to the mass of catalyst comprised between 1 and 10 h−1,
b) an effluent containing ethylene and propylene is drawn off from said dehydration unit.

2. Process according to claim 1, in which the mixture contains between 1 and 75% by weight of ethanol and between 99 and 25% by weight of n-propanol with respect to the total weight of ethanol and n-propanol.

3. Process according to claim 1, in which the aluminas (A) and (B) are gamma aluminas.

4. Process according to claim 1, in which the alumina (A) has a mean mesopore diameter comprised between 6 and 12 nm and preferably comprised between 7 and 11 nm.

5. Process according to claim 1, in which the alumina (B) has a BET specific surface area measured according to the standard ASTM D 3663-03 comprised between 150 and 180 m2/g.

6. Process according to claim 1, in which the alumina (B) has a mean mesopore diameter comprised between 15 and 20 nm.

7. Process according to claim 1, in which before stage a) the mixture is brought into contact with an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms, in a separation unit comprising a liquid-liquid extraction column, so as to separate from said extraction column an aqueous fraction and an organic fraction containing the aromatic cut, ethanol, n-propanol and said organic fraction is sent into a distillation column configured in order to provide an effluent containing the aromatic cut and a mixture containing ethanol and n-propanol and said mixture is sent into the dehydration unit.

8. Process according to claim 7, in which the aromatic cut is a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene.

9. Process according to claim 7, in which the mixture containing ethanol, n-propanol and water is brought into contact with the aromatic cut is carried out in counter-current.

10. Process according to claim 1, in which before stage a) the mixture containing ethanol, n-propanol and water is sent into a separation unit comprising a distillation column so as to separate from the distillation column an aqueous fraction and an effluent containing a mixture of ethanol, n-propanol and water with a water content comprised between 30 and 75% by weight with respect to the total weight of the mixture and the effluent is sent into the dehydration unit.

11. Process according to claim 1 in which the mixture containing ethanol and n-propanol originates from a hydrogenation of ethyl propanoate.

12. Process according to claim 11, in which the ethyl propanoate is obtained by esterification of propanoic acid with ethanol, the propanoic acid and the ethanol being of biological origin.

13. Process according to claim 1, in which the bringing into contact of stage a) is carried out in at least one reactor at a temperature comprised between 350 and 450° C., at a total pressure comprised between 0.2 and 1 MPa, and with a weight hourly space velocity (whsv) comprised between 2 and 8 h−1.

14. Process according to claim 1 in which stage a) is carried out in two adiabatic reactors in series.

15. The process according to claim 4 has a mean mesopore diameter of between 7 and 11 nm.

16. The process according to claim 13 wherein at least one reactor is at a temperature at 375 and 425° C., at a total pressure comprised between 0.2 and 1 MPa.

17. The process according to claim 13 wherein at least one reactor is at a pressure between 0.2 and 0.7 MPa.