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    • 专利摘要:
    The invention relates to a process for producing a mixture of ethylene and propylene from a mixture containing ethanol and isopropanol and having a water content of between 30 and 75% by weight. relative to the total weight of the mixture, wherein: 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 ASTM D 3663- 03 between 200 and 350 m2 / g, a mesoporous average diameter of between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulfur content of less than 40 ppm by weight; and an alumina (B) having a BET surface area measured according to ASTM D 3663-03 of between 130 and 180 m 2 / g, a mesoporous mean diameter of between 14 and 20 nm, a sodium content of between 300 and 600. ppm weight and a sulfur content of between 800 and 1300 ppm by weight; the contacting being carried out at a temperature between 350 and 500 ° C, at a total pressure between 0.2 and 2 MPa and with a weight hourly weight (pph) defined as the ratio of the mass flow rate ethanol and isopropanol on the catalyst mass of between 1 and 10 h -1, b) an effluent containing ethylene and propylene from said dehydration unit is withdrawn.
    公开号:FR3013707A1
    申请号:FR1361684
    申请日:2013-11-27
    公开日:2015-05-29
    发明作者:Nicolas Aribert；Laure Brandhorst；Vincent Coupard；Sylvie Maury；Tom Vivien
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a process for producing a mixture of ethylene and propylene from an aqueous mixture containing ethanol and isopropanol. The process according to the invention makes it possible in particular to treat an aqueous mixture of ethanol and isopropanol which is obtained by a fermentation of the type IBE (Isopropanol-Butanol-Ethanol) of sugars.
    [0002] State of the art Light olefins are important intermediates in the chemical industry and are mainly produced by catalytic cracking or steam cracking of hydrocarbons.
    [0003] For example, propylene is widely used in the chemical industry in the production of acrylonitrile, acrylic acid and especially polypropylene. The same is true for ethylene, which is used for the synthesis of a large number of polymers and plastics, such as polyvinyl chloride (PVC) and polyethylene (PE).
    [0004] To respond to future challenges related to the decline of oil resources and environmental concerns, much research is currently being conducted to develop alternative technologies for synthesizing these intermediates from renewable resources. One of the most currently studied routes for the production of olefins is that of the catalytic dehydration of alcohols. The dehydration reaction of ethanol in ethylene is known and detailed since the end of the 19th century. It is known that this reaction is very endothermic, balanced and displaced to ethylene at high temperature. The reference catalyst often used is a monofunctional catalyst of an acidic nature. Gamma alumina is the most cited catalyst. The article "The Dehydration of Alcohols over Alumina." The reaction scheme, H. Knozinger, R. Kohne, Journal of Catalysis (1966), 5, 264270 is considered as the basic publication on alcohol dehydration work. including ethanol. Zeolites are also used for this application, and in particular ZSM5 since the 1980s, as described in "Reactions of ethanol over ZSM-5" S.N. Chaudhuri et al., Journal of Molecular Catalysis 62: 289-295 (1990). The dehydration route of alcohols responds well to the problem of producing olefins alternately and in a "green" way. Indeed ethanol can be synthesized by fermentation of sugars obtained from renewable sources such as starch or sugar plants (eg corn, sugar cane respectively) or from lignocellulosic biomass such as for example chips of wood or crop residues (wheat straw).
    [0005] WO 2004/078336 discloses a method for producing α-olefins by dehydration of linear or branched alcohols having 4 to 14 carbon atoms in the presence of an alumina comprising: a pore volume greater than 0.9 ml / g (determined according to the method DIN 66133); pores in the mesoporous domain (maximum diameter of between 20 and 90 Å); pores in the macroporous domain (maximum diameter greater than 250 Å). Application WO 2011/162717 relates to a process for producing olefins by dehydration of a mixture of alcohols by means of a catalyst comprising a zeolite doped with a metal 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. It is envisaged in this document to use alcohols obtained by the biomass treatment. Finally, patent application FR 2 961 202 describes a process for producing C4 olefins from a C4 monoalcohol feedstock by dehydration reaction of said alcohol in the presence of an alumina catalyst. controlled porosity. An object of the present invention is to provide a process for producing a mixture of ethylene and propylene directly from a mixture containing water, ethanol and isopropanol. According to the invention, the method applies in particular to a mixture of ethanol and isopropanol of biological origin obtained from the treatment of biomass. SUMMARY OF THE INVENTION The present invention thus relates to a process for producing a mixture of ethylene and propylene from a mixture containing ethanol, isopropanol and having a water content between and 75% by weight relative to the total weight of the mixture, wherein: 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 ASTM D 3663-03 standard of between 200 and 350 m 2 / g, a mesoporous mean diameter of between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulfur content of less than 40 ppm by weight; and an alumina (B) having a BET specific surface area measured according to ASTM D 35 3663-03 of between 130 and 180 m2 / g, a mesoporous mean diameter of between 14 and 20 nm, a sodium content of between 300 and 600 ppm weight and a sulfur content of between 800 and 1300 ppm by weight; the contacting being carried out at a temperature between 350 and 500 ° C, at a total pressure between 0.2 and 2 MPa and with a weight hourly weight (pph) defined as the ratio of the mass flow rate ethanol and isopropanol on the catalyst mass of between 1 and 10 h -1 b), an effluent containing ethylene and propylene from said dehydration unit is withdrawn. The method 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, from a mixture of alcohols which can be of origin organic. Surprisingly, the inventors have found that a catalyst having the characteristics mentioned above has a high activity in dehydration, while also being selective towards the desired olefins. The process according to the invention has the advantage that it avoids a step of separating ethanol from isopropanol before the dehydration step. Indeed, thanks to the catalysts according to the invention, it is possible, in a single catalytic step, to dehydrate the mixture of said alcohols and thus to produce an effluent comprising ethylene and propylene. The process is therefore economically and energetically advantageous when it is contemplated to produce ethylene and propylene for petrochemicals. Indeed it is not necessary thanks to the process to achieve a prior separation of ethanol and isopropanol from the aqueous mixture before dehydration. This separation of the two alcohols is particularly costly in investment because to be effective, because of the existence of azeotropic compositions, it requires not only to concentrate the mixture of alcohols so as to obtain a concentration of alcohols greater than 50% by weight, but also to implement 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 the petrochemical industry by bringing into play a smaller number of unit operations, hence a considerable economic advantage. Thus, after the dehydration step according to the invention, a stream containing propylene and ethylene is obtained which are easily separable by distillation.
    [0006] The method according to the invention makes it possible to dehydrate a mixture containing water, ethanol and isopropanol and to advantageously use the water contained in said mixture as a thermal fluid during the dehydration step. The dehydration reaction is highly endothermic and the fact that the feed is diluted with water makes it possible to reduce the reaction endotherm and thus to effect the reaction with a limited number of reactors. The water also makes it possible, thanks to the charge / effluent exchangers, to recover the condensation energy of the reaction products in order to bring the charge to be dehydrated to the required temperature.
    [0007] Preferably, the alumina (A) has a BET specific surface area measured according to ASTM D 3663-03 of between 200 and 280 m 2 / g and more preferably between 200 and 230 m 2 / g. Preferably, the alumina (A) has a mesoporous mean diameter of between 6 and 12 nm and more preferably between 7 and 11 nm.
    [0008] Preferably, the alumina (B) has a BET surface area measured according to ASTM D 3663-03 of between 150 and 180 m 2 / g. Preferably, the alumina (B) has a mesoporous mean diameter of between 15 and 20 nm.
    [0009] 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 consist of gamma-alumina. The aluminas according to the invention may be prepared by any method known to those skilled in the art. For example, they may be obtained from an alumina gel (or alumina gel) which essentially comprises an oxy (hydroxide) aluminum precursor (A10 (OH)) - also called boehmite. The alumina gel (or otherwise known as boehmite gel) is for example synthesized by precipitation of basic solutions and / or acid salts of aluminum induced by pH change or any other method known to those skilled in the art (P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, JL Le Loarer, JP Jolivet, C. Froidefond, Alumina, Handbook of Porous Solids, Eds F. Schut, KSW Sing, Weitkamp J., Wiley-VCH, Weinheim , Germany, 2002, pp. 15911677). The gel obtained is then subjected to one or more heat treatment steps which notably comprises drying and calcination in order to form an alumina having the structural characteristics required according to the invention. It should be noted that the aluminas according to the invention can also be obtained from other precursors of alumina such as, for example, bauxite, bayerite or by oxidation of aluminum. According to one particular embodiment, when the mixture additionally contains n-butanol, a butanol separation step is carried out before step a), for example by sending said mixture to a distillation column from which An effluent containing water, ethanol and isopropanol is withdrawn at the top of the column and at the bottom an effluent containing butanol. The effluent containing water, ethanol and isopropanol is then treated in the dehydration unit according to step a) of the process. According to a particular embodiment, before step a), a step is taken to reduce the water content (drying step) of the ethanol-isopropanol / water mixture which comprises contacting, in a column of liquid-liquid extraction of the mixture with an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms. The aromatic section is preferably a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene. Alternatively, the aromatic cut is a heavy reformate cut resulting from a separation of the reforming product from a gasoline cut. The contacting of the alcohol mixture with the aromatic section in the extraction column is preferably countercurrent and preferably with a contact temperature of between 70 and 90 ° C. This extraction step makes it possible to separate from the column an aqueous fraction and an organic fraction containing the aromatic section, ethanol, isopropanol, optionally butanol and traces of water. The organic fraction is then sent to a distillation column configured to separate an effluent containing the aromatic cut and an effluent containing ethanol, isopropanol and optionally butanol. Finally, the effluent containing ethanol and isopropanol is sent to the dehydration unit of step a). If the effluent containing the mixture of ethanol and isopropanol also comprises butanol, a butanol separation step of the effluent is preferably carried out before the dehydration step.
    [0010] Alternatively, before step a), a step is performed to reduce the water content of the ethanol-isopropanol / water mixture, which consists in sending the mixture to a distillation column so as to separate an aqueous fraction and an effluent having a reduced water content and containing ethanol, isopropanol. The effluent thus recovered is treated in the dehydration unit in accordance with step a). If the effluent containing the mixture of ethanol and isopropanol also comprises butanol, a step is taken to separate butanol from the effluent before the dehydration step. Preferably the mixture containing ethanol, isopropanol is derived from an Isopropanol-Butanol-Ethanol fermentation unit (IBE fermentation) of sugars which are obtained by treatment of biomass, for example lignocellulosic. Preferably, the process is carried out in two adiabatic reactors in series. Detailed description of the invention The filler treated in the process according to the invention is a mixture containing between 30 and 75% by weight of water relative to the total weight of the mixture, ethanol and isopropanol. The mixture which is treated by dehydration according to the invention can comprise any proportion of ethanol and isopropanol. Preferably, the mixture contains between 1 and 75% by weight of ethanol and between 99 and 25% by weight of isopropanol relative to the total weight of ethanol and isopropanol. Very preferably, the mixture contains at least 25% by weight of ethanol and at least 75% by weight of isopropanol. The charge may advantageously come from non-fossil resources. Preferably the filler is a product resulting from the biological treatment of biomass. Preferably, the ethanol / isopropanol feedstock is a feedstock produced by a fermentation of the IBE type of sugars resulting for example from crops of sugar plants such as sugar cane (sucrose, glucose, fructose, and sucrose), beets, or also starchy plants (starch) or lignocellulosic biomass or hydrolysed cellulose (majority glucose and xylose, galactose). According to the invention, the conversion of ethanol and isopropanol respectively to ethylene and propylene is carried out, for example in a reactor, by bringing the charge into contact with a catalyst chosen from: an alumina (A) having a BET surface area measured according to ASTM D 3663-03 of between 200 and 350 m2 / g, a mesoporous mean diameter of between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulfur content of less than 40 ppm weight; and an alumina (B) having a BET specific surface area measured according to ASTM D 3663-03 of between 130 and 180 m 2 / g, a mesoporous mean diameter of between 14 and 20 nm and a sodium content of between 300 and 600. ppm weight and a sulfur content of between 800 and 1300 ppm by weight; The determination of the mesoporous average diameter is made by mercury porosimetry according to ASTM D 4284-03 with a contact angle of 140 °. The mercury porosimetry analysis corresponds to the intrusion of a volume of mercury characteristic of the existence of mesopores and macropores in said catalyst according to ASTM D4284-03, the pores being assumed to be cylindrical in shape. This technique makes it possible to access the value of the mesoporous mercury volume defined as the volume of mercury adsorbed by all the pores having a diameter comprised in the range of mesopores, namely between 2 and 50 nm. This mesoporous mean diameter is obtained from the derivative curve dV / dlog (D) (V being the mercury volume adsorbed and D the pore diameter) as a function of the diameter of the pores D and corresponds to the ordinate for which the abscissa dV / dlog (D) is maximal.
    [0011] The dehydration catalyst used in step a) of the process according to the invention is advantageously shaped in the form of grains of different shapes and sizes. It is advantageously used in the form of cylindrical or multi-lobed extrusions such as bilobed, trilobed, straight-lobed or twisted, but can optionally be manufactured and used in the form of crushed powder, tablets, rings, beads, wheels, spheres. Preferably, said catalyst is in the form of extrudates.
    [0012] Said dehydration catalyst used in step a) of the process according to the invention is advantageously used in at least one reactor, in a fixed bed or in a moving bed. In the context of the invention, the catalyst may include at least one oxide type matrix, also called binder. Said matrix is advantageously chosen from the elements of the group formed by clays (such as, for example, natural clays such as kaolin or bentonite), magnesia, aluminas, silicas, silica-aluminas, aluminates, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, and coal.
    [0013] According to a preferred embodiment, the alumina designated "A" has a BET specific surface area measured according to ASTM D 3663-03 of between 200 and 280 m 2 / g and preferably between 200 and 230 m 2 / g. Preferably, the alumina designated "A" has a mesoporous mean diameter of between 6 and 12 nm and more preferably between 7 and 11 nm.
    [0014] According to another embodiment, the alumina designated "B" has a BET specific surface area measured according to ASTM D 3663-03 of between 150 and 180 m2 / g. Preferably, the alumina designated "B" has a mesoporous mean diameter of between 15 and 20 nm. Preferably, the catalysts according to the invention, before their implementation are subjected to a calcination step which aims to eliminate the species possibly adsorbed on their surface. The calcination step is for example to bring the catalyst to a temperature of at least 500 ° C under a stream of air or nitrogen for at least 1 hour. The dehydration reaction involving the following reactions: C2H5OH CH2 = CH2 + H2O and C3H80 CH3-CH = CH2 + H2O is carried out: at a temperature of between 350 and 500 ° C, preferably between 350 and 450 ° C and more preferably between 375 and 425 ° C; at a total pressure of between 0.2 and 2 MPa, preferably between 0.2 and 1 MPa and more preferably between 0.2 and 0.7 MPa; and with a weight hourly weight (pph), which is defined as the ratio of the mass flow rate of alcohols (ie ethanol and isopropanol) to the catalyst mass, of between 1 and 1011-1, preferably of between 2 and 811.degree. 1.
    [0015] Conversions of ethanol and isopropanol are preferably greater than 90%, preferably greater than 95% and more preferably greater than 99%. The conversions are calculated using the following formula: (mC alcohol so * 100 mCalcohol input Alcohol conversion = 1 = Alcohol mass * Molar mass Carbone and with mCalcool Molar mass alcohol It has been found that the catalysts used according to The invention also makes it possible to achieve selectivities towards the desired olefins (ethylene and propylene) of greater than 95%, preferably greater than 99%, The selectivities for ethylene and propylene are calculated in terms of carbon equivalent and, based on the corresponding alcohol, the formulas: Selectivityethylene = MC ethylene outlet * 100 mC ethanol inlet mCethanol outlet and (mCpropylenesorption * 100 mC opropanol inlet mCisopropanol outlet Propylenepropylene The dehydration reaction is generally conducted in a unit comprising at least one isothermal or adiabatic reactor containing a bed, for example fixed, dehydration catalyst.
    [0016] Preferably, the dehydration reaction is carried out in two adiabatic reactors in series, as described in document FR 2 978 146. According to this preferred embodiment, the feedstock comprising the mixture of ethanol and isopropanol is mixed with part of the stream of purified recycled water and part of the flow of ethanol and isopropanol that have not been converted, from a purification zone. The mixture is introduced under pressure into a first gas / liquid exchanger in which said mixture undergoes a heat exchange with the effluent from the last adiabatic reactor. The latent heat or enthalpy of condensation of the effluent from the last adiabatic reactor is used to vaporize the charge of alcohols mixed with the flow of purified recycled water and a flow of ethanol / isopropanol unconverted (not dehydrated), without external heat input. The alcohol feed mixed with a stream of purified recycled water and an unconverted stream of ethanol / isopropanol (non-dehydrated) is then generally sent to a compressor.
    [0017] Said vaporized and compressed mixture is then sent to a second monophasic gas-type exchanger, wherein said mixture is heated by heat exchange with the effluent from the last adiabatic reactor. In said exchanger, for example monophasic gas, said vaporized and compressed charge is superheated and the effluent in the gaseous state, from the last adiabatic reactor is "desuperheated" without being condensed. Said mixture of the feedstock and the two streams, vaporized, compressed and heated in the monophasic gas type exchanger is then heated, for example in an oven so as to bring it to an inlet temperature in the first adiabatic reactor of dehydration compatible with the temperature of the dehydration reaction. The effluent from the first reactor is sent to a second heating means before being introduced into the second adiabatic dehydration reactor. The effluent 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 to a gas / liquid separation column where it is separated into an effluent comprising ethylene and propylene and an effluent comprising water. Part of the effluent comprising water is optionally recycled, after cooling, into the separation column. The portion of the effluent comprising non-recycled water in the column is sent to a purification and separation step. At least one stream of purified water and at least one stream of ethanol / isopropanol unconverted are then separated. A portion of said unreacted ethanol / isopropanol stream from the purification step is mixed with at least a portion of the recycled purified water stream. The mixture of these two streams is carried upstream of the first exchanger, with the aqueous charge of alcohols to be dehydrated.
    [0018] The process according to the invention advantageously makes it possible to treat a mixture containing ethanol and isopropanol which is derived from a so-called "IBE" fermentation unit. This IBE fermentation of sugars is generally carried out in strict anaerobiosis using microorganisms of the genus Clostridium. The fermentable sugars are preferably obtained after pretreatment of a biomass of the lignocellulosic type and enzymatic hydrolysis. Lignocellulosic biomass is one of the most abundant renewable resources on earth. The substrates considered are very varied, since they concern both woody substrates (hardwood and softwood), agricultural by-products (straw) or lignocellulosic waste-generating industries (agro-food industries, paper mills). The fermentation must from the fermentation reactor undergoes a solid / liquid separation step for separating a fermentative aqueous effluent (or wine) containing the mixture of alcohols and a solid fraction. The wine resulting from the IBE fermentation is an aqueous solution generally containing 15 to 45 g / l of alcohols including 2 to 30% by weight of ethanol, 10 to 60% by weight of isopropanol and 20 to 60% by weight of butanol. In the case where the treated feedstock is an aqueous solution containing ethanol, isopropanol with more than 80% by weight of water relative to the total weight of the aqueous solution, the process according to the invention comprises before step a) of dehydrating ethanol and isopropanol, a step of separating the water (or drying) from the aqueous solution. This step can be performed according to any technique known to those skilled in the art. For example according to a first embodiment, this separation consists of a distillation in a column. According to a second embodiment, the separation step consists of a solvent extraction step by means of an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms. Preferably, the aromatic section comprises a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene. This extraction is preferably conducted at a temperature between 50 and 120 ° C and preferably in a countercurrent extraction mode. From the extraction column is extracted an aromatic section containing the mixture of isopropanol, ethanol and optionally butanol and an aqueous fraction. The aromatic section containing the mixture of alcohols is then sent to a distillation unit whose purpose is to separate the extraction solvent from the mixture of alcohols.
    [0019] In the case where the mixture of alcohols additionally contains butanol, the said mixture is treated in another separation unit, for example a distillation column, in order to separate the butanol and obtain a low-grade mixture of ethanol and isopropanol. butanol which is then treated in the dehydration unit of ethanol and isopropanol.
    [0020] In the context of the invention, the effluent from the partial drying step may optionally contain acetone (for example between 0.3 and 1% by weight), which is a co-product of the "IBE" fermentation. Before the butanol separation step of the ethanol-isopropanol mixture, the effluent is pretreated in a distillation unit operated to specifically separate the acetone from the mixture.
    [0021] Other features and advantages of the invention will be better understood and will become clear from reading the description given below with reference to the drawings in which: FIG. 1 shows a first embodiment of the method according to the invention; ; FIG. 2 diagrammatically represents a second embodiment of the method according to the invention; - Figure 3 shows another embodiment of Figure 1comprenant further a butanol purification step.
    [0022] Generally, similar elements are denoted by identical references in the figures. Referring to Figure 1, an aqueous effluent (or wine) containing a mixture of ethanol, isopropanol and butanol, which is derived from a fermentation unit "IBE" 1, is sent via line 2 to a separation unit 3, which is in the example of Figure 1 a distillation column. The objective of this first step, which can be described as "partial drying", is to reduce the water content of the effluent (or wine) IBE whose composition depends not only on the origin of the sugars but also microorganisms used for IBE fermentation.
    [0023] The stream 2 entering the distillation column 3 can thus comprise up to 98% weight in water. With reference to FIG. 1, an aqueous fraction is extracted from the distillation column 3 which is discharged at the bottom of the column via line 5 and a head fraction containing an aqueous mixture of alcohols via line 4. The aqueous mixture of alcohol typically has a mass content of water relative to the total weight of the aqueous mixture of up to 70% by weight. The distillation column 3 is designed and operated so as to recover preferably 99% by weight of the alcohols at the top of the column. For example, a distillation column which processes an "IBE" mixture makes it possible to remove a fraction containing up to 65% by weight of mixture of alcohols and in the bottom an aqueous fraction containing a few tens of ppm (weight) of alcohols. The aqueous mixture of ethanol, isopropanol and butanol is then fed to a distillation column 6 which is designed to separate butanol from the aqueous mixture of alcohols. Typically distillation column 6 is operated at a temperature between 110 and 145 ° C and at a pressure between 0.4 and 0.7 M'a. Preferably the distillation column is operated at a pressure of at least 0.5 MPa in order to maintain a temperature of at least 110 ° C in the column to avoid liquid-liquid-vapor demixing phenomena.
    [0024] Correctly operated, the distillation column makes it possible to recover, at the bottom of said column 6 via line 8, a fraction containing 99% by weight of the butanol contained in the fraction introduced and, at the top by line 7, at least 99% by weight of the isopropanol and ethanol contained in the fraction introduced. According to an alternative embodiment also shown in Figure 1, the mixture containing ethanol, isopropanol and butanol from the first step called "partial drying" is first sent through line 9 in a distillation column 10 which is operated to extract the acetone. With reference to FIG. 1, the acetone is recovered at the top of column 10 via line 11 and the fraction containing the mixture of ethanol, isopropanol and butanol and depleted of acetone is recovered at the bottom of column 10 and is sent via line 12 to distillation column 6.
    [0025] With reference to FIG. 1, the mixture comprising water, isopropanol and ethanol extracted from the distillation column 6 is heated and vaporized by means of a heat exchanger 14 and then compressed by means of a compressor 15 before being sent to the dehydration step, in the dehydration unit 13, to convert said alcohols to ethylene and propylene. It should be noted that the effluent containing the mixture of isopropanol and ethanol from the distillation column 6 can optionally be sent to an adsorber (not shown) to further dry the effluent if necessary, before the step dehydration so that the mixture of ethanol and isopropanol has a water content of between 30 and 75% by weight of water relative to the total weight of the mixture.
    [0026] The dehydration reaction is carried out in a dehydration unit comprising at least one reactor in which ethanol and isopropanol are contacted with a catalyst capable of dehydrating ethanol and isopropanol. In the case where the mixture of ethanol and isopropanol has a water content of less than 30% by weight relative to the total weight of the mixture, it is intended to bring water to said mixture before dehydrating it. For this purpose, as shown in FIG. 1, a line 40 is provided upstream of the dewatering unit 13 for injecting water into the mixture at the outlet of the compressor 15. Preferably, the water is supplied in vapor form to the mixture of ethanol and isopropanol. According to the invention, this step of conversion of ethanol and isopropanol to olefins uses an alumina chosen from: an alumina (A) having at least 50% by weight of alumina y, a BET specific surface area measured according to the ASTM D 3663-03 standard of between 200 and 350 m 2 / g, a mesoporous mean diameter of between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulfur content of less than 40 ppm by weight; and an alumina (B) having at least 50% by weight of alumina y, a BET specific surface area measured according to ASTM D 3663-03 of between 130 and 180 m2 / g, a mesoporous mean diameter of between 14 and 20 nm, a sodium content of between 300 and 600 ppm by weight and a sulfur content of 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 a thorough drying of the mixture of ethanol / isopropanol to the extent that its water content is between 30 to 75% by weight relative to the weight total of the mixture. The water contained in the mixture of alcohols is advantageously used in the dehydration process according to the invention as a thermal fluid.
    [0027] The catalytic dehydration reaction is carried out at a temperature between 350 and 500 ° C, at a total pressure of between 0.2 and 2 MPa and with a weight hourly weight (pph) defined as the ratio of the mass flow rate of the mixture ( ethanol and isopropanol) on the catalyst mass of between 1 and 10 h -1. The dehydration step 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 operates (s) either in a fixed bed or in a moving bed, but preferably in a bed fixed. The dehydration step of the alcohols is preferably carried out according to the method described in the patent application FR 2961202 which involves at least one adiabatic dehydration reactor. The method implies that the effluent from the last dehydration reactor is sent to the heat exchanger and that the charge to be dehydrated is introduced into the preliminary vaporization stage at a pressure lower than the pressure of the effluent at the outlet of the last dehydration reactor, so as to maximize the heat exchange between the feedstock and the effluent from the last reactor, that is to say to exchange the entire enthalpy of vaporization of the feedstock and the enthalpy of condensation said effluent. At the end of the dehydration step, an effluent gas 16 containing a mixture of propylene and ethylene and an effluent comprising water from the dehydration unit 13 and after a distillation step is recovered at the end of the distillation step. line 17. This gaseous effluent of propylene and ethylene can subsequently be subjected to a distillation step in order to separate the two olefins, which are then recoverable as a petrochemical raw material. As mentioned above, the process according to the invention is advantageous from the economic point of view since it makes it possible to produce ethylene and propylene from an aqueous mixture of isopropanol and ethanol while avoiding an expensive step of separation of alcohols. Thanks to the process according to the invention, ethanol and isopropanol are converted concomitantly in order to produce a flow of ethylene mixed with propylene which are olefins easily separable, in particular by distillation.
    [0028] 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 unit is a solvent extraction unit comprising an extraction column. liquid-liquid supplemented preferably by a distillation column.
    [0029] Referring to Figure 2, the fermenting juice containing ethanol, isopropanol, butanol, from unit 1 IBE fermentation is sent through line 2 in a liquid-liquid extraction column 30 and in which a solvent which is an aromatic cut comprising a mixture of aromatic compounds having 7 to 10 carbon atoms, is preferably injected countercurrently, for example at the bottom of the extraction column 30, via the line 31. carbon. The solvent according to the invention has the capacity to absorb ethanol, isopropanol and butanol and also has a practically zero solubility in water. For example, the solvent is a heavy reformate from a catalytic gasoline reforming unit which processes a naphtha fraction of crude oil to increase the content of aromatic compounds. This catalytic reforming stage (aromatization of gasoline) is accompanied by a heavier gasoline. Also, in order to guarantee a boiling point of the gasoline according to the commercial specification, it is customary to redistill these species to eliminate the heaviest fraction which is called "heavy reformate".
    [0030] By difference of density and thanks to the affinity of the solvent vis-à-vis ethanol, isopropanol and butanol, is recovered at the top of the extraction column an organic effluent 32 containing the aromatic section and the sought-after spirits and in the background, via line 5, a stream of water. For carrying out the liquid-liquid extraction, the mass ratio between the filler and the solvent is generally between 0.5 and 5. The contacting with the solvent is generally carried out at a temperature of between 60 and 120 ° C and at a corrected pressure between 0.5 and 5 MPa. As shown in FIG. 2, a line 36 makes it possible to add solvent if this is necessary for the operation of the column 30. Thus, at the top of the liquid-liquid extraction column, an effluent containing at least 99% is recovered. weight of the alcohols present in the mixture of alcohols.
    [0031] In accordance with FIG. 2, the organic effluent extracted at the top of the liquid-liquid extraction column 30 is sent via line 32 to a distillation column 34 configured to separate at the top the mixture comprising ethanol and isopropanol. and butanol of the extraction solvent which is withdrawn from the bottom of said distillation column 34. The solvent which is recovered from the distillation column via line 37 is recycled via line 31 into the liquid-liquid extraction column 30 This distillation is preferably carried out at reduced pressure, preferably 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" vapor as a reboiling fluid. The process according to the embodiment of FIG. 2 has the advantage of being less energy consuming compared to the first embodiment because unlike distillation, the use of the liquid-liquid extraction column does not require Heat the mixture of alcohols thoroughly to dry. In the embodiment of Figure 2, the organic effluent withdrawn through the line 35 and consisting essentially of ethanol, isopropanol and butanol is sent to a separation unit 6 butanol. The separation unit 6, for example a distillation column, is operated to provide a mixture consisting essentially of ethanol and isopropanol which is withdrawn via line 7 and an effluent consisting essentially of butanol via line 8. in FIG. 2, the mixture consisting essentially of ethanol and isopropanol is heated by the heat exchanger 14 and then compressed by the compressor 15 before being sent with water brought by the line 40 into the dehydration unit 13. The addition of water, via line 40, makes it possible to regulate the water content of the alcohol charge so as to provide an ethanolisopropanol-water mixture whose water content is between 30 and 75 % weight of water relative to the total weight of the mixture.
    [0032] FIG. 3 shows an embodiment complementary to that of FIG. 1. As indicated in FIG. 3, the aqueous flow of butanol 8, which is extracted at the bottom of the distillation column 6, is treated in a separation unit in order to recover butanol. For this purpose, the aqueous flow of butanol is cooled, for example at a temperature of 60 ° C. to a flask 18 in order to demix the mixture in two phases, namely an organic phase containing essentially butanol (for example at least 70% by weight). butanol) and an aqueous phase. The two phases are treated in a hetero-azeotropic distillation system which comprises two columns 21, 22 operating in parallel. The organic phase containing mainly butanol is sent via line 19 to the hetero-azeotropic distillation column 21 which preferably operates at a pressure of between 0.3 and 10 MPa and at a temperature of between 115 and 150 ° C. in order to avoid liquor-liquid vapor separation problems. An effluent having a content by weight of at least 99% butanol and at the top, via line 24, an aqueous effluent which is returned to the separating flask 18 is withdrawn at the bottom of the said column 21 via line 23. The aqueous phase still containing butanol, which is withdrawn from the biphasic separator flask 18, is sent via line 20 to the hetero-azeotropic distillation column 22. A flow rich in water is recovered at the bottom of the said column 22, and at the top an effluent which is recycled via the line 25 into the biphasic separator flask 18. The column 22 is operated under less severe conditions, for example at a pressure lower than that of the column 21. Advantageously, all or part of the butanol which is recovered from the hetero-azeotropic distillation unit is sent to a catalytic butanol dehydration unit 27 for conversion to butene and preferably butene-2. According to an advantageous embodiment (not shown), butene-2 thus produced is reacted with ethylene in a reactor to form propylene through a metathesis reaction known to those skilled in the art. EXAMPLES Various catalysts are tested for the dehydration of a mixture containing 25% by weight of ethanol, 25% by weight of isopropanol and 50% by weight of water relative to the total weight of the mixture. The catalysts are in the form of trilobal extrudates of 1.6 mm in diameter.
    [0033] Table 1 below gives the characteristics of the catalysts tested. Catalyst Type of alumina Average diameter, Specific surface Mesoporous content (nm) (m2 / g) measured according to sodium (ppm sulfur (ppm ASTM D 3663-03 weight) weight) Cl (according to Alumina y 10.3 208 Lower to less than 40 the invention) pseudo cubic C2 (according to alumina y 8,5 216 28 less than 40 the invention) cubic C3 (according to alumina y 7.432 35 less than 40 the invention) cubic C4 Alumina y 5.7 155 417 Less than 40 (comparative) cubic and alumina x C5 Alumina y 8.7 C7 (Comparative) cubic C6 (according to Alumina y 15.7 175 550 903 the invention) cubic C7 (according to alumina y The invention is directed to the invention that the invention is a tetragonal + alumina 0 C8 alumina S and 25.8 154 401 less than 40 (comparative) alumina x C9 alumina and 18.3 143 222 1121 (comparative) cubic Table 1 C1 catalysts, C2 and C3 conform to an alumina (A) according to the invention and the catalysts C6 and C7 conform to an alumina (B) according to the invention. Catalyst C4 is non-compliant with an alumina (A) according to the invention because its specific surface area and its sodium content are outside the ranges claimed. In addition, the catalyst D is non-compliant with an alumina (B) according to the invention because its mesoporous mean diameter is outside the range 14-20 nm. The non-conforming C5 catalyst is distinguished from an alumina (A) according to the invention by the sodium and sulfur contents which are higher than the upper limit of the ranges claimed. Catalyst C5 is also non-compliant with an alumina (B) according to the invention and is distinguished by its mesoporous mean diameter and its specific surface area.
    [0034] Catalyst C8 does not meet the definition of an alumina (A) according to the invention because the mesoporous average diameter, the specific surface area and the sodium content are outside the ranges claimed. The catalyst C8 is also non-compliant with an alumina (B) according to the invention because it has a mesoporous average diameter greater than the claimed range and a sulfur content of less than 800 ppm by weight. The catalyst C9 is non-compliant with a alumina (A) according to the invention by its mesoporous mean diameter, its specific surface area, its sodium content and sulfur. Catalyst I is distinguished from an alumina (B) according to the invention by its sodium content.
    [0035] Before their implementation in the dehydration test of the alcohol mixture, all the catalysts have undergone a conditioning phase which comprises the following steps: i) heating the catalyst from an ambient temperature up to 550 ° C. under a flow of air at 5 N / h with a temperature ramp of 20 ° C per hour; ii) maintaining at a temperature of 550 ° C under airflow for 2 hours; iii) cooling the catalyst to the test temperature under a flow of nitrogen at 100 NI / h; iv) maintaining the catalyst at the test temperature under a flow of nitrogen at 100 NI / h for 5 hours.
    [0036] 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 = 375 ° C; relative pressure in the reactor = 0.2 MPa; - hourly weight speed (pph), which is defined as the ratio of the mass flow rate (ethanol + isopropanol) on the catalyst mass = 211-1. The effluent leaving the dehydration reactor is sent to a high pressure separator (HP) to separate a first gas stream and a liquid stream. The liquid stream is then transferred to a low pressure separator (LP) from which a second gas stream and a second liquid stream are separated. The two gas streams are mixed before being analyzed. The liquid and gaseous streams are analyzed by gas phase chromatography. Table 2 gives the catalytic performances of the aluminas tested after 72 hours of test. The conversions and selectivities were calculated from the formulas described above.
    [0037] Finally, the purity of the cuts C2 is calculated with respect to ethylene, ethane and methane while the purity of the C3 cut is calculated relative to propylene, propane and cyclopropane. Thus the ethylene purities of the C2 and C3 cut of the C3 cut are expressed as follows: Ethylene purity = mC ethylene output * 100 * 100 Propylene purity, mC ethylene outlet + mCethane outlet + mC methane mC outlet propylene outlet mC propylene outlet + MC propane outlet + mCyclopropane outlet Catalyst Cl C2 C3 C4 C5 C6 C7 C8 C9 Conversion of iso-propanol (%) 100 100 100 100 100 100 100 99.90 100 Propylene selectivity 99.88 99 , 92 99.81 99.56 99.62 99.62 99.85 98.48 98.39 Selectivity to Dipropylether 0 0 0 0 0 0 0 0.15 0 Propane Selectivity 0.07 0.03 0.09 0 , 0.21 0.12 0.07 0.06 0.96 Propanal selectivity 0.04 0.05 0.10 0.15 0.10 0.24 0.06 0.12 0.60 Selectivity to Ethoxypropane 0.01 0 0 0 0 0 0 0 0 Composition C3 cut (% wt) Propylene 99.93 99.97 99.91 99.80 99.79 99.88 99.93 99.93 99.03 Propane 0.07 0.03 0.09 0.2 0.21 0.12 0.07 0.07 0.97 Cyclopropane 0 0 0 0 0 0 0 0 0 Conversion of ethanol (%) 92.02 97,16 97, 60 83.00 86.20 90.80 91.68 59.48 89.50 Methane Selectivity 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Selectivity Ethylene 98 , 96 99.65 99.65 97.84 98.17 98.70 98.97 81.82 96.84 Selectivity Ethane 0.16 0.10 0.13 0.23 0.26 0.19 0.09 0 , 1.10 Selectivity Diethylether 0.54 0.16 0.12 1.45 1.10 0.75 0.64 16.10 0.71 Selectivity EthylPropylEther 0.03 0 0 0.12 0.09 0.08 0.05 1.70 0.09 Selectivity Butane 0.17 0.13 0.16 0.22 0.17 0.11 0.13 0.15 0.49 Selectivity Butene 0.08 0.04 0.10 0 , 11 0.16 0.12 0.10 0.04 0.65 Selectivity C5 + 0.02 0.01 0.01 0.03 0.05 0.05 0.02 0.01 0.12 Composition C 2 ( % by weight) Ethylene 99.84 99.90 99.87 99.77 99.74 99.81 99.91 99.78 98.88 Ethane 0.16 0.10 0.13 0.23 0.26 0.19 0.09 0.22 1.12 Methane 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Table 2 The use of the catalysts according to the invention ( C1, C2, C3, C6 and C7) make it possible to obtain excellent conversion rates of isopropanol but also of ethanol which are respectively d e 100% and order 90%. On the other hand, it is constant that, with the catalysts outside the invention (D, E, H, I), the conversion rates of ethanol are less than 90%. On the other hand, it is observed that the purity of propylene in a C3 cut and that of ethylene in a C2 cut are better when the catalysts according to the invention are used. 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.
    权利要求:
    Claims (16)
    [0001]
    REVENDICATIONS1. Process for producing a mixture of ethylene and propylene from a mixture containing ethanol and isopropanol and having a water content of between 30 and 75% by weight relative 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 ASTM D 3663-03 standard of between 200 and 350 m2 / g, a mesoporous mean diameter of between 5 and 15 nm, a sodium content of less than 50 ppm by weight and a sulfur content of less than 40 ppm by weight; and an alumina (B) having a BET specific surface area measured according to ASTM D 3663-03 of between 130 and 180 m2 / g, a mesoporous average diameter of between 14 and 20 nm, a sodium content of between 300 and 600 ppm weight and a sulfur content of between 800 and 1300 ppm by weight; the contacting being carried out at a temperature between 350 and 500 ° C, at a total pressure between 0.2 and 2 MPa and with a weight hourly weight (pph) defined as the ratio of the mass flow rate ethanol and isopropanol on the catalyst mass of between 1 and 10 h -1, b) an effluent containing ethylene and propylene from said dehydration unit is withdrawn.
    [0002]
    2. Method according to claim 1, wherein the mixture contains between 1 and 75% by weight of ethanol and between 99 and 25% by weight of isopropanol relative to the total weight of ethanol and isopropanol.
    [0003]
    3. Method according to one of claims 1 or 2, wherein the aluminas (A) and (B) are gamma aluminas.
    [0004]
    4. Method according to one of the preceding claims, wherein the alumina (A) has a BET specific surface area measured according to ASTM D 3663-03 of between 200 and 280 m2 / g.
    [0005]
    5. Method according to one of the preceding claims, wherein the alumina (A) has a mesoporous mean diameter of between 6 and 12 nm and preferably between 7 and 11 nm.
    [0006]
    6. Method according to one of claims 1 to 3, wherein the alumina (B) has a BET specific surface area measured according to ASTM D 3663-03 of between 150 and 180 m2 / g.
    [0007]
    7. Method according to one of claims 1 to 3 or claim 6, wherein the alumina (B) has a mean mesoporous diameter of between 15 and 20 nm.
    [0008]
    8. A method according to one of the preceding claims, wherein when the mixture further comprises butanol, said mixture is treated to separate the butanol before step a) dehydration.
    [0009]
    9. Process according to claim 8, wherein butanol is separated off by distillation.
    [0010]
    10. Method according to one of the preceding claims, wherein before step a) is brought into contact in a separation unit comprising a liquid-liquid extraction column (30), the mixture with an aromatic section comprising a mixture of aromatic compounds having 7 to 10 carbon atoms so as to separate from said extraction column (30) an aqueous fraction (5) and an organic fraction containing the aromatic section, ethanol, isopropanol and said organic fraction in a distillation column (34) configured to extract an effluent (37) containing the aromatic cut and a mixture (35) containing ethanol, isopropanol and said mixture is fed to the dehydration unit .
    [0011]
    11. The process according to claim 10, wherein the aromatic cut is a mixture of 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene.
    [0012]
    12. Method according to one of claims 10 or 11, wherein the contacting of the mixture containing ethanol, isopropanol, water with the aromatic section is made against the current.
    [0013]
    13. Method according to one of claims 1 to 9, wherein before step a) is sent the mixture containing ethanol, isopropanol, water in a separation unit comprising a distillation column (3) so as to separate from the distillation column an aqueous fraction and an effluent containing a mixture of ethanol, isopropanol and water with a water content of between 30 and 75% by weight relative to the total weight of the mixture and the effluent is sent to the dehydration unit.
    [0014]
    14. Method according to one of the preceding claims wherein the mixture containing ethanol, isopropanol is derived from a fermentation unit IBE.
    [0015]
    15. Method according to one of the preceding claims, wherein the contacting of step a) is performed in at least one reactor at a temperature between 350 and 450 ° C and more preferably between 375 and 425. ° C, at a total pressure of between 0.2 and 2 MPa and more preferably between 0.2 and 1 MPa, and with a weight hourly weight (pph) of between 1 and 10 h -1, and preferably between 2 and 8 h-1.
    [0016]
    16. Process according to one of the preceding claims, in which step a) is carried out in two adiabatic reactors in series.
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    同族专利:
    公开号 | 公开日
    BR112016010980B1|2021-07-13|
    UA117770C2|2018-09-25|
    KR20160090851A|2016-08-01|
    CN106061927A|2016-10-26|
    CA2931704C|2021-11-16|
    EP3074369A1|2016-10-05|
    US20170022124A1|2017-01-26|
    US9902663B2|2018-02-27|
    BR112016010980A2|2017-08-08|
    KR102233329B1|2021-03-29|
    CN106061927B|2018-07-24|
    FR3013707B1|2016-07-29|
    CA2931704A1|2015-06-04|
    WO2015078624A1|2015-06-04|
    EP3074369B1|2017-12-27|
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    法律状态:
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    2016-04-22| TQ| Partial transmission of property|Owner name: IFP ENERGIES NOUVELLES, FR Effective date: 20160318 Owner name: TOTAL RESEARCH & TECHNOLOGY FELUY SA, BE Effective date: 20160318 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1361684A|FR3013707B1|2013-11-27|2013-11-27|METHOD FOR DEHYDRATING A MIXTURE CONTAINING ETHANOL AND ISOPROPANOL|FR1361684A| FR3013707B1|2013-11-27|2013-11-27|METHOD FOR DEHYDRATING A MIXTURE CONTAINING ETHANOL AND ISOPROPANOL|
    US15/039,613| US9902663B2|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
    CN201480074217.5A| CN106061927B|2013-11-27|2014-10-08|The method that will be dehydrated containing the mixture of ethyl alcohol and isopropanol|
    EP14786825.1A| EP3074369B1|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
    UAA201606893A| UA117770C2|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
    PCT/EP2014/071550| WO2015078624A1|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
    CA2931704A| CA2931704C|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
    BR112016010980-5A| BR112016010980B1|2013-11-27|2014-10-08|DEHYDRATION PROCESS OF A MIXTURE, CONTAINING ETHANOL AND ISOPROPANOL|
    KR1020167016707A| KR102233329B1|2013-11-27|2014-10-08|Method for dehydrating a mixture containing ethanol and isopropanol|
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