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    • 专利摘要:
    simultaneous dehydration and isomerization of the isobutanol backbone in acid catalysts. The present invention (in a first embodiment) relates to a process of simultaneous dehydration and isomerization of the isobutanol backbone to produce substantially olefins having the same carbon number and consisting essentially of a mixture of n-butenes and iso-butene. a process comprising: a) introducing into a reactor a chain (a) comprising isobutanol, optionally water, optionally an inert component, b) contacting said chain with a catalyst in said reactor under conditions effective to dehydrate and isomerize the backbone, at least one isobutanol portion to produce a mixture of n-butenes and iso-butene, c) recovering from said reactor a chain (b), removing water, the inert component (if any) and uncovered isobutanol (if any) to obtain a a mixture of n-butenes and iso-butene, wherein the isobutanol whsv (hourly space velocity by weight) is at least 1h ^ 1- ^ or the temperature is 200 <ca. It is capable of simultaneously dehydrating and isomerizing the butene backbone. the catalyst is a fer group crystalline silicate, mww, euo, mfs, zsm-48, mtt, mfi, honey or ton having si / al higher than 10, or an aluminous fer group crystalline silicate, mww, euo, mfs , zsm-48, mtt, mfi, honey or ton having si / al higher than 10, or modified phosphorus silicate of the fer group, mww, euo, mfs, zsm-48, mtt, honey or ton, having si / al higher than 10, or a group AEL molecular sieve silicoaluminophosphate, or a silicate, zirconated, titanated or fluorinated aluminum. advantageously, strand (b) is fractionated in step d) to produce an n-butene strand (n) and remove the essential part of isobutene optionally recycled with strand (a) to the dehydration / isomerization reactor of step b).
    公开号:BR112012023262B1
    申请号:R112012023262-2
    申请日:2011-03-15
    公开日:2018-06-19
    发明作者:Adam Cindy；Minoux Delphine；Nesterenko Nikolai；Van Donk Sander；Dath Jean-Pierre
    申请人:Total Research & Technology Feluy；
    IPC主号:
    专利说明:

    (54) Title: SIMULTANEOUS DEHYDRATION AND ISOMERIZATION OF THE ISOBUTANOL SKELETON IN ACID CATALYSTS (51) Int.CI .: C07C 1/24; C07C 11/00; C07C 11/08; C07C 9/11; B01J 29/06; B01J 29/40; B01J 29/85 (30) Unionist Priority: 04/09/2010 EP 10159463.8, 03/15/2010 EP 10156537.2, 27/04/2010 EP 10161125.9 (73) Holder (s): TOTAL RESEARCH & TECHNOLOGY FELUY (72) Inventor (s): CINDY ADAM; DELPHINE MINOUX; NIKOLAI NESTERENKO; SANDER VAN DONK; JEAN-PIERRE DATH
    1/19
    Invention Patent Descriptive Report for; “SIMULTANEOUS DEHYDRATION AND ISOMERIZATION OF THE ISOBUTANOL SKELETON IN ACID CATALYSTS”. FIELD OF THE INVENTION
    The present invention relates to the simultaneous dehydration and isomerization of the isobutanol backbone to produce a corresponding olefin, having considerably the same number of carbons, but a different backbone structure. The limited stock and rising cost of crude oil spurred demand for alternative processes to produce hydrocarbon products such as isobutene and n-butene. Isobutanol can be obtained by fermenting carbohydrates or by condensing lighter alcohols, obtained by fermenting carbohydrates. Made from organic matter from living organisms, biomass is the world's leading renewable energy source. BACKGROUND OF THE INVENTION
    Isobutanol (2-methyl-1-propanol) has historically been found in limited applications and its use is similar to that of 1-butanol. It was used as a solvent, diluents, wettable agent, cleaner additive and as an additive for paints and polymers. Recently, isobutanol has gained interest as a fuel or fuel component since it exhibits a high octane number (Octane Mixture R + M / 2 is 102-103) and a low vapor pressure (RVP is 3.8-5, 2 psi).
    Isobutanol is usually considered a byproduct of industrial production of 1-butanol (Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2002). It is produced from propylene through hydroforming in the oxo process (Rh-Baseou catalyst) or through carbonylation in the Reppe process (Co based catalyst). Hydroforming or carbonylation produces n-butanol and iso-butanol in ratios ranging from 92/8 to 75/25. To obtain isobutanol, iso-butanol is hydrogenated over a metal catalyst. Isobutanol can also be produced from synthetic gas (mixture of CO, H 2 and CO 2 ) by a process similar to Fischer-Tropsch, resulting in a mixture of higher alcohols, although normally a preferential formation of isobutanol occurs (Applied Catalysis A, general, 186, pp. 407, 1999 and Chemiker Zeitung, 106, p. 249, 1982). Yet another route to obtain isobutanol is the condensation of methanol-based catalyst based Guerbet and / or propanol ethanol. (J. of Molecular Catalysis A: Chemical 200, 137, 2003 and Applied Biochemistry and Biotechnology, 113-116, p. 913, 2004).
    Recently, new biochemical routes have been developed to selectively produce isobutanol from carbohydrates. The new strategy uses the highly active amino acid biosynthetic route of microorganisms and diverts their 2-keto acid intermediates from alcohol synthesis. 2-keto acids are intermediates in biosynthetic amino acid routes. These metabolites can be converted to aldehydes by 2-ketodecarboxylase acids (KDCs) and then to alcohols by alcohols dehydrogenases (ADHs). Two
    2/19 unnatural steps are required to produce alcohols by diverting intermediates from the biosynthetic routes of amino acids for the production of alcohol (Nature, 451, p. 86, 2008 and US patent US2008 / 0261230). Recombinant microorganisms are required to improve the flow of carbon towards the synthesis of 2-keto acids. In the biosynthesis of valine 2 ketoisovalerate is an intermediate. Carbohydrate glycolysis results in pyruvate which is converted to acetolactate by acetolactate synthase. 2,4-Dihydroxyisovalerate is formed outside of acetolactate, catalyzed by isomeroreductase. A dehydratase converts 2,4-dihydroxyisovalerate to 2-keto-isovalerate. In the next step, a keto decarboxylase acid produces 2-keto isovalerylate isobutyraldehyde. The last step is the hydrogenation of isobutyraldehyde by an isobutanol dehydrogenase.
    Of the routes described in relation to the isobutanol above, the Guerbet condensation, the hydrogenation of synthetic gas and the 2-keto acid route of carbohydrates are routes that can use biomass as primary raw material. Biomass gasification results in synthetic gas that can be converted into methanol or directly into isobutanol. Ethanol is already on a very large scale produced by fermenting carbohydrates or by directly fermenting synthetic gas in ethanol. Then, methanol and ethanol from biomass can still be condensed to isobutanol. The 2-keto acid direct route can produce isobutanol from carbohydrates that are isolated from biomass. Simple carbohydrates can be obtained from plants such as sugar cane, sweet beets. More complex carbohydrates can be obtained from plants such as corn, wheat and other plants that produce grains. Even more complex carbohydrates can be considerably isolated from any biomass, by shedding cellulose and hemicellulose from lignocelluloses.
    In the mid-nineties, many oil companies tried to produce more isobutene for the production of MTBE. For this reason, many isomerization backbone catalysts for converting n-butenes to iso-butene have been developed (Adv. Cat. 44, p. 505, 1999; Oil & Gas Science and Technology, 54 (1) p. 23, 1999 and Applied Catalysis A; General 212, 97, 2001). Promising catalysts include 10-membered ring zeolites and modified aluminum. Reverse isomerization of the isobutene backbone into n-butenes was not mentioned.
    The dehydration reactions of alcohols to produce alkenes have been known for a long time (J. Catai. 7, p. 163, 1967 and J. Am. Chem. Soc. 83, p. 2847, 1961). Many available solid acid catalysts can be used to dehydrate alcohol (Stud. Surf. Sci. Cat. 51, p. 260, 1989). However, y-aluminum is also generally used, especially for longer-chain alcohols (with more than three carbon atoms). This is because catalysts with stronger acidity, such as silica-aluminum, molecular sieves, zeolites or resin catalysts can promote double-bond alteration, skeletal isomerization and other olefin inter-conversion reactions. The primary product of isobutanol acid catalysis dehydration is iso-butene:
    CH3-CH-CH2-OH <- »CH3-C = CH 2 + h 2 o II ch 3 ch 3
    The dehydration of alcohols with four or more carbons over solid acid catalysts is expected to be accompanied by the double-bonding reaction reaction of the alkene product. This is because the two reactions occur easily and at comparable rates (Carboniogenic Activity of Zeolites, Elsevier Publishing Company, Amsterdam (1977) p. 169). The primary product, iso-butene is very reactive in the presence of an acid catalyst because of the presence of a double bond linked to a tertiary carbon. This allows for easy protonation, as the tertiary structure of the resulting carbocation is the most favorable among possible carbocation structures (tertiary> secondary> primary carbocations). The resulting t-butyl cation undergoes oligo / easy polymerization or other electrophilic substitution in aromatic or aliphatic or electrophilic addition reactions. The reorganization of the t-butyl cation is not a clear reaction as, without being limited to any theory, it involves an intermediate formation of secondary or primary butyl-cation and therefore the probability of secondary reactions (substitutions or additions) is very high and would reduce selectivity for the desired product.
    Dehydration of butanols has been described in aluminum-type catalysts (Applied Catalysis A, General, 214, p. 251, 2001). Both double-bonding and skeleton isomerization changes were obtained at very low space velocity (or very long reaction time) corresponding to a GHSV (Space velocity per gas hour = feed rate ratio (gram / h) to catalyst weight (ml) less than 1 gram. ΜΓ 1 . Η 1 . The international patent application W02005 / 110951 describes a process for the production of propylene through metathesis of n-butenes which were obtained through the isomerization of the iso-butene backbone that is produced from t-butanol through dehydration. All steps in the present application are performed separately.
    It has now been discovered that dehydration and isomerization of the iso-butyl fraction backbone in isobutanol can be performed simultaneously.
    By way of example it was discovered that for simultaneous dehydration and isomerization of the isobutanol backbone, the crystalline silicates of the FER, MWW, EUO, MFS, ZSM-48, MTT or TON group having Si / AI higher than 10, or a Silicate crystalline crystalline group FER, MWW, EUO, MFS, ZSM-48, MTT or TON having Si / AI higher than 10, or a modified phosphorous crystalline silicate from group FER, MWW, EUO, MFS, ZSM-48, MTT or TON having Si / AI higher than 10, or molecular sieves of AEL group type silicoaluminophosphate or silicate, zirconated or titanated aluminum
    4/19 or fluorinated aluminum has many advantages. Said dehydration can be done with a WHSV (Spatial speed per hour of weight = ratio of feed index (gram / h) to the weight of the catalyst (ml)) less than 1 h ' 1 , at a temperature of 200 to 600 ° C and using an isobutanol-diluent composition of 30 to 100% isobutanol at a total operating pressure of 0.05 to 1 0.0 MPa.
    By way of example, the dehydration / isomerization of isobutanol in a ferrierite having a Si / AI ratio of 10 to 90 and with a WHSV less than 2 h ' 1 producing nbutenes alongside iso-butene, the conversion of isobutanol is at least 98% and normally 99%, advantageously the yield of butenes (iso and n-butenes) is at least 90%, the selectivity of n-butenes is between 5% and the thermodynamic balance under the given reaction conditions.
    The conversion of isobutanol is the ratio (isobutanol introduced in the reactor -isobutanol leaving the reactor) / (isobutanol introduced in the reactor).
    The yield of n-butenes is the ratio, on a carbon basis, (n-butenes leaving the reactor) / (isobutanol introduced into the reactor).
    The selectivity of n-butenes is the ratio, based on carbon, (n-butenes leaving the reactor) / (isobutanol converted in the reactor).
    The simultaneous dehydration / isomerization of isobutanol results in a mixture of nbutenes (but-1-ene and but-2-ene) and iso-butene. According to the present invention, normally a composition close to thermodynamic equilibrium is obtained while maintaining the high yield of the total butenes. The thermodynamic balance for n-butenes varies between 50 and 65% and for iso-butene between 35 and 50% depending on operating conditions. An important advantage of the present invention is that the composition resembles the composition of a cut of I C4 raffinate obtained from a "steam naphtha cracker". Raffinate is obtained by removing butadiene from the rough cut of C4 produced in a “steam naphtha cracker”. Typical compositions are: 35-45% isobutene, 3-15% butanes and the remaining 52-40% nbutenes. It is evident that the simultaneous dehydration / isomerization product can easily replace the use of fossil rafinate I in existing petrochemical plants. The result is that capital investment can be reduced and that derivatives of such an iso-butene / n-butene mixture can be produced from renewable resources instead of fossil resources simply by replacing fossil raffinate I with the product of the present invention. .
    EP 2090561 A1 describes the dehydration of an alcohol in crystalline silicates to receive the corresponding olefin. Ethanol, propanol, butanol and phenylethanol are mentioned. Only ethanol is used in the examples. Nothing is said about isobutanol and its isomerization.
    BRIEF DESCRIPTION OF THE INVENTION
    The present invention (in a first embodiment) relates to a process for the
    5/19 simultaneous dehydration and isomerization of the isobutanol backbone to produce substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and iso-butene, said process comprising:
    a) to introduce into a reactor a chain (A) comprising isobutanol, optionally water, optionally an inert component,
    b) contacting said chain with a catalyst in said reactor under conditions effective to dehydrate and isomerize the skeleton at least a portion of the isobutanol to produce a mixture of n-butenes and iso-butene,
    c) recovering from said reactor a chain (B), removing water, the inert component (if any) and uncovered isobutanol (if any) to obtain a mixture of n-butenes and iso-butene.
    The present invention (in a second embodiment) relates to a process for the simultaneous dehydration and isomerization of the isobutanol backbone to produce substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and iso-butene, said process comprising:
    a) to introduce into a reactor a chain (A) comprising isobutanol, optionally water, optionally an inert component,
    b) contacting said chain with a catalyst in said reactor under conditions effective to dehydrate and isomerize the skeleton, in at least a portion of the isobutanol to produce a mixture of n-butenes and iso-butene,
    c) recover from said reactor a chain (B), removing water, the inert component (if any) and uncovered isobutanol (if any) to obtain a mixture of n-butenes and iso-butene, where the temperature varies 200 ° C to 600 ° C and the catalyst is capable of simultaneously dehydrating and isomerizing the butene backbone.
    The catalyst, in both modalities, is a crystalline silicate of the group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, HONEY or TONNES having Si / AI higher than 10, or an unaluminated crystalline silicate of the group FER , MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si / AI higher than 10, or a modified phosphorous crystalline silicate from the FER, MWW, EUO, MFS, ZSM-48, MTT group, MFI, MEL or TON having Si / AI higher than 10, or a silicoaluminophosphate from the molecular sieve of the AEL group, or a silicate, zirconated or titanated or fluorinated aluminum.
    A preferred catalyst, in both modalities, is a crystalline silicate of the FER or MFI group having Si / AI higher than 10, or an unaluminated crystalline silicate of the FER or MFI group having Si / AI higher than 10, or a crystalline silicate. of modified phosphorus from the FER or MFI group having Si / AI higher than 10.
    In a specific modality the crystalline silicate of the FER, MWW, EUO group, the M of FS, ZSM-48, MTT, MFI, MEL or TON is vaporized to remove the aluminum from the structure of the
    6/19 crystalline silicate. The steam treatment is conducted at an elevated temperature, preferably in the range of 425 to 870 ° C, more preferably in the range of 540 to 815 ° C at atmospheric pressure and at a partial pressure of water between 13 to 200kPa. Preferably, the steam treatment is conducted in an atmosphere comprising from 5 to 100% steam. The steam atmosphere preferably contains 5 to 100% vol steam with 0 to 95% vol. of an inert gas, preferably nitrogen. A more preferred atmosphere is 72% vol. of steam and 28% vol. of nitrogen, that is, 72kPa of steam at atmospheric pressure. The steam treatment is preferably carried out for a period of 0.1 to 200 hours, more preferably of 0.5 hour to 100 hours. As determined above, steam treatment tends to reduce the amount of tetrahedral aluminum in the silicate's crystalline structure as well as improving the catalyst's resistance to regeneration. In a more specific modality, the crystalline silicate of the FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON group is de-aluminated by steam heating to remove the aluminum from the silicate crystalline structure and extract the aluminum from the catalyst contacting the catalyst with an acid or a complex agent to remove the aluminum from the aluminum pores of the structure deposited there during the vaporization step to thereby increase the atomic silicon / aluminum ratio of the catalyst. The catalyst having a high atomic silicone / aluminum ratio for use in the catalytic process of the present invention is produced by removing aluminum from a commercially available crystalline silicate. Consequently, following the vaporization step, the crystalline silicate is subjected to an extraction step in which amorphous aluminum is removed from the pores and the volume of the micropore is, at least in part, recovered. The physical removal, by a step of dissolving the amorphous aluminum from the pores by the formation of a water-soluble aluminum complex, produces a total de-illumination effect of the crystalline silicate. In this way, removing the aluminum from the crystalline structure of the silicate and then removing aluminum formed there from the pores, the process aims to perform a considerably homogeneous de-alumination by all the entire pore surfaces of the catalyst. This reduces the acidity of the catalyst. The acidity reduction occurs ideally homogeneously through all the pores defined in the crystalline structure of the silicate. Following the steam treatment, the extraction process is carried out in order to de-illuminate the catalyst through dissolution. Aluminum is preferably extracted from the crystalline silicate by a complex agent that tends to form a soluble complex with aluminum. The complex agent is preferably in an aqueous solution thereof. The complex agent may constitute an organic or inorganic acid such as citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, fumaric acid, nitrilotriacetic acid , hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, trichloroacetic acid, trifluoroacetic acid or a salt of such an acid (for example the sodium salt) or a mixture of
    7/19 two or more of such acids or salts. The acidic agent may constitute an inorganic acid such as nitric acid, halogenic acids, sulfuric acid, phosphoric acid or salts of such acids or a mixture of such acids. The complex agent can also constitute a mixture of such organic and inorganic acids or their corresponding salts. The aluminum complex agent preferably forms a water soluble complex with aluminum, and in particular removes aluminum which is formed during the steam treatment step of the crystalline silicate. A particularly preferred complex agent can be an amine, preferably ethylene diamino tetraacetic acid (EDTA) or a salt thereof, in particular the sodium salt thereof.
    Following the aluminum dissolution step, the crystalline silicate can then be washed, for example, with distilled water, and then dried, preferably at a high temperature, for example around 110 ° C.
    In addition, if, during the preparation of the catalysts of the invention, alkaline earth or alkali metals were used, the molecular sieve may be subjected to an ion exchange step. Conventionally, ion exchange is carried out in aqueous solutions using ammonium salts or inorganic acids.
    Following the de-alumination step, the catalyst is then calcined, for example, at a temperature of 400 to 800 ° C in atmospheric pressure for a period of 1 to 10 hours.
    Not departing from the scope of the invention, the raw material for isobutanol can consist of one or more other C4 alcohols such as 2-butanol, tertiobutanol and n-butanol. Advantageously, isobutanol is the important component among alcohols as a raw material, that is, the ratio of isobutanol to all C4 alcohols in the raw material is 42% or above. Most advantageously, the prior ratio is 70% or more and preferably 80% or more. Naturally, if the proportion of isobutanol is too low, the invention becomes of low interest, and there are many catalysts in the state of the art capable of dehydrating 2butanol and n-butanol to produce n-butenes.
    In an advantageous embodiment, the chain (B) is fractionated in a step d) to produce a chain of n-butenes (N) and remove the essential part of isobutene optionally recycled with the chain (A) to the dehydration / isomerization reactor of step b ). The recycling isobutene to the dehydration / isomerization reactor in step b) increases the production of n-butenes.
    In a specific embodiment, in the fractionation of step d), the iso-butene is removed by selective iso-butene oligomerization.
    In a specific embodiment, in the fractionation of step d) the iso-butene is removed by selective etherification with methanol or ethanol. In a specific modification in the fractionation of step d) the iso-butene is removed by selective hydration in t-butanol. Optionally said t-butanol is recycled to the step dehydration / isomerization reactor
    8/19
    B).
    In a specific embodiment, fractionation of step d) is done by a catalytic distillation column in which the essential part of 1-butene isomerized to 2-butene, isobutene is recovered as the upper part and 2-butene is recovered as the lower part of said column . Advantageously, the iso-butene is recycled to the dehydration / isomerization reactor in step b).
    DETAILED DESCRIPTION OF THE INVENTION
    With reference to chain (A), the isobutanol can be subjected to simultaneous dehydration and isomerization of the skeleton alone or in mixture with an inert medium. The inert component is any component supplied and is not substantially converted to the catalyst. Since the dehydration step is endothermic, the inert component can be used as an energy vector. The inert component allows to reduce the partial pressure of isobutanol and another intermediate reaction and therefore will reduce side reactions such as oligo / polymerization. The inert component can be selected from water, nitrogen, hydrogen, CO 2 and saturated hydrocarbons. It may be such that some inert components are already present in isobutanol because they were used or co-produced during the production of isobutanol. Examples of inert components that may already be present in isobutanol are water and CO 2 . The inert component can be selected from saturated hydrocarbons having up to 10 carbon atoms, Naphtene is advantageously a saturated hydrocarbon or a mixture of saturated hydrocarbons having from 3 to 7 carbon atoms, more advantageously having from 4 to 6 carbon atoms and is preferably pentane. An example of an inert component can be any individual saturated compound, a synthetic mixture of the individual saturated compounds as well as some balanced refinery streams such as simple naphtha, butanes etc. Advantageously, the inert component is a saturated hydrocarbon having 3 to 6 carbon atoms and is preferably pentane. The weight ratios of isobutanol and inert component are, for example, 30-100 / 70-0 (the total being 100). The stream (A) can be liquid or gaseous.
    With reference to the reactor, it can be a fixed bed reactor, a moving bed reactor or a fluidized bed reactor. A typical fluid bed reactor is one of the FCC type used for catalytic fluid bed breakdown at the oil refinery. A typical moving bed reactor is of the type of continuous catalytic reform. Simultaneous dehydration / isomerization can be performed continuously in a fixed bed reactor configuration using a pair of parallel scale reactors. The various preferred catalysts of the present invention have been found to exhibit high stability. This enables the dehydration process to be carried out continuously in two parallel scale reactors in which when one reactor operates, the other reactor undergoes catalyst regeneration. The catalyst for this
    9/19 invention can also be regenerated several times.
    Simultaneous dehydration / isomerization can be carried out continuously in a moving bed reactor in which the catalyst circulates from a reaction zone to a regeneration zone backwards with a residence time of the catalyst in the reaction zone of at least 12 hours. In each zone, the catalyst behaves substantially as in a fixed bed reactor, but the catalyst moves slowly, by gravity or pneumatically through the respective zone. The use of a moving bed reactor allows continuous operation with no exchange of raw material and regeneration gas from one reactor to another. The reaction zone continuously receives the raw material while the regeneration zone continuously receives the regeneration gas.
    Simultaneous dehydration / isomerization can be performed continuously in a fluidized bed reactor in which the catalyst circulates from a reaction zone to a regeneration zone and backwards with a residence time of the catalyst in the reaction zone of less than 12 hours . In each zone the catalyst is in a fluidized state and exhibits such a shape and size that it remains fluidized in the flow of raw material and reaction products or regeneration gas. The use of a bed-bed reactor allows the catalyst deactivated by regeneration in the regeneration zone to be regenerated very quickly.
    With reference to pressure, it can be any pressure, but it is easier and more economical to operate at moderate pressure. For example, the pressure of the reactor varies from 0.5 to 10 bars absolute (50 kPa to 1 MPa), advantageously from 0.5 to 5 bars absolute (50 kPa to 0.5 MPa), more advantageously from 1, 2 to 5 bars absolute (0.12 MPa to 0.5 MPa) and preferably 1.2 to 4 bars absolute (0.12 MPa to 0.4 MPa). Advantageously, the partial pressure of isobutanol is 0.1 to 4 bars absolute (0.01 MPa to 0.4 MPa), more advantageously from 0.5 to 3.5 bars absolute (0.05 MPa to 0.35 MPa ).
    With reference to temperature, and the first modality that varies from 200 ° C to 600 ° C, advantageously from 250 ° C to 500 ° C, more advantageously from 300 ° C to 450 ° C. With reference to temperature and the second modality varies from 200 ° C to 600 ° C, advantageously from 250 ° C to 500 ° C, more advantageously from 300 ° C to 450 ° C.
    These reaction temperatures refer considerably to the average catalyst bed temperature. Dehydration of isobutanol is an endothermic reaction and requires the input of heat from the reaction to keep the catalyst activity high enough and changes the dehydration thermodynamic balance to sufficiently high levels of conversion.
    In the case of fluidized bed reactors: (i) for stationary fluidized beds without catalyst circulation, the reaction temperature is considerably homogeneous throughout the catalyst bed; (ii) in the case of circulating fluidized beds where the catalyst circulates between a reaction conversion section and a regeneration section of the
    10/19 catalyst, depending on the degree of reflux mixing of the catalyst, the catalyst bed temperature approaches homogeneous conditions (a lot of reflux mixing) or approaches buffer flow conditions (almost no reflux mixing) and therefore a decreasing temperature profile will install itself as the conversion proceeds.
    In the case of fixed bed or moving bed reactors, a decreasing temperature profile will be installed as the conversion of isobutanol proceeds. To compensate for the temperature drop and consequently decrease the catalyst activity or approach the thermodynamic equilibrium, the heat of reaction can be introduced using several catalyst beds in series with internal heating of the effluent from the first bed reactor to higher temperatures and introduce the effluent heated in a second catalyst bed, etc. When fixed bed reactors are used, a multi-tubular reactor can be used where the catalyst is loaded into small diameter tubes that are installed in a reactor structure. On the side of the structure, a heating medium is introduced that supplies the necessary heat of reaction by transferring heat through the wall of the reactor tubes to the catalyst.
    With reference to the WHSV of isobutanol, and the first embodiment, it advantageously ranges from 1 to 30 h ' 1 , preferably from 2 to 21 h' 1 , more preferably from 7 to 12 h ' 1 . With reference to the second embodiment, it advantageously ranges from 1 to 30 h ' 1 , more advantageously from 2 to 21 h' 1 , preferably from 5 to 15 h ' 1 , more preferably from 7 to 12 h' 1 .
    With reference to chain (B), it essentially constitutes water, olefin, the inert component (if any) and uncovered isobutanol. Said discovered isobutanol is supposed to be as small as possible. The olefin is recovered by normal fractionation means. Advantageously, the inert component, if any, is recycled in chain (A) as well as the discovered isobutanol, if any. The discovered isobutanol, if any, is recycled to the reactor in chain (A). Advantageously among butenes, the proportion of n-butenes is above 20%, advantageously above 30%, more advantageously above 40%, preferably above 50%.
    With reference to the catalyst, it is a crystalline silicate of the FER group (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, UE -1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-11) or TON (ZSM-22, Theta-1, NU-10) , or a de-illuminated crystalline silicate of the FER group (ferrierite, FU-9, ZSM-35), MWW (MCM22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, UE-1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-1 1) or TON (ZSM-22, Theta-1, NU-10), or a silicate phosphorus modified crystalline group FER (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-11) or TON (ZSM-22, Theta-1, NU-10), or a molecular sieve
    11/19 AEL group silicoaluminophosphate (SAPO-1 1), or a silicate, zirconated or titanated or fluorinated aluminum.
    On the FER structure crystalline silicate (ferrierite, FU-9, ZSM-35) it can be the lamellar precursor that becomes FER by calcination.
    The Si / AI ratio is advantageously higher than 10.
    Crystalline silicate is such as the Si / AI ratio scales most advantageously from 10 to 500, preferably from 12 to 250, more preferably from 15 to 150.
    The acidity of the catalyst can be determined by the amount of residual ammonia in the next contact of the catalyst catalyst with ammonia that adsorbs in the acidic sites of the catalyst with subsequent ammonia desorption at high temperature measured by thermogravimetric differential analysis or analysis of ammonia concentration in the desorbed gases .
    Crystalline silicate can be subjected to various treatments prior to use in dehydration including, ion exchange, modification with metals (in a non-restrictive manner, alkaline earth elements, transition, or rare earths), external surface passivation, modification with P compounds , vaporization, acid treatment or other methods of de-alumination, or combination thereof.
    In a specific embodiment, the crystalline silicate is vaporized to remove the aluminum from the crystalline structure of the silicate. The steam treatment is conducted at a high temperature, preferably in the range of 425 to 870 ° C, more preferably in the range of 540 to 815 ° C and in atmospheric pressure and in a water partial pressure of 13 to 200kPa. Preferably, the steam treatment is conducted in an atmosphere consisting of 5 to 100% vol. of steam. The steam atmosphere preferably contains from 5 to 100% vol. of steam with 0 to 95% vol. of an inert gas, preferably nitrogen. The steam treatment is preferably carried out for a period of 1 to 200 hours, more preferably 4 hours to 10 hours. As determined above, steam treatment tends to reduce the amount of tetrahedral aluminum in the silicate's crystalline structure, forming aluminum.
    In a more specific embodiment, the crystalline silicate is de-illuminated by heating the catalyst in steam to remove the aluminum from the crystalline structure of the silicate and extract the aluminum from the catalyst by contacting the catalyst with a complex aluminum agent to remove the pores of the aluminum from the structure deposited there during the vaporization step thus increasing the atomic silicon / aluminum ratio of the catalyst. According to the present invention, crystalline silicate is commercially available modified by a vaporization process that reduces the tetrahedral aluminum in the crystalline structure of the silicate and converts the aluminum atoms into octahedral aluminum in the form of amorphous aluminum. Although in the vaporization stage the aluminum atoms are chemically removed from the crystalline structure of the silicate structure to form aluminum particles, these particles cause partial obstruction of the pores or channels in the structure. This can prevent
    12/19 dehydration process of the present invention. Consequently, following the vaporization step, the crystalline silicate is subjected to an extraction step where amorphous aluminum is removed from the pores and the volume of the micropore is, at least in part, recovered. The physical removal, by a step of dissolving the amorphous aluminum from the pores by the formation of a water-soluble aluminum complex, results in the total de-alumination effect of the crystalline silicate. In this way, removing the aluminum from the crystalline silicate structure and then removing an aluminum formed from there of the pores, the process aims to achieve a considerably homogeneous de-alumination for all the pore surfaces of the catalyst. This reduces the acidity of the catalyst. The acidity reduction occurs ideally considerably homogeneously through all the pores defined in the crystalline silicate structure. The following vaporization treatment, the extraction process is carried out in order to de-aluminum the catalyst through dissolution. Aluminum is preferably extracted from the crystalline silicate by a complex agent that tends to form a soluble complex with aluminum. The complex agent is preferably in an aqueous solution thereof. The complex agent may constitute an organic acid such as citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, fumaric acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, trichloroacetic acid, trifluoroacetic acid or a salt of such an acid (for example the sodium salt) or a mixture of two or more of such acids or salts. The complex agent can constitute an inorganic acid such as nitric acid, halogenic acids, sulfuric acid, phosphoric acid or salts of such acids or a mixture of such acids. The complex agent can also constitute a mixture of such organic and inorganic acids or their corresponding salts. The complex agent for aluminum preferably forms a water-soluble complex with aluminum, and in particular removes aluminum which is formed during the steam treatment step of the crystalline silicate.
    Following the aluminum dissolution step, the crystalline silicate can therefore be washed, for example, with distilled water, and then dried, preferably at a high temperature, for example, around 110 ° C.
    Additionally, if during the preparation of the catalysts of the invention, alkaline earth or alkali metals are used, the molecular sieve may be subjected to an ion exchange step. Conventionally, ion exchange is done in aqueous solutions using ammonium salts or inorganic acids.
    Following the de-illumination step, the catalyst is then calcined, for example, at a temperature of 400 to 800 ° C in atmospheric pressure for a period of 1 to 10 hours.
    Another convenient catalyst for the present process is the molecular sieve of silicoaluminophosphate from the AEL group with a typical example the SAPO-11 molecular sieve. O
    13/19 SAPO-11 molecular sieve is based on ALPO-11, essentially having an Al / P ratio of 1 atom / atom. During synthesis, the silicone precursor is added and the insertion of silicone into the ALPO structure results in an acidic spot on the surface of the 10-membered ring sieve micropores. The silicone content ranges from 0.1 to 10% atom (Al + P + Si is 100).
    In another specific embodiment, the crystalline silicate or silicoaluminophosphate molecular sieve is mixed with a binder, preferably an inorganic binder, and formed with a desired shape, for example, pellets. The binder is selected in order to be resistant to temperature and other conditions employed in the dehydration process of the invention. The binder is an inorganic material selected from clays, silica, metal silicates, metal oxides such as Zr0 2 and / or metals, or gels including mixtures of silica and metal oxides. If the binder that is used in conjunction with the crystalline silicate is catalytically active, this can alter and / or convert the selectivity of the catalyst. Inactive materials for the binder can adequately serve as diluents to control the amount of conversion so that the products can be obtained economically and in order without using other means to control the reaction rate. It is desirable to provide a catalyst having a good grinding force. This is because in commercial use, it is desirable to prevent the catalyst from breaking down into powder-like materials. Such clay or oxide binders were normally used only to improve the grinding strength of the catalyst. A particularly preferred binder for the catalyst of the present invention is silica. The relative proportions of the precisely divided silicate crystalline material and the inorganic matrix of the binder oxide can vary widely. Generally, the content of the binder ranges from 5 to 95% by weight, more generally from 20 to 75% by weight, based on the weight of the catalyst compound. Such a mixture of crystalline silicate and an inorganic oxide binder is referred to as a formulated crystalline silicate. When mixing the catalyst with a binder, the catalyst can be formulated into pellets, pressed in other forms, or formed into spheres or a spray dried powder. Generally, the binder and crystalline silicate are mixed together by a stirring process. In such a process, the binder, for example, silica, in the form of a gel is mixed with the crystalline silicate material and the resulting mixture is pressed into the desired shape, for example, cylindrical or multi-lobe bars. Spherical shapes can be made by rotating granulators or by oil drip technique. Small spheres can also be made by spray drying a suspension of the catalyst-binder. After that, the formulated crystalline silicate is calcined in air or an inert gas, usually at a temperature of 200 to 900 ° C for a period of 1 to 48 hours.
    In addition, mixing the catalyst with the binder can be carried out before or after vaporization and extraction steps.
    14/19
    Another family of catalysts suitable for simultaneous dehydration and isomerization of the skeleton are aluminum which have been modified by surface treatment with silicone, zirconium or titanium. Aluminum is generally characterized by a fairly wide acid strength distribution and having both Lewis Type and Bronsted Type acid sites. The presence of a wide acidic force distribution catalyzes various reactions, requiring a different, possible acidic force. This usually results in low selectivity for the desired product. The deposition of silicone, zirconium or titanium on the aluminum surface makes the catalyst significantly more selective. For the preparation of the aluminum-based catalyst, convenient commercial aluminum can be used, preferably beta aluminum or gamma aluminum, having a surface area of 10 to 500 m 2 / gram and an alkaline content of less than 0.5%. The catalyst according to the present invention is prepared by adding 0.05 to 10% silicone, zirconium or titanium. The addition of these metals can be done during the preparation of the aluminum or can be added to the existing aluminum, possibly already activated. The addition of the metal during the preparation of the aluminum can be done by dissolving the metal precursor together with the aluminum precursor before the precipitation of the final aluminum or by adding the metal precursor to the aluminum hydroxide gel. A preferred method adds metal precursors to the formed aluminum. The metal precursors are dissolved in a suitable solvent, aqueous or organic, and contacted with the aluminum by incipient impregnation of moisture or by wet impregnation or by contacting an excess solute for a certain time, followed by removing the excess solute. Aluminum can also be contacted with steam from the metal precursor. Convenient metal precursors are silicon, zirconium or titanium halides, zirconium or titanium oxyhalides; silicon, zirconium or titanium alkoxides; zirconium or titanium oxalates or citrates or mixtures of the above. The solvent is selected according to the solubility of the metal precursor. The contact can be made at a temperature of 0 ° C to 500 ° C, more preferred from 10 ° C to 200 ° C. After contact, the aluminum is eventually washed, dried and finally calcined in another to improve the surface reaction between silicon, zirconium or titanium and aluminum and the removal of binders from the metal precursor. The use of silicate, zirconated or titanated or fluorinated aluminum for simultaneous dehydration and isomerization of the isobutanol backbone is preferably done in the presence of water. The weight ratio of water to isobutanol ranges from 1/25 to 3/1. Fluorinated aluminum is known properly and can be made according to the state of the art.
    With reference to the use of the product, the mixture of n-butenes and iso-butene can replace the use of raffinate I in the refinery or plant petrochemical product. Fig. 1 shows the main applications of n-butenes and isobutene. The most typical application of such a mixture is
    15/19 conversion of the iso-butene contained in ether (MTBE and ETBE), in t-butyl alcohol (TBA) or oligomers (for example, di / tri-iso-butenes), all being components of gasoline. The higher iso-butene oligomers can be used for jet fuel applications. High purity iso-butene can also be done by decomposing ether (backcracking) or TBA (dehydration). High purity iso-butene finds applications in the production of Butyl Rubber, Plastic-isobutene, Methylmethacrylate, Isoprene, Hydrocarbon resins, t-Butylamine, Alkyl-phenols and t-butyl-mercaptan.
    N-butenes, having not reacted during the production of ether or TBA and considerably not only to a limited extent during oligomerization, have applications in the production of sec-butanol, alkylate (addition of isobutane to butenes), Poligasolina, Oxo- Alcohols and Propylene (metathesis with ethylene or auto-metathesis between but-1ene and but-2-ene). By means of superfractionation or extractive distillation or separation by absorption, but-1 -ene can be isolated from the mixture of n-butenes. But-1 -eno is used as a comonomer for the production of polyethylenes, for poly-but-1 -ene and n-butylmercaptan.
    n-Butenes can also be separated from iso-butene by means of catalytic distillation. This involves an isomerization catalyst that is located in the distillation column and continuously converts but-1-ene to but-2-ene, being a heavier component than but-1-ene. In doing so, a low product rich in but-2-ene and superior product poor in but-1-ene and rich in iso-butene is produced. The inferior product can be used as described above. A major application of such a but-2-ene-rich stream is metathesis with ethylene to produce propylene. If iso-butene of high purity is desired the superior product can be superfractionated into considerably pure iso-butene and pure but-1 -ene or iso-butene can be isolated through the formation of ether or TBA which is therefore decomposed into iso- pure butene.
    The corerents rich in n-butenes can be used for the production of butadiene through dehydrogenation or oxidative dehydrogenation.
    The mixture of isobutene and butenes can be conducted to a catalytic break that is selective towards the light olefins in the effluent, the process constituting to contact said isobutene and mixture of butenes with an appropriate catalyst to produce an effluent with a weight olefin content lower molecular weight than raw material. Said break catalyst can be a silicalite (MFI or type of MEL) or a P-ZSM5. EXAMPLES
    Experimental:
    The stainless steel ballast tube has an internal diameter of 10mm. 10ml of catalyst, like 35-45 mesh pellets, is loaded into the tubular reactor. The empty spaces before and after the catalyst is filled with 2 mm SiC granules. The profile of
    16/19 temperature is controlled with the help of a thermocouple well placed inside the reactor. The reactor temperature is increased by 60 ° C / h to 550 ° C in air, kept for 2 hours at 550 ° C and then purified by nitrogen. The nitrogen is then replaced by the feed under the indicated operating conditions. The catalytic tests are carried out by low flow, at 1.5 and 2.0 bar, on a temperature scale of 280-380 ° C and with a velocity in space weight hour (WHSV) ranging from 7 to 21 h ' 1 .
    Product analysis is performed using gas chromatography.
    Example 1 (according to the invention)
    The catalyst used here is a crystalline silicate of the FER structure. H-FER having a Si / AI of 33 in the form of powder. The catalyst is calcined with air at 550 ° C for 4 hours before formulation in 35-45 mesh pellets.
    An isobutanol / water mixture having a composition of 95/5% by weight was processed on a catalyst under 2 bar, at temperatures between 350 and 375 ° C, and with a spatial velocity of isobutanol from 7 to 21 h ' 1 .
    In this set of operating conditions, the conversion of isobutanol is almost complete, with a selectivity of butenes greater than 95% by weight, and an isobutene selectivity of around 41-43%. Small amounts of C compounds are formed.
    FEED iButOH / H 2 0 (95/5)% by weight P (bar) 2 2 2 2 2 T (° C) 350.0 350.0 350.0 375.0 375.0 WHSV (H-1) 7.3 12.6 21.0 21.0 12.6 Conversion (% weight CH2) 100.0 99.4 89.7 99.8 99.2 Oxygen base C (% weight CH 2 ) - average Ether 0.0 0.0 0.0 0.0 0.0 Other alcohol 0.1 0.1 0.2 0.1 0.1 Aldehyde + Ketone 0.1 0.1 0.1 0.1 0.1 Yield on base C (% weight CH 2 ) - average Paraffins 1.0 0.4 0.2 0.4 0.4 C2 = 0.8 0.5 0.3 0.7 0.4 C3 = 0.2 0.1 0.0 0.1 0.1 C4 = 95.9 97.4 88.7 97.8 97.5 C5 + olef 1.4 0.6 0.3 0.5 0.5 Dienos 0.4 0.2 0.0 0.1 0.1 Aromatic 0.1 0.0 0.0 0.0 0.0 unknown 0.1 0.0 0.0 0.0 0.0 Base C selectivity (% weight CH2) - average
    17/19
    Paraffins 1, the 0.4 0.2 0.4 0.4 C2 = 0.8 0.5 0.3 0.7 0.4 C3 = 0.2 0.1 0.0 0.1 0.1 C4 = 95.9 98.0 98.8 97.9 98.3 C5 + olef 1.4 0.6 0.3 0.5 0.5 Dienos 0.4 0.2 0.0 0.1 0.1 Aromatic 0.1 the, the 0.0 0.0 0.0 unknown 0.1 the, the 0.0 0.0 0.0 C4 = distribution (% weight CH2) i-C4 = 43.4 42.2 42.4 42.2 41.6 n-C4 = 56.6 57.8 57.6 57.8 58.4 t-2-C4 = 27.0 27.7 27.9 27.0 28.0 C-2-C4- 18.4 18.7 18.6 18.7 18.9 1-C4 = 11.2 11.4 11.1 12.1 11.5
    Comparative Example 2:
    The catalyst is made of gamma aluminum with the form of a Sasol® cylinder formulated. The catalyst has a specific surface of 182 m 2 / g and a porous volume of 0.481 5 ml / g. The impurities present in aluminum in small quantities are summarized below:
    0.25% Si weight; 0.02% weight of P; 0.02% fe weight, 29 ppm Na.
    An isobutanol / water mixture having 95/5% by weight of composition was processed in the catalyst under 2 bar, at temperatures between 350 and 380 ° C, and with a spatial speed of 7 to 12h ' 1 .
    In this set of operating conditions, the conversion of isobutanol is almost complete, with a selectivity of butenes greater than 98% by weight, and an isobutene selectivity of around 90-94%. Thus, very low amounts of n-butenes are produced on this catalyst. Low amounts of C 5 + compounds are formed.
    FEED iButOH / H 2 0 (95/5)% by weight P (bar) 2 2 2 2 T (° C) 380.0 350.0 350.0 325.0 WHSV (H-1) 12.4 7.4 12.4 7.4 Conversion (% weight CH2) 99.98 99.96 99.93 99.85 C-based oxygen % weight CH 2 ) - average Other Oxygenates 0.0 0.0 0.0 0.0 Other alcohol 0.0 o, 1 0.1 o, 1 Base C selectivity (% weight CH2) - average Paraffins 0.3 0.3 0.1 0.3
    18/19
    C2 = 0.3 0.2 0.2 0.1 C3 = 0.2 0.1 0.0 0.0 C4 = 98.2 98.6 99.1 98.6 C5 + olef 0.7 0.5 o, 1 0.3 Dienos 0.1 0.0 0.0 0.1 Aromatic 0.0 0.0 0.0 0.0 Unknown 0.1 0.1 0.3 0.4 C4 = distribution (% weight CH2) iC4 = 90.2 92.5 92.7 94.0 t-2-C4 = 3.0 1.8 1.4 1.2 C-2-C4- 3.9 3.2 3.3 2.7 1-C4 = 2.9 2.5 2.6 2.1 n-c4 = 9.8 7.5 7.3 6.0
    Example 3 (according to the invention)
    The catalyst is a modified phosphorus zeolite (P-ZSM5), prepared according to the following recipe. A sample of ZSM-5 zeolite (Si / AI = 13) in the form was vaporized at 550 ° C for 6h in 100% H 2 0. The vaporized solid was subjected to contact with the aqueous solution of H3PO4 (85% by weight) for 2h under reflux condition (4ml / 1g zeolite). Then 69.9 g of CaCO 3 were introduced while maintaining a pH of 2.52. Then, the solution was evaporated dry for 3 days at 80 ° C. 750g of the dry sample was extruded with 401.5g of Bindzil and 0.01% by weight of extrusion additives. The extruded solid was dried at 110 ° C for 16h and calcined at 600 ° C for 10h.
    An isobutanol / water mixture having 95/5% by weight of the composition was processed on the catalyst under 1.5 bar, at temperatures between 280 and 350 ° C, and with a spatial isobutanol speed of approximately 7h ' 1 .
    In this set of operating conditions, the conversion of isobutanol is almost complete, with a selectivity of butenes of more than 90% by weight, and an selectivity of iso-butene of approximately 66-67%. Thus, approximately 90% or more butenes are produced, of which a significant amount is skeletally isomerized into n-butenes. The largest production is limited to 10% or less.
    Power: i-But0H / H20 (95/5)% weight
    P (baraj 1.5 1.5 T (° C) 300 280 WHSV (H-1) 7.4 7.4 Conversion (% weight CH2) 100.0 83.5 Oxygenates (% weight CH2) - Medium Other alcohols 0.01 0.00
    19/19
    Other Oxygenates 0.03 0.08 Base C selectivity (% weight CH2) - Average Paraffins C1-C4 0.1 0.1 C2 = 0.0 0.0 C3 = 0.5 0.3 C4 = 89.9 93.9 i-Butene 60.3 61.9 1-Butene 5.0 6.1 2-Butene 24.6 26.0 C5 + olef 4.8 2.7 C5 + paraf 1.9 1.1 Dienos 0.5 0.4 Aromatic 0.5 0.2 Unknown 1.6 1.1 C4 = distribution - Average i-Butene 67.1 65.9 n-butenes 32.9 34.1 1-Butene 5.5 6.5 2-Butene 27.4 27.7
    1/3
    权利要求:
    Claims (18)
    [1]
    1. Simultaneous dehydration process and isomerization of the isobutanol backbone to produce substantially corresponding olefins, having the same number of carbon and composed essentially of a mixture of n-butenes and iso-butene, said process comprising:
    a) to introduce a chain reactor (A) comprising isobutanol, optionally water, optionally an inert component,
    b) contacting said chain with a catalyst in said reactor under conditions effective to dehydrate and isomerize the skeleton at least a portion of the isobutanol to produce a mixture of n-butenes and iso-butene,
    c) recover from said reactor a chain (B), removing water, the inert component (if any) and uncovered isobutanol (if any) to obtain a mixture of n-butenes and iso-butene, in which, the WHSV of the isobutanol is at least 1h 1 and the catalyst is capable of simultaneously performing the dehydration and isomerization of the butene backbone and is a crystalline silicate of the FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON group Si / AI higher than 10, or an unaluminated crystalline silicate from the FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON group having Si / AI higher than 10, or a modified phosphorous silicate group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si / AI higher than 10, or a molecular sieve silicoaluminophosphate group AEL, or a silicate, zirconated or titanated or fluoride aluminum .
    [2]
    Process according to claim 1, characterized in that the WHSV of the isobutanol is from 1 to 30 h 1 .
    [3]
    Process according to claim 2, characterized in that the WHSV of the isobutanol is from 2 to 21 h 1 .
    [4]
    4. Simultaneous dehydration process and isomerization of the isobutanol backbone to produce substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and iso-butene, said process characterized by comprising:
    a) introducing into a reactor a chain (A) comprising isobutanol, optionally water, optionally an inert component,
    b) contacting said chain with a catalyst in said reactor under conditions effective to dehydrate and isomerize the skeleton, in at least a portion of the isobutanol to produce a mixture of n-butenes and iso-butene,
    c) recover from said reactor a chain (B), removing water, the inert component (if any) and uncovered isobutanol (if any) to obtain a mixture of n-butenes and iso-butene, where the temperature varies between 200 ° C and 600 ° C and the catalyst is capable of simultaneously dehydrating and isomerizing the butene backbone and is a
    2/3 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON crystalline silicate having Si / AI higher than 10, or an unaluminated crystalline silicate from FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si / AI higher than 10, or a modified phosphorous crystalline silicate from the group FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON having Si / AI higher than 10, or a molecular sieve silicoaluminophosphate of the AEL group, or a silicate, zirconated or titanated or fluorinated aluminum.
    [5]
    Process according to any one of claims 1 to 4, characterized in that the reactor pressure varies between 0.5 to 10 bars absolute.
    [6]
    Process according to any one of claims 1 to 5, characterized in that the temperature varies from 250 ° C to 500 ° C.
    [7]
    Process according to claim 6, characterized in that the temperature varies between 300 ° 0 to 450 ° C.
    [8]
    Process according to any one of claims 1 to 7, characterized in that the chain (B) is fractionated in a step d) to produce a chain of n-butenes (N) and remove the essential part of the optionally recycled isobutene with the chain (A) for the dehydration / isomerization reactor in step b).
    [9]
    Process according to claim 8, characterized in that in the fractionation of step d) the iso-butene is removed by selective iso-butene oligomerization.
    [10]
    Process according to claim 8, characterized in that in the fractionation of step d) the iso-butene is removed by selective etherification with methanol or ethanol.
    [11]
    Process according to claim 8, characterized in that in the fractionation of step d) the iso-butene is removed by selective hydration in t-butanol.
    [12]
    Process according to claim 11, characterized in that said t-butanol is recycled to the dehydration / isomerization reactor of step b).
    [13]
    Process according to claim 8, characterized in that the fractionation of step d) is carried out by a catalytic distillation column in which the essential part of 1 butene is isomerized to 2-butene, the iso-butene is recovered as the part upper and 2butene is recovered at the bottom of said column.
    [14]
    Process according to claim 13, characterized in that the iso-butene is recycled to the dehydration / isomerization reactor of step b).
    [15]
    Process according to any one of the preceding claims, characterized in that the proportion of n-butenes among the butenes produced in step c) is above 20%.
    [16]
    Process according to claim 15, characterized in that the proportion of n-butenes among the butenes produced in step c) is above 30%.
    [17]
    Process according to claim 16, characterized in that the proportion of n-butenes among the butenes produced in step c) is above 40%.
    3/3
    [18]
    Process according to claim 17, characterized in that the proportion of n-butenes among the butenes produced in step c) is above 50%.
    1/1
    Main applications of C4
    SBR; styrene-butadiene rubber PB: Poé & üíadfeno NSR: nfírite-butadiene rubber SSS / SEBS: es-irero-huiabíer.o-ssjsfano
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    同族专利:
    公开号 | 公开日
    EP2547638A1|2013-01-23|
    JP2013522270A|2013-06-13|
    MY158968A|2016-11-30|
    JP5784646B2|2015-09-24|
    EP2547638B1|2016-08-17|
    ES2603029T3|2017-02-23|
    CA2791218C|2014-11-25|
    CA2791218A1|2011-09-22|
    PL2547638T3|2017-02-28|
    US20130204057A1|2013-08-08|
    KR101544257B1|2015-08-12|
    WO2011113834A1|2011-09-22|
    AR080756A1|2012-05-09|
    EA201270737A1|2013-02-28|
    CN102892729A|2013-01-23|
    DK2547638T3|2016-12-12|
    CO6602154A2|2013-01-18|
    EA025806B1|2017-01-30|
    KR20120128685A|2012-11-27|
    US9233886B2|2016-01-12|
    PE20130759A1|2013-06-21|
    CN102892729B|2015-08-05|
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    法律状态:
    2018-04-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-06-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|
    2020-01-07| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |
    2020-08-25| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: REFERENTE AO DESPACHO 21.6 PUBLICADO NA RPI 2557 DE 2020-01-07 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10156537.2|2010-03-15|
    EP10156537A|EP2366682A1|2010-03-15|2010-03-15|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|
    EP10159463A|EP2374781A1|2010-04-09|2010-04-09|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|
    EP10159463.8|2010-04-09|
    EP10161125|2010-04-27|
    EP10161125.9|2010-04-27|
    PCT/EP2011/053902|WO2011113834A1|2010-03-15|2011-03-15|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|
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