propylene production by dehydration and simultaneous isomerization of the isobutanol backbone over a

专利摘要:
propylene production through dehydration and simultaneous isomerization of the isobutanol backbone over acid catalysts followed by metathesis. The present invention relates to a process for the production of propylene where, in a first step, isobutanol is subjected to dehydration and isomerization of the skeleton simultaneously to the production of essentially corresponding olefins having the same number of carbons and consisting essentially of in a mixture of n-butenes and isobutane and where, in a second step, the n-butenes are metathesised, which process comprises: a) introducing into a reactor a stream (a) comprising isobutanol, optionally water, optionally a inert component, b) contacting said stream with a catalyst in said reactor under conditions effective to dehydrate and isomerize the backbone of at least one isobutanol moiety to produce a mixture of n-butenes and isobutene, c) recover from said reactor, a stream (b), remove water, the inert component, if any, and unprocessed isobutanol, if present, to obtain a mixture d) fractionating said mixture to produce a stream of n-butenes (n) and to remove the essential part of isobutene optionally recycled with stream (a) to the dehydration / isomerization reactor of step (b, e) transferring the stream (n) to a metathesis reactor and contacting the stream (n) with a catalyst in said metathesis reactor, optionally in the presence of ethylene, under conditions effective to produce propylene, f) recovering, from said metathesis reactor, a stream (p) containing essentially propylene, unreacted n-butenes, heavy hydrocarbons, optionally unreacted ethylene, g) fractionate the stream (p) to recover propylene and optionally recycle unreacted n-butenes and unreacted ethylene for the metathesis reactor.
公开号:BR112012023261B1
申请号:R112012023261
申请日:2011-03-15
公开日:2018-09-18
发明作者:Adam Cindy；Minoux Delphine；Vermeiren Walter
申请人:Total Res & Technology Feluy；
IPC主号:

专利说明:

(54) Title: PROPYLENE PRODUCTION THROUGH DEHYDRATION AND SIMULTANEOUS ISOMERIZATION OF THE ISOBUTANOL SKELETON ON ACID CATALYSTS FOLLOWED WITH METATHESIS (51) Int.CI .: C07C 1/24; C07C 11/00; C07C 11/08; C07C 9/11; B01J 29/06; B01J 29/40; B01J 29/85; C07C 6/04; C07C 11/06 (30) Unionist Priority: 09/04/2010 EP 10159461.2, 09/04/2010 EP 10159463.8, 03/15/2010 EP 10156537.2, 23/04/2010 EP 10160840.4, 27/04/2010 EP 10161125.9 ( 73) Holder (s): TOTAL RESEARCH & TECHNOLOGY FELUY (72) Inventor (s): WALTER VERMEIREN; CINDY ADAM; DELPHINE MINOUX (85) National Phase Start Date: 14/09/2012
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Descriptive Report of the Invention Patent for: “PRODUCTION OF PROPYLENE THROUGH DEHYDRATION AND SIMULTANEOUS ISOMERIZATION OF THE ISOBUTANOL SKELETON ON ACID CATALYSTS FOLLOWED BY METATHESIS”.
[Invention area]
The present invention relates to the production of propylene through simultaneous dehydration and isomerization of the isobutanol backbone to produce a corresponding olefin, having essentially the same number of carbons but a different backbone structure, which is followed by a metathesis step. The limited supply and rising cost of crude oil has prompted the search for alternative processes for the production of hydrocarbon products such as propylene. It is possible to obtain isobutanol through fermentation of carbohydrates or through condensation of lighter alcohols, obtained through fermentation of carbohydrates. Being made up of organic matter from living organisms, biomass is the main renewable energy source worldwide.
[Background of the Invention]
Isobutanol (2-methyl-1-propanol) has had limited applications in historical terms and its use is similar to that of 1-butanol. It was used as a solvent, diluent, humidifier, cleaning additive and additive for paints and polymers. Recently, isobutanol has gained interest as a fuel and fuel component because it has a high octane number (Blend Octane R + M / 2 is 102-103) and a low vapor pressure (RPV is 3.8-5.2 psi).
Often isobutanol is considered a byproduct of industrial production of 1-butanol (Ullmann's Encyclopedia of Industrial Chemistry, 6. edition, 2002). It is produced from propylene through hydroformylation in the oxo process (Rh based catalyst) or through carbonylation in the Reppe process (Co based catalyst). Hydroformylation or carbonylation produces n-butanal and isobutanal in ratios from 92/8 to 75/25. To obtain isobutanol, the isobutanal is hydrogenated with a metallic catalyst. It is also possible to produce isobutanol from synthesis gas (mixture of CO, H ₂ and CO ₂ ) through a process similar to Fischer-Tropsch, resulting in a mixture of higher molecular weight alcohols, although preferential formation often occurs of isobutanol (Applied Catalysis A, general, 186, p. 407, 1999 and Chemiker Zeitung, 106, p. 249, 1982). Yet another way to obtain isobutanol is Guerbet's condensation of alkaline methanol catalysis with ethanol and / or propanol (J. of Molecular Catalysis A: Chemical 200, 137, 2003 and Applied Biochemistry and Biotechnology, 113-116, p. 913, 2004).
Recently, new biochemical pathways have been developed to selectively produce isobutanol from carbohydrates. The new strategy uses the highly active amino acid biosynthesis pathway of microorganisms and diverts their intermediates from the 22/29 keto acid for alcohol synthesis. 2-keto acids are intermediates in the amino acid biosynthesis pathways. These metabolites can be transformed into aldehydes through 2-keto acid decarboxylases (KDC) and then into alcohols through alcohol dehydrogenases (ADH). Two non-native steps are required to produce alcohols through derivatives of amino acid biosynthesis pathways for the production of alcohol (Nature, 451, p. 86, 2008 and US patent 2008/0261230). It is necessary that recombinant microorganisms increase the flow of carbon towards the synthesis of 2 keto acids. In valine biosynthesis, 2-ketoisovalerate is an intermediate. The glycolysis of carbohydrates results in pyruvate which is converted to acetolactate through acetolactate synthase. 2,4-dihydroxy-isovalerate is formed from acetolactate, is catalyzed through the isomer reductase. A dehydratase transforms 2,4-dihydroxyisovalerate into 2-ketoisovalerate. In the next step, a keto acid decarboxylase produces isobutyralaldehyde from 2-ketoisovalerate. The last step is the hydrogenation of isobutyroaldehyde, through a dehydrogenase, in isobutanol.
Of the routes described towards isobutanol, Guerbet condensation, hydrogenation of synthesis gas and the 2-acetoacid route from carbohydrates are routes that can use biomass as the main raw material. Gasification of biomass results in synthesis gas that can be transformed into methanol or directly into isobutanol. Ethanol is already produced on a huge scale through fermentation of carbohydrates or through direct fermentation of synthesis gas in ethanol. Thus, methanol and ethanol produced from biomass can be further condensed to isobutanol. The direct 2-keto acid pathway is able to produce isobutanol from carbohydrates that are isolated from biomass. It is possible to obtain simple carbohydrates from plants such as sugar cane, sugar beet. It is possible to obtain more complex carbohydrates from plants such as corn, wheat and other grain plants. Even more complex carbohydrates can be isolated from essentially any biomass, by separating cellulose and hemicellulose from lignocelluloses.
In the mid-nineties, many oil companies tried to produce more isobutene for the production of MTBE. Thus, many skeletal isomerization catalysts have been developed for the transformation of n-butenes to isobutenes (Adv. Catai. 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-element ring zeolites and modified alumines. Isomerization of the isobutene reverse skeleton in n-butenes has not been reported.
The dehydration reactions of alcohols to produce alkenes have long been known (J. Catai. 7, p. 163, 1967 and J. Am. Chem. Soc. 83, p. 2847, 1961). It is possible to use many solid acid catalysts available in dehydrating alcohols
3/29 (Stud. Surf. Sei. Catai. 51, p. 260, 1989). However, γ-alumines are the most commonly used, especially in the case of longer chain alcohols (with more than three carbon atoms). This is due to the fact that catalysts with a stronger acidity, such as silica-aluminins, molecular sieves, zeolites or resin catalysts, are capable of promoting double bond change, isomerization of the skeleton and other inter-transformation reactions of olefins. The primary product of isobutanol-acid-catalyzed dehydration is isobutene:
CH ₃ -CH-CH ₂ -OH CH ₃ -C = CH ₂ + H ₂ OII
CH ₃ CH ₃
The dehydration of alcohols with four or more carbons with solid acid catalysts is expected to be accompanied by the double bond change reaction of the alkene product. This is because the two reactions occur promptly and with comparable ratios {Carboniogenic Activity of Zeolites, Elsevier Scientific Publishing Company, Amsterdam (1977) p. 169). The primary product, isobutene, is very reactive in the presence of an acid catalyst, due to the presence of a double bond linked to a tertiary carbon. This allows for easy protonation, since the tertiary structure of the resulting carbocation is the most favorable among the possible carbocation structures (tertiary> secondary> primary carbocations). The resulting t-butyl cation undergoes an oligomerization / polymerization or other electrophilic substitution in electrophilic or aromatic or aliphatic addition reactions. The rearrangement of the t-butyl cation is not a direct reaction in that, without pretending to be bound by any theory, it implies an intermediate formation of a secondary or primary butyl cation and, thus, the probability of secondary reactions (substitutions or additions) is very high and would reduce the selectivity of the desired product.
The dehydration of butanols has been described in catalysts of the genus alumina {Applied Catalysis A, General, 214, p. 251, 2001). Both the double bond change and the skeleton isomerization were obtained at a very low spatial speed (or very long reaction time) corresponding to a GHSV {Gas Hourly Space Velocity = feed rate ratio (gram / h) for weight of catalyst (mL)) less than 1 gram. mL ¹ .h ' ¹ .
US3365513 discloses that tungsten on silica is an appropriate metathesis catalyst.
Patent FR2608595 discloses a process for the production of propylene through metathesis of 2-butene with ethylene, with a catalyst containing rhenium supported on a support containing alumina in a reaction zone of moving bed, at 0 to 100 ° C, followed by reoxidation of the catalyst at a higher temperature and reuse of the catalyst.
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ΕΡ 45304515 reveals a metathesis process to react 1-butene with 2butene to give propene and pentenes, which is carried out in a reactive distillation equipment using Re ₂ O ₇ / AI ₂ O ₃ as a catalyst.
US3526676 reveals the metathesis with MoO ₃ and COO on AI ₂ O ₃ of 1-butene with 2butene to give propene and pentene.
US7473812 discloses a process for removing isobutene from a mixture of butenes, through a process for the co-production of butene oligomers and tert.-butyl ethers, through partial oligomerization of the isobutene with an acid catalyst, to give rise to butene oligomers and subsequently etherify the remaining isobutene with an alcohol under acid catalysis, giving rise to tert-butyl ethers.
US615933 discloses a process for transforming C4 or C5 fractions into an alkyl-t-butyl ether or alkyl-t-amyl ether and propylene by metathesis. The plant comprises four successive steps: (i) selective hydrogenation of diolefins with simultaneous isomerization of alpha olefins in internal olefins, (ii) etherification of isoolefins, (3) elimination of oxygen-containing impurities and (4) methane olefin synthesis with ethylene.
US6495732 discloses a process for isomerizing monoolefins in aliphatic hydrocarbon streams at 40 to 300 ° F, under low hydrogen partial pressure between about 0.1 psi and less than 70 psi at 0 to 350 psig, in a Distillation column reactor containing a distillation catalyst, which serves as a component of a distillation structure, such as supported PdO coated with tubular wire mesh. Essentially there is no hydrogenation of monoolefins.
US4469911 discloses a process for isobutene oligomerization in the presence of a fixed bed cation exchange resin, at a temperature between 30 ° and 60 ° C and at an hourly spatial liquid velocity (LHSV) of 2.5 to 12 h ' ¹ .
US5895830 describes an increased dimer selectivity of a butene oligomerization process using SPA (supported phosphoric acid), by diluting the butene feed with a heavy saturated stream containing paraffins, having a number of carbons of at least 8 .
US5877372 discloses isobutene dimerization in the presence of isooctane thinner and tert-butyl alcohol (at least 1% by weight and preferably 5 to 15% by weight), with an ion exchange resin of the sulfonic acid genus such as Amberlyst A15 , Dowex 50 or similar, at temperatures between 10 ° and 200 ° C, and at pressures between 50 and 500 psig. It is suggested that tert-butyl alcohol improves the selectivity of dimer formation and reduces the formation of trimer oligomers and of higher molecular weight.
US6689927 describes a low butene oligomerization process
5/29 temperature, having a better selectivity of dimerization and a better selectivity of the preferred 2,4,4-trimethylpentene isomer, caused by performing oligomerization in the presence of a SPA catalyst at a temperature below 112 ° C in the presence of a saturated hydrocarbon diluent, having a carbon number of at least 6.
US7220886 discloses a process for the production of propylene from ethylene and 2-butene metathesis, where a mixed C4 stream is first treated to enrich and separate 2-butene from 1-butene and isobutene, and fractional distillation competitor of 2-butene and isobutene, to supply the 2-butene feed to ethylene metathesis. In addition, it is possible to treat the mixed C4 stream to remove mercaptans and dienes prior to 2-butene enrichment.
US6686510 discloses a process for pre-treating metathesis feed and forming a very pure isobutene product. The olefinic C4 stream is selectively hydrogenated to remove the dienes and butines and is then distilled into a reaction distillation column that incorporates a catalyst for the hydroisomerization of butene-1 to butene-2.
The international patent application WO 2005-110951 describes a process for the production of propylene through metathesis of n-butenes, which were obtained through isomerization of the isobutene backbone, which is produced from t-butanol through dehydration.
The metathesis reaction (co-metathesis) between ethylene and butene-2 allows the production of propylene from n-butenes. However, it is necessary to minimize the presence of isobutene in a metathesis reaction, since the isobutene results in heavier hydrocarbons and, thus, in the loss of potential butene-2, which would be able to produce more propylene. The following shows several metathesis reactions:
Co-metathesis> 2
Self-synthesis
Formation of heavy hydrocarbons during metathesis in the presence of isobutene
6/29
₊

Ung tungsten based catalyst is one of the most preferred catalysts used in the industry. In particular, US4575575 and Journal of Molecular Catalysis, Vol. 28, p. 117 (1985) describe the metathesis reaction between ethylene and 2-butene at 330 ° C, with tungsten oxide catalyst with silica support, but the transformation of butene is only 31%, while, when magnesium oxide is used as co-catalyst, the transformation increases to 67%. In addition, US4754098 reports that, for the metathesis reaction at 330 ° C, the use of magnesium oxide, supported by γ-alumina, increases the transformation of butene to 75%. It is also reported in US4684760 that a temperature below 270 ° C (butene transformation is maintained at 74%) can be used when both magnesium oxide and lithium hydroxide are supported on γ-alumina.
Several techniques have been proposed to remove isobutene upstream from a metathesis reactor. A first is to transform the isobutene into methyl-t-butyl ether or ethyl-t-butyl ether, by reacting with methanol or ethanol respectively with catalysts of the acid genus. It is possible to use ethers as components of gasoline. A second is to transform isobutene into oligomers with catalysts of the acid genus. Oligomers, especially iso-octenes and isododecenes, can be used as a gasoline component, as such or after hydrogenation. A third is the catalytic hydration of isobutene in tertiary butyl alcohol with an acid catalyst. A fourth is to distill the C4 fraction in a superfractionator. Since the boiling points of isobutene and 1-butene are very close, the same can be done in a catalytic distillation column that transforms 1-butene continuously into 2-butene with a catalyst, the latter being significantly heavier than isobutene and going to the bottom of the distillation tower. In a preferred method, the isobutene is removed through catalytic distillation combining hydroisomerization and superfractionation. Hydroisomerization transforms 1-butene into 2-butene, and superfractionation removes isobutene, leaving a relatively pure stream of 2-butene. The advantage of transforming 1-butene to 2butene in this system is that the boiling point of 2-butene (1 ° C for the trans isomer, 4 ° C for the cis isomer) is still further away from the boiling point of the isobutylene ( -7 ° O)
7/29 than 1-butene (-6 ° C), thus making isobutene removal through superfractionation easier and less expensive, and avoiding the loss of 1butene head product with isobutylene. The isomerization catalyst, placed in the distillation column, can be any catalyst that has isomerization activity under the typical conditions of the distillation column. Preferred catalysts are palladium containing catalysts which are known to isomerize mono-olefins in the presence of small amounts of hydrogen. Often, traces of olefins can be transformed into mono-olefins at the same time in the presence of hydrogen.
It has now been discovered that the dehydration of isobutanol and the isomerization of the isobutyl radical of the isobutanol can be carried out simultaneously and that the resulting mixture of isobutene and n-butenes can be optionally devoid of isobutene, so that the n- remaining butenes can be used efficiently in metathesis with ethylene or in autometathesis to produce propylene.
It is also part of the present invention that, if an isobutene-enriched fraction is produced by distillation, that isobutene fraction can be further transformed into n-butenes through its recycling with the dehydration / isomerization reactor simultaneously.
As an example, it was found that, for the dehydration and isomerization of the skeleton simultaneously with isobutanol, the crystalline silicates of the FER group; MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having an Si / AI greater than 10, or an unaluminated crystalline silicate of the FER group; MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having a Si / AI greater than 10, or a phosphorus-modified crystalline silicate of the FER group; MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having a Si / AI greater than 10, or molecular sieves of the AEL silicoaluminophosphate genus or silicated, zirconated, titanated or fluorinated alumines have many advantages.
Said dehydration can be carried out at a WHSV (Weight Hourly Space Velocity = ratio of feed rate (gram / h) to weight of catalyst) of at least 1 h ' ¹ , at a temperature of 200 to 600 ° C and using a isobutanol diluent composition of 30 to 100% isobutanol at a total operating pressure of 0.05 to 1.0 MPa.
As an example, in the dehydration / isomerization of isobutanol on a ferrierite, having a Si / AI ratio of 10 to 90 and at a WHSV of at least 2 h ' ¹ to produce n-butenes in addition to isobutene, the transformation of isobutanol is at least 98% and often 99%, but the yield of butenes (isobutenes and n-butenes) is at least 90%, the selectivity of n-butenes is between 5% and the thermodynamic equilibrium, under the reaction conditions in question.
The transformation of isobutanol is the ratio (isobutanol introduced in the isobutanol reactor that leaves the reactor) / (isobutanol introduced in the reactor).
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The yield of n-butenes is the ratio, based on carbon, (n-butenes leaving the reactor) / (isobutanol introduced in the reactor).
The selectivity of n-butenes is the ratio, based on carbon, (n-butenes that leave the reactor) / (isobutanol transformed in the reactor).
Simultaneous dehydration / isomerization of isobutanol results in a mixture of n-butenes (but-1-ene and but-2-ene) and isobutene. According to the present invention, a composition is often obtained close to the thermodynamic equilibrium, while maintaining the high yield of total butenes. The thermodynamic balance for butenes varies between 50 and 65% and for isobutene between 35 and 50%, depending on operational conditions. An important advantage of the present invention is that the composition resembles the composition of a fraction of C4 of refined I obtained from a steam-cracker. Refined I is obtained by removing butadiene from the crude C4 fraction produced in a steam naphtha cracker. Typical compositions are: 35-45% isobutene, 3-15% butanes and the remaining 52-40% nbutenes. The said product of simultaneous dehydration / isomerization can easily replace the use of refined I in existing petrochemical plants. The result is that it becomes possible to minimize capital investment and that the derivatives of this mixture of isobutene / n-butenes can thus be produced from renewable sources instead of fossil resources, by simply replacing the refined fossil I with the product of present invention.
EP 2090561 A1 describes the dehydration of an alcohol in crystalline silicates to give 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.
[Summary of the invention]
The present invention relates to a process for the production of propylene where, in a first step, isobutanol is subjected to dehydration and isomerization of the skeleton simultaneously for the production of essentially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and isobutene and, in a second stage, n-butenes are subject to metathesis, and this process will include:
a) to introduce into a reactor a stream (A) comprising isobutanol, optionally water, optionally an inert component,
b) contacting said stream with a catalyst in said reactor, under conditions effective to dehydrate and isomerize backbone shape at least a portion of the isobutanol, to produce a mixture of n-butenes and isobutene,
c) recover, from said reactor, a current (B), remove the water, the component
9/29 inert, if any, and unprocessed isobutanol, if any, in order to obtain a mixture of n-butenes and isobutene,
d) fractionating said mixture to produce a stream of n-butenes (N) and to remove the essential part of isobutene optionally recycled with the stream (A) for the dehydration / isomerization reactor of step b),
e) transfer the current (N) to a metathesis reactor and make the current (N) contact with a catalyst in said metathesis reactor, optionally in the presence of ethylene, under conditions effective to produce propylene,
f) recover, from said metathesis reactor, a stream (P) containing essentially propylene, unreacted n-butenes, heavy hydrocarbons, optionally unreacted ethylene,
g) fractionate the current (P) to recover propylene and optionally recycle unreacted n-butenes and unreacted ethylene to a metathesis reactor.
In a first embodiment, the WHSV of the isobutanol is at least 1 h ' ¹ and the catalyst in the dehydration / isomerization reactor is able to simultaneously perform the dehydration and isomerization of the butene backbone.
In a second embodiment, whatever the WHSV of the isobutanol, the temperature varies between 200 ° C and 600 ° C and the catalyst in the dehydration / isomerization reactor is able to simultaneously perform the dehydration and isomerization of the butene backbone.
Advantageously, the dehydration / isomerization catalyst is a crystalline silicate from the group FER MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having a Si / AI greater than 10, or a de-illuminated crystalline silicate from the group FER; MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having a Si / AI greater than 10, or a phosphorus-modified crystalline silicate of the FER group; MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON, having a Si / AI greater than 10, or a molecular sieve of silicoaluminophosphate of the AEL group, or a silicated, zirconated or titanated or fluorinated alumina.
The invention will also cover cases in which the isobutanol raw material comprises one or more of the other C4 alcohols, such as 2-butanol, tert-butanol and n-butanol. Advantageously, isobutanol is the main component among the alcohols in the raw material, which means that the isobutanol ratio for all C4 alcohols in the raw material is about 42% or more. Most advantageously, the previous ratio is 70% or more and, preferably, 80% or more. Obviously, if the proportion of isobutanol is too low, the invention will have little interest, since in that case it would be better for dehydration to be carried out without the occurrence of skeletal isomerization, and there are many catalysts in the state of the art capable of dehydrating isobutanol, 2butanol and n-butanol to produce the corresponding butenes. Dehydration of terc.butanol in isobutene, followed by isomerization of the skeleton of at least part of the
10/29 terc.-butanol is described in WO 2005110951.
In a specific embodiment, the mixture of n-butenes and isobutene is fractionated in a stream rich in isobutene and in a stream rich in n-butanes, or isobutene is selectively transformed into an easily separable product (iso-octenes, isododecenes, t-butanol, MTBE or ETBE). The isobutene-rich stream can be recycled back to the simultaneous dehydration / isomerization reactor to produce more n-butenes.
The n-butenes are transferred to a metathesis reactor, where they are transformed into propylene by self-synthesis or are transferred to a metathesis reactor, where they are transformed, in the presence of added ethylene, into propylene.
In a specific embodiment, the n-butene stream (N) from step d) comprises less than 10% by weight of isobutene and, preferably, less than 5% by weight.
In a specific embodiment, in the fractionation of step d), the isobutene is removed through selective isobutene oligomerization. Said oligomerization advantageously produces mainly iso-octenes and isododecenes.
In a specific embodiment, in the fractionation of step d) isobutene is removed through selective etherification with methanol or ethanol.
In a specific embodiment, in the fractionation of step d), isobutene is removed through selective hydration in t-butanol. Optionally, said t-butanol is recycled to the dehydration / isomerization reactor in step b).
In a specific embodiment, the metathesis is performed as a self-synthesis with only butenes as the raw material.
In a specific embodiment, the stream of n-butenes (N) recovered in step d) is transferred to an isomerization unit to produce a stream of n-butenes, having a reduced content of 1-butene and an increased content of 2- butene, the current being transferred to the metathesis reactor.
In a specific embodiment, the fractionation of step d) is carried out through a catalytic distillation column, where the essential part of 1-butene is isomerized in 2butene, with isobutene recovered as a head product and 2-butenno being recovered in final distillation fractions of that column. Advantageously, the isobutene is recycled to the dehydration / isomerization reactor in step b).
In a specific embodiment, metathesis is performed by adding ethylene to butenes. Advantageously, butenes are essentially 2-butene.
[Detailed description of the invention]
In relation to the current (A), the isobutanol may be subjected to simultaneous dehydration and isomerization of the skeleton, alone or in mixture with an inert medium. The inert component is any component as long as it is not essentially
11/29 transformed on the catalyst. Because the dehydration stage is endothermic, it is possible to use the inert component as an energy vector. The inert component allows to reduce the partial pressure of isobutanol and other reaction intermediates and will thus reduce secondary reactions, such as oligomerization / polymerization. It is possible to select the inert component from water, nitrogen, hydrogen, CO2 and saturated hydrocarbons. It may be such that some inert components are already present in isobutanol, due to being used or co-produced during the production of isobutanol. Examples of inert components that may already be present in isobutanol are water and CO2. It is possible to select the inert component among saturated hydrocarbons having up to 10 carbon atoms, naphthenes. Advantageously, it is a saturated hydrocarbon or a mixture of saturated hydrocarbons having 3 to 7 carbon atoms, most advantageously having 4 to 6 carbon atoms and being preferably pentane. An example of an inert component could be any individual saturated compound, a synthetic mixture of individual saturated compounds, as well as some balanced refinery streams, such as linear 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.
Regarding the reactor for simultaneous dehydration / isomerization, it can be a fixed bed reactor, a moving bed reactor or a fluidized bed reactor. A typical fluidized bed reactor is one of the FCC genre used for catalytic fluidized bed cracking at the oil refinery. A typical moving bed reactor is of the continuous catalytic reform type. Simultaneous continuous dehydration / isomerization is possible in a fixed bed reactor configuration using a pair of parallel swing reactors. It has been found that the various preferred catalysts of the present invention have great stability. This allows the dehydration process to be carried out continuously in two parallel swing reactors, where one reactor is operating and the other reactor is undergoing catalyst regeneration. The catalyst of the present invention can also be regenerated several times.
It is possible to carry out simultaneous continuous dehydration / isomerization in a moving bed reactor, where the catalyst circulates from a reaction zone to a regeneration zone and the reverse, with a catalyst residence time in the reaction zone of at least 12 hours. In each zone, the catalyst behaves essentially like a fixed bed reactor, but the catalyst moves slowly, by gravity or pneumatically through the respective zone. The use of a moving bed reaction allows continuous operation to be achieved, without switching the raw material and
12/29 regeneration from one reactor to another. The reaction zone receives the raw material continuously, while the regeneration zone receives the regeneration gas continuously.
Simultaneous continuous dehydration / isomerization is possible in a fluidized bed reactor, where the catalyst circulates from a reaction zone to a regeneration zone and the reverse, with a catalyst residence time in the reaction zone of at least 12 hours. In each zone, the catalyst is in a fluidized state and has a size and shape that makes it remain fluidized in the flow of the raw material and in the reaction products or regeneration gas. The use of a fluidized bed makes it possible to regenerate the deactivated catalyst very quickly through regeneration in the regeneration zone.
Regarding the pressure for simultaneous dehydration / isomerization, it can be any pressure, but it is easier and more economical to operate at a moderate pressure. As an example, the reactor pressure ranges 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), with a greater advantage from 1.2 to 5 absolute bars (0.12 MPa to 0.5 MPa) and preferably from 1.2 to 4 absolute bars (0.12 MPa to 0.4 MPa). Advantageously, the partial pressure of isobutanol ranges from 0.1 to 4 bars absolute (0.01 MPa to 0.4 MPa), with a greater advantage of 0.5 to 3.5 bars absolute (0.05 MPa to 0 , 35 MPa).
Regarding the temperature for simultaneous dehydration / isomerization, the first time it goes from 200 ° C to 600 ° C, with an advantage of 250 ° C to 500 ° C, with a greater advantage of 300 ° C to 450 ° C. Regarding the temperature and the second realization, it goes from 200 ° C to 600 ° C, with advantage of 250 ° C to 500 ° C, with greater advantage of 300 ° C to 450 ° C.
These reaction temperatures refer essentially to the average temperature of the catalyst bed. Dehydration of isobutanol is an endothermic reaction and requires the input of reaction heat in order to keep the catalyst activity high enough and to change the thermodynamic balance of dehydration to sufficiently high levels of transformation.
In the case of fluidized bed reactors: (i) for stationary fluidized beds without catalyst circulation, the reaction temperature is essentially homogeneous throughout the catalyst bed: (ii) in the case of circulating fluidized beds, where the catalyst circulates between a transformation reaction section and a catalyst regeneration section, depending on the degree of catalyst remixing, the temperature in the catalyst bed comes close to homogeneous conditions (a lot of mixing) or comes close to continuous flow conditions (practically without remixing), and thus a decreasing temperature profile will be installed as the transformation proceeds.
In the case of fixed bed reactors or moving bed reactors, a decreasing temperature profile will be installed as the transformation of isobutanol proceeds. In
13/29 In order to compensate for the drop in temperature and consequently the reduction of catalyst activity or to get close to the thermodynamic equilibrium, it will be possible to introduce reaction heat using several catalyst beds in series with inter-heating of the reactor effluent from the first bed to higher temperatures, and introducing the heated effluent into a second catalyst bed, etc. When using fixed bed reactors, it will be possible to use a multi-tube reactor, in which the catalyst is loaded in small diameter tubes that are installed in a reactor housing. On the side of the housing, a heating medium is introduced which provides the necessary reaction heat through heat transfer through the wall of the reactor tubes to the catalyst.
Regarding the mass hourly space velocity (WHSV) of isobutanol for simultaneous dehydration / isomerization, and at the first time it is advantageously from 1 to 30 h ' ¹ , preferably from 2 to 21 h' ¹ , with a greater preference of 7 to 12 h ' ¹ . In relation to the second embodiment, it goes advantageously from 1 to 30 h ' ¹ , with a greater advantage from 2 to 21 h' ¹ , preferably from 5 to 15 h ' ¹ , more preferably from 7 to 12 h' 1
In relation to the simultaneous dehydration / isomerization stream B, it essentially comprises water, olefin, the inert component (if any) and unprocessed isobutanol. Said unprocessed isobutanol is supposed to be in the least amount possible. The olefin is recovered using usual fractionation means. Advantageously, the inert component, if any, is recycled into the stream (A), as well as the unprocessed isobutanol, if any. Unprocessed isobutanol, if any, is recycled to the reactor in the stream (A).
Advantageously, among butenes, the proportion of n-butenes is greater than 20%, favorably greater than 30%, with greater advantage greater than 40%, preferably greater than 50%.
Regarding the catalyst for simultaneous dehydration / isomerization, it is advantageously a crystalline silicate of the FER group (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 de-illuminated crystalline silicate of the FER group (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 (ZSM5), MEL (ZSM-11) or TON (ZSM-22, Theta- 1, NU-10), or a phosphoromodified crystalline silicate of the FER group (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM49), 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 of silicoaluminophosphate of the AEL group (SAPO-11), or a silicated, zirconated or titanated or fluorinated alumina.
A preferred catalyst is a crystalline silicate of the FER or MFI group, having a
14/29
Si / AI greater than 10, or an unaluminated crystalline silicate of the FER or MFI group, having an Si / AI greater than 10, or a phosphor-modified crystalline silicate of the FER or MFI group, having an Si / AI greater than 10.
About the crystalline silicate with FER structure (ferrierite, FU-9, ZSM-35, it can be the lamellar precursor that becomes FER through calcination).
The Si / AI ratio of the crystalline silicate is advantageously greater than 10.
Crystalline silicate is one in which the Si / AI ratio is most advantageously between 10 and 500, preferably between 12 and 250, most preferably between 15 and 150.
It is possible to determine the acidity of the catalyst by the amount of residual ammonia on the catalyst, following the contact of the catalyst with ammonia, which adsorbs on the acidic sites of the catalyst with subsequent ammonium desorption at high temperature, measured by differential thermogravimetric analysis or analysis of ammonia concentration in the desorbed gases.
Crystalline silicate can be subjected to several treatments before use in dehydration, including ion exchange, modification with metals (in a non-restrictive way, alkaline, alkaline earth, transition or rare earth elements), external surface passivation, modification with P compounds , vaporization, acid treatment or other methods of de-alumination, or combinations thereof.
In a specific embodiment, the crystalline silicate is vaporized to remove aluminum from the crystalline silicate skeleton. The steam treatment is carried out at an elevated temperature, preferably between 425 and 870 ° C, more preferably between 540 and 815 ° C and with an atmospheric pressure and a partial water pressure of 13 to 200 kPa. Preferably, the steam treatment is carried out in an atmosphere comprising from 5 to 100% vol. of steam. The steam atmosphere preferably contains 5 to 100% vol. of steam with 0 to 95% vol. of an inert gas, preferably nitrogen. The steam treatment is preferably carried out over a period of 1 to 200 hours, more preferably from 4 hours to 10 hours. As mentioned above, steam treatment tends to reduce the amount of tetrahedral aluminum in the crystalline silicate skeleton by forming alumina.
In a more specific embodiment, the crystalline silicate is de-illuminated by heating the catalyst in steam to remove the aluminum from the crystalline silicate backbone, and by extracting aluminum from the catalyst, by contacting the catalyst with an aluminum complexing agent, in order to remove from the pores of the skeleton the alumina deposited there during the vaporization step, with a view to increasing the atomic silicon / aluminum ratio of the catalyst. According to the present invention, the crystalline silicate available on the market is modified through a vaporization process, which
15/29 reduces the tetrahedral aluminum in the crystalline silicate skeleton and transforms the aluminum atoms into octahedral aluminum in the form of amorphous alumina. Although in the vaporization stage the aluminum atoms are chemically removed from the crystalline silicate skeleton structure to form alumina particles, these particles cause partial pore or channel obstruction in the skeleton. This may inhibit the dehydration process of the present invention. Accordingly, after the vaporization step, the crystalline silicate is subjected to an extraction step, where amorphous alumina is removed from the pores and the volume of micropores is recovered, at least in part. The physical removal, through a leaching step, of the amorphous alumina from the pores, through the formation of a water-soluble aluminum complex gives rise to the general effect of de-illumination of the crystalline silicate. Thus, by removing aluminum from the crystalline silicate skeleton and then removing alumina, formed from there, from the pores, the process aims to achieve essentially homogeneous de-illumination on all pore surfaces of the catalyst. This reduces the acidity of the catalyst. The acidity reduction occurs ideally especially homogeneously in all the pores defined in the crystalline silicate skeleton. Following the steam treatment, the extraction process is carried out in order to de-illuminate the catalyst through leaching. Aluminum is preferably extracted from the crystalline silicate through a complexing agent, which tends to form a soluble complex with alumina. The complexing agent is preferably an aqueous solution. The complexing agent may contain 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 one of these acids (for example, the sodium salt) or a mixture of two or more of these acids or salts. The complexing agent may comprise an inorganic acid such as nitric acid, halogenic acids, sulfuric acid, phosphoric acid or salts of those acids or a mixture of these acids. The complexing agent may also comprise a mixture of these organic and inorganic acids or their corresponding salts. The complexing agent for aluminum preferably forms a water-soluble complex with aluminum, and in particular removes alumina that forms during the steam treatment step from the crystalline silicate.
Following the aluminum leaching step, the crystalline silicate can subsequently be washed with, for example, distilled water, and then dried, preferably at an elevated temperature of, for example, about 110 ° C.
In addition, if, during the preparation of the catalysts of the invention, alkali metals or alkaline earth metals were used, the molecular sieve may be subjected to a step
16/29 ion exchange. Conventionally, ion exchange is carried out in aqueous solutions using ammonium salts or inorganic acids.
Following the de-illumination step, the catalyst is then calcined at a temperature, for example, from 400 to 800 ° C at atmospheric pressure, for a period of 1 to 10 hours.
Another suitable catalyst for the present process consists of molecular sieves of silicoaluminophosphate of the AEL group with the typical example of the SAPO-11 molecular sieve. The SAPO-11 molecular sieve is based on ALPO-11, essentially having an Al / P ratio of 1 atom / atom. During synthesis, silicon precursor is added and the insertion of silicon in the ALPO skeleton results in an acidic spot on the surface of the 10-element annular sieve micropores. The silicon content ranges from 0.1 to 10% atom (Al + P + Si is 100).
In another specific embodiment, the crystalline silicate or the silicoaluminophosphate molecular sieve is mixed with a binder, preferably an inorganic binder, and is placed in the desired form, for example, in the form of pellets. The binder is selected so as to be resistant to temperature and other conditions used in the dehydration process of the invention. The binder is an inorganic material selected from clays, silica, metal silicates, metal oxides such as ZrO ₂ and / or metals, or gels including mixtures of silica and metal oxides. If the binder that is used together with the crystalline silicate is itself catalytically active, this may alter the transformation and / or selectivity of the catalyst. Inactive materials for the binder may be used as appropriate diluents to control the amount of transformation, so that the products can be obtained in an economical and organized manner without using other means to control the reaction rate. It is desirable to provide a catalyst having a good compressive strength. This is because in terms of commercial use it is desirable to prevent the catalyst from being decomposed into materials in powder form. These clay or oxide binders were normally used only with the intention of imparting compression resistance to the catalyst. A particularly preferred binder for the catalyst of the present invention contains silica. The relative proportions of the finely divided crystalline silicate material and the inorganic oxide matrix of the binder can vary widely. Typically, the content of the binder ranges from 5 to 95% by weight, more typically from 20 to 75% by weight, based on the weight of the composite catalyst. A mixture of this kind of crystalline silicate and inorganic oxide binder is called formulated crystalline silicate. By mixing the catalyst with a binder, the catalyst can be formulated in the form of pellets, extruded in other forms, or put in spherical form or in a spray dried powder. Typically, the binder and crystalline silicate are mixed with each other through a mixing process. In this process, the binder, for example, silica, in the form of a gel is mixed with
17/29 the crystalline silicate material and the resulting mixture is extruded in the desired shape, for example, cylindrical or multilobular bars. Spherical shapes can be produced in rotary granulators or by using the oil drop technique. Small beads can also be produced by spray drying a catalyst-binder suspension. Thereafter, the formulated crystalline silicate is calcined in air or in an inert gas, typically at a temperature of 200 to 900 ° C for a period of 1 to 48 hours.
In addition, it is possible to mix the catalyst with the binder before or after the vaporization and extraction steps.
Another family of catalysts suitable for simultaneous dehydration and isomerization of the skeleton is that of aluminas that have been modified through surface treatment with silicon, zirconium, titanium or fluorine. Alumines are generally characterized by a very wide distribution of acid strength and by having Lewis and Bronsted acid sites. The presence of a wide acid strength distribution makes it possible to catalyze several reactions, each requiring a different acid strength. This often results in reduced selectivity for the desired product. The deposition of silicon, zirconium, titanium or fluorine on the surface of the alumina makes the catalyst significantly more selective. For the preparation of the alumina-based catalyst, it is possible to use appropriate commercial aluminum, preferably eta-aluminum or gamma-aluminum, having a surface area of 10 to 500 m2 / 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% silicon, zirconium or titanium. The addition of these metals can be carried out during the preparation of the alumina or it can be added to the existing alumina, possibly already activated. It is possible to perform the addition of the metal during the preparation of the alumina by dissolving the metal precursor together with the aluminum precursor, before the precipitation of the final alumina or by adding the metal precursor to the aluminum hydroxide gel. A preferred method is the addition of metallic precursors to the molded alumina. The metal precursors are dissolved in an appropriate solvent, whether aqueous or organic, and come into contact with alumina through impregnation with incipient wetting or through wetting impregnation or through contact with an excess of solute for a certain period of time. following removal of excess solute. Alumina can also come in contact with vapor from the metal precursor. Suitable 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, with total
18/29 preferably from 10 ° C to 200 ° C. After contact, the alumina is eventually washed, dried and finally calcined in another to increase the surface reaction between silicon, zirconium or titanium and alumina and the removal of metal precursor ligands. The use of silicated, zirconated or titanated or fluorinated aluminas for the simultaneous dehydration and isomerization of the isobutanol skeleton occurs preferably in the presence of water. The weight ratio of water to isobutanol ranges from 1/25 to 371. Fluorinated alumina is known per se and can be produced according to the state of the art.
Regarding the use of the product from simultaneous dehydration / isomerization, the mixture of n-butenes and isobutene can replace the use of refined I in the refinery or in the petrochemical plants. Figure 1 shows the main applications of nbutenes and isobutene. The most typical application of this mixture is the transformation of the isobutene present in ethers (MTBE and ETBE), in t-butyl alcohol (TBA) or oligomers (for example, diisobutenes / triisobutenes), all of which are components of gasoline. The higher molecular weight oligomers of isobutene can be used in aviation / kerosene fuel applications. High purity isobutene can also be produced by decomposing ethers (backcracking) or TBA (dehydration). High purity isobutene can be applied in the production of butyl rubber, polyisobutene, methyl methacrylate, isoprene, hydrocarbon resins, t-butylamine, alkylphenols and t-butylmercaptan.
N-butenes, which did not react during the production of ethers or TBA, and which did not react or which only reacted to a limited extent during oligomerization, can be applied in the production of sec.-butanol, alkylate (addition of isobutane to butenes) , polygassoline, oxo-alcohols and propylene (metathesis with ethylene or autometathesis between but-1-ene and but-2-ene). Through superfractionation or extractive distillation or absorbent separation, it is possible to isolate but-1-ene from the mixture of n-butenes. But-1-ene is used as a comonomer in the production of polyethylene, for poly-but-1-ene and n-butylmercaptan.
N-butenes can also be separated from isobutene through catalytic distillation. This implies an isomerization catalyst that is located in the distillation column and continuously turns but-1-ene into but-2-ene, being a heavier component than but-1-ene. Thus, a final distillation product rich in but-2-ene and a top fraction product low in but-1-ene and rich in isobutene are produced. It is possible to use the final distillation fraction product as described above. A main application of this but-2-ene-rich current is metathesis with ethylene, in order to produce propylene. If high purity isobutene is desired, the top fraction product can be further superfractionated into essentially pure isobutene and pure but-1-ene, or the isobutene can be isolated through the production of ethers or TBA, which is subsequently decomposed into isobutene pure.
The current rich in n-butenes can be used in the production of butadiene through
19/29 dehydrogenation or oxidative dehydrogenation.
The mixture of isobutene and butenes can be transferred to a catalytic cracking, which is selective with respect to light olefins in the effluent, the process comprising understanding to contact said mixture of isobutene and butenes with an appropriate catalyst, to produce an effluent with a content of olefin less molecular weight than raw material. Said cracking catalyst can be a silicalite (genus MFI or MEL) or a P-ZSM5.
Regarding the preparation of the metathesis raw material, it is preferred to remove the isobutene before the metathesis. This can be accomplished through a selective chemical transformation of isobutene or through distillation. The selective chemical transformations are: (i) oligomerization, (ii) etherification or (iii) hydration or their combinations. The resulting products are respectively: (i) iso-octenes for use in gasoline, trimers, tetramers or pentamers of essentially isobutene, for use in aviation fuel or kerosene: (ii) methyl-t-butyl ether or ethyl-t ether -butyl; (iii) t-butanol. The oligomers are eventually hydrogenated in the respective paraffins. The t-butanol can eventually be recycled back to the simultaneous dehydration / isomerization reaction sections of the skeleton.
A preferred distillation method is catalytic distillation during which 1-butene is continuously transformed into 2-butenes, in order to optimize the yield of 2butenes and minimize the entrainment of 1-butene with the isobutene head product. The isobutene-rich head product can be recycled back to the simultaneous dehydration / isomerization reaction sections of the skeleton.
Regarding the metathesis catalyst, three types of catalysts containing metal may be appropriate to carry out the dismutation reaction. The reaction of ethylene comethesis with butene-2 or the self-synthesis of a mixture of 1-butene and 2butene can be catalyzed through three metal oxides that are dispersed in supports: through molybdenum (possibly in combination with cobalt and rhenium), tungsten or rhenium.
A first type of catalyst is rhenium supported on a support containing alumina. The rhenium content can be from 0.5 to 15% by weight. The rhenium catalyst is, before use, pretreated at a temperature of at least 400 ° C, preferably at least 500 ° G. Optionally, the catalyst can be activated, before use, through treatment with alkyl-boron, alkyl-aluminum or alkyl-tin. Rhenium oxide is deposited on a substrate containing a refractory oxide, containing at least alumina and having an acidic nature, such as, for example, alumina, silica-aluminum or zeolites.
In preferred examples, catalysts contain rhenium heptoxide which is deposited on a gamma-alumina, such as those described in US4795734. Rhenium content can
20/29 is from 0.01 to 20% by weight, preferably from 1 to 15% by weight.
Catalysts containing Rhenium heptoxide, which is deposited on an alumina, can also be modified by the addition of a metal oxide. It is possible to add 0.01 to 30% by weight of at least one metal oxide of the niobium group or tantalum according to FR2709125. FR2740056 describes that it is possible to add 0.01 to 10% by weight of aluminum of the compound with the Formula (RO) _q AIR , where R is a hydrocarbyl radical of 1 to 40 carbon atoms, R 'is an alkyl radical of 1 at 20 carbon atoms, eqer are equal to 1 or 2, where q + r is equal to 3.
The metathesis reaction with rhenium heptoxide catalysts is preferably carried out in a liquid phase, in the absence of compounds containing oxygen and moisture, at a temperature of 0 to 150 ° C, preferably of 20 to 100 ° C, at a pressure that at least keep the reaction mixture at the reaction temperature in the liquid state.
A second type of catalyst is tungsten supported on silica support. The tungsten content can be from 1 to 15% by weight. The tungsten-based catalyst is thermo-treated, before use, at least at 300 ° C, preferably at least at 500 ° C. The catalyst can also be activated through treatment with hydrogen, carbon monoxide or ethylene.
Tungsten-based catalysts are used to advantage in combination with a co-catalyst. Examples of co-catalysts used in the invention include metal compounds belonging to group Ia (alkali metals), group IIa (alkaline earth metals), group IIb and group IIa from the periodic table or combinations of the latter. Preference is given to lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, lanthanum and yttrium. These metals are generally used as oxides, as such or deposited on a support, or as mixed oxides. Examples of the latter are hydrotalcites which are aluminum and magnesium double layer hydroxide, and solid solutions of aluminum oxide and magnesium oxide, obtained by calcining the corresponding hydrotalcite. Metal oxides, mixed oxides, hydroxides, double hydroxides, nitrates and acetates can be supported on supports having a large surface area.
The patents US4575575, 4754098 and 4684760 describe that magnesium oxide is essentially used as a co-catalyst. In all US4575575, 4575575, 4754098, 4754098 and 488760, magnesium oxide containing a promoter is mentioned as an essential component.
The support for the co-catalyst is preferably a compound that does not have acidity, because acidic sites may induce oligomerization of olefins. Preferred examples of supports for co-catalysts include carbon, alkaline zeolites, γalumina, silica, alkaline earth silicates or alkaline silicates, aluminophosphates, zirconia and titania. The amount of the co-catalyst metal oxide deposited on the support will generally
21/29 from 0.01 to 40% by weight, preferably from 0.1 to 20% by weight.
The metallic compound to produce the co-catalyst can be supported on the support by several methods. Metal precursors can be any salt, for example, nitrates, halides, oxyhalides or hydroxides. The alkoxy compounds (RO) can also be used as a precursor. The starting material is dissolved in an appropriate solvent, preferably an aqueous solution, and the support is impregnated with it. The excess solvent, if any, is then evaporated to a dry state, and the residue is calcined at a temperature of 300 ° C or higher in an oxygen atmosphere.
When preparing the support from a metal outlet or alkoxy precursors, it is possible to use a co-precipitation method. For this, the metal salts or the alkoxy compounds or both the support and the metal of catalytic activity are mixed and undergo precipitation simultaneously.
The shapes of the co-catalyst can be essentially any one, such as spherical shapes, cylindrical shapes, extruded shapes and pellets. It is preferred that the shape of the particles be one that allows for easy mixing of the co-catalyst with the metathesis catalyst or can be installed above or below the catalyst bed containing the metathesis catalyst.
In the metathesis process, the weight ratio of the co-catalyst to the metathesis catalyst is favorably from 0.1 to 15, preferably from 1 to 8.
Without pretending to be linked to any theory, it is believed that the co-catalyst presents, due to its basic nature, two activities: (i) the isomerization of alpha-olefins in internal olefins, the latter will lead to the dismutation reaction with ethylene, the alpha- shorter desired olefin, namely propylene, (ii) the capture of toxic substances for metathesis, like any compound with some acidic nature, such as CO ₂ , H ₂ S, H ₂ O, etc.
When the catalyst and metathesis co-catalyst are inserted into a fixed bed flow reactor, it will be possible to load a physical mixture of the catalyst and metathesis cocatalyst, as described in the Journal of Molecular Catalysis, volume 28, p. 177 (1985), or it will be possible to insert a layer of the co-catalyst on the metathesis catalyst. In addition, a combination of these methods can be used.
A third type of catalyst is molybdenum supported on alumina or on silica support. Suitable molybdenum oxide based catalysts are disclosed in US3658927 and US4568788. The dismutation catalyst in the present invention is prepared using at least one of molybdenum, possibly combined with cobalt or rhenium, supported on an inorganic oxide support. The inorganic oxide support comprises a substantial amount of silica or alumina. Synthetic refractory oxides comprise silica, alumina, silica-alumina, silica-magnesia, silica-titania, alumina-titania, alumina-magnesia, boria-alumina-silica, alumina-zirconia, thorium or silica-titania-zirconia. O
22/29 molybdenum, possibly in combination with cobalt or rhenium, can be dispersed on the inorganic oxide support using any conventional method, such as impregnation, dry mixing, ion exchange, co-precipitation. For example, alumina can be impregnated with an aqueous solution containing molybdenum salts, such as ammonium heptamolybdate or ammonium dimolybdate. Once the molybdenum is dispersed on the support, it is calcined at least at 300 ° C and, before use in the metathesis reaction, it can be activated by contact with alkyl-boron, alkyl-aluminum or alkyl-tin compounds. The metallic compound for the production of metathesis catalyst based on molybdenum, rhenium or tungsten can be supported on a support through several methods. Metal precursors can be any salts, such as, for example, nitrates, halides, oxyhalides or hydroxides. It is also possible to use polyacids or isopoly acids or the respective ammonium salt of the polyacid, or ammonium salt of the isopoly acid as the starting material. Alkoxy compounds (RO) can also be used as a precursor. The starting material is dissolved in an appropriate solvent, preferably an aqueous solution, and the support is impregnated with it. The excess solvent, if any, is then evaporated to a dry state, and the residue is calcined at a temperature of 300 ° C or more in an oxygen atmosphere.
If the support is prepared from a metallic salt or alkoxy precursors, it is possible to use a co-precipitation method. For this, metallic salts or alkoxy compounds of both the support and the metal of catalytic activity are mixed and are caused to precipitate simultaneously.
The support is generally molded into essentially any shape, such as spherical shapes, cylindrical shapes, extruded shapes and pellets. The size of the molded particles is related to the reactor genus and generally ranges from 0.01 to 10 mm.
The metathesis catalyst activity generally decreases due to polar compounds, such as moisture, carbon dioxide, carbon monoxide, diene compounds, sulfur and nitrogen compounds, alcohols, aldehydes and carboxylic compounds. Accordingly, olefins used as a raw material should preferably be purified from impurities. These impurities are removed by distillation, adsorption, extraction or washing. Other materials used during the process, such as nitrogen gas and hydrogen gas, which are introduced into the reactor also require extensive purification. Often nitrogen is required to purge moisture reactors, to reduce agents (carbon monoxide, ethylene or hydrogen) and waste resulting from this reduction.
The most appropriate adsorbent to be used is γ-alumina or promoted alumines, which are particularly suitable for the removal of polar substances, such as water, mercaptans, aldehydes and alcohols. Magnesium oxide-based adsorbents are also
23/29 suitable for removing not only neutral polar substances, such as water and the like, but also acidic substances such as carbon dioxide, organic acids and the like. Equally zeolite compounds, for example, Molecular Sieve molecular sieve 4A, 5A, 13X and the like, are not only excellent at adsorbing neutral polar substances, such as water and the like, but also very effective at adsorbing basic compounds, thanks to their acidic property. Suitable non-limiting examples of used zeolite are of the genus A, X, Y, USY, ZSM-5 and the like.
In addition, the metathesis catalyst activity can be further increased or stabilized through the presence of hydrogen. The amount of hydrogen in the combined raw material of olefins (butenes and ethylene) is favorably between 0.1 and 10% vol. and, preferably, between 0.2 and 5% vol.
It is possible to carry out the metathesis reaction in liquid phase, gas phase, and mixed gas-liquid phase, which is determined through temperature and reaction pressure. The rhenium-based catalyst works preferably between 0 and 150 ° C at a pressure that keeps the raw material in a liquid state. The molybdenum-based catalyst works preferably at 100 to 250 ° C in a gas phase under a pressure of 1 to 30 bars. Catalysts based on tungsten operate preferably at 150 to 400 ° C at a pressure of 5 to 35 bars. It is possible to perform continuous metathesis in a fixed bed reactor configuration, using a pair of parallel swing reactors, provided that the catalyst has a sufficient stability of at least 2 days. This allows the continuous metathesis process to be carried out in two parallel swing reactors, where a reactor is in operation; the other reactor is undergoing catalyst regeneration. When the stability of the catalyst is less than about 2 days, it will also be possible to perform continuous metathesis in a moving bed reactor, where the catalyst circulates from a reaction zone to a regeneration zone and the reverse, with a time of catalyst stay in the reaction zone for at least 5 hours. In each zone, the catalyst behaves essentially 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 reaction allows to achieve continuous operation without switching the raw material and the regeneration gas from one reactor to another. The reaction zone receives the raw material continuously, while the regeneration zone receives the continuous regeneration gas.
Metathesis is possible with only a mixture of n-butenes and it is commonly known as self-synthesis. The products are propylene and pentenes. The desired propylene product is recovered, while the pentenes can be recycled back to the metathesis reaction section. It is also possible to perform metathesis by adding ethylene to the raw material of n-butenes, commonly known as co-metathesis. THE
The molar ratio of ethylene to n-butenes is advantageously 0.75 to 5, preferably 1 to 2.5.
Regarding the metathesis reaction products, the reactor effluent contains untransformed ethylene, if one has been added to the reaction section, and butenes, as well as heavy hydrocarbons and the desired propylene product. In a desetanizer, ethylene, and eventually hydrogen, if used, is produced at the head and is recycled from voite to the metathesis reactor. The final distillation fraction product is further separated in a depropanizer, where the head product is the intended propylene. The final fraction fraction product is typically butenes and some heavier olefins. Butenes can be recycled back to the metathesis reactor for a greater reaction.
Figure 2 shows the procedural chain with implementation of oligomerization to remove isobutene. After simultaneous dehydration / simultaneous skeletal isomerization, the aqueous product is separated and the butene mixture, possibly containing some heavy hydrocarbons, is oligomerized. The oligomerization effluent contains oligomers, unreacted n-butenes and smaller amounts of unprocessed isobutene. The essentially unreacted n-butenes are purified and transferred to the metathesis reactor alone or mixed with ethylene. The effluent from the metathesis reactor is fractionated: ethylene is recycled back to the metathesis reactor; the remaining n-butenes can also be recycled in part, while a purge of heavy butenes and hydrocarbons leaves the recycling loop and propylene is obtained as the desired product.
Figure 3 shows the procedural chain with implementation of etherification to remove isobutene. After simultaneous dehydration / isomerization of the skeleton, the aqueous product is separated and the mixture of butenes, possibly containing some heavy hydrocarbons, is etherified by mixing with methanol or ethanol. The etherification effluent contains ethers, unreacted n-butenes and smaller amounts of unprocessed isobutene. The essentially unreacted n-butenes are purified and transferred to the metathesis reactor alone or in a mixture with ethylene. The effluent from the metathesis reactor is fractionated: ethylene is recycled back to the metathesis reactor; the remaining n-butenes can also be partially recycled, while a purge of heavy butenes and hydrocarbons leaves the recycling loop and propylene is obtained as the desired product.
Figure 4 shows the procedural chain with the implementation of hydration to remove isobutene. After simultaneous dehydration / isomerization of the skeleton, the aqueous product is eventually separated and the butene mixture, possibly containing some heavy hydrocarbons, is hydrated by adding water. The hydration effluent contains t-butanol, unreacted n-butenes and smaller amounts of isobutene
25/29 unprocessed. The essentially unreacted n-butenes are purified and transferred to the metathesis reactor alone or in a mixture with ethylene. The effluent from the metathesis reactor is fractionated: ethylene is recycled back to the metathesis reactor; the remaining n-butenes can also be partially recycled, while a purge of butenes and heavy hydrocarbons leaves the recycling loop and propylene is obtained as the desired product. Eventually, the t-butanol can be recycled back to the section of the simultaneous skeleton dehydration / isomerization reactor, where it will be simultaneously dehydrated and isomerized to the skeleton shape.
Figure 5 shows the procedural chain with implementation of catalytic distillation to remove isobutene. After simultaneous dehydration / isomerization of the skeleton, the aqueous product is separated and the butene mixture, possibly containing some heavy hydrocarbons, is distilled in catalytic distillation. The catalytic distillation head product is an isobutene-rich stream and the final distillation fraction product is a 2-butene-rich stream. The 2-butene stream is purified and transferred to the metathesis reactor alone or in a mixture with ethylene. The effluent from the metathesis reactor is fractionated: ethylene is recycled back to the metathesis reactor; the remaining n-butenes can also be partially recycled, while a purge of butenes and heavy hydrocarbons leaves the recycling loop and propylene is obtained as the desired product. The isobutene-rich head product stream can eventually be recycled back to the simultaneous skeleton dehydration / isomerization reactor section, where it will be further transformed into n-butenes.
[Examples]
Experimental:
The stainless steel reactor tube has an internal diameter of 10 mm. 10 mL of catalyst, like pellets with a 35-45 mesh, are loaded into the tubular reactor. The empty spaces before and after the catalyst are filled with 2 mm SiC granules. The temperature profile is monitored with a thermocouple well placed inside the reactor. The reactor temperature is increased at a rate of 60 ° C / h to 550 ° C under air, being maintained for 2 hours at 550 ° C and then purging through nitrogen is carried out. The nitrogen is then replaced by the feed under the indicated operating conditions.
The catalytic tests are carried out downstream, under 1.5 to 2.0 bars, at a temperature of 280-380 ° C and at a spatial speed / hour / weight (WHSV) of 7 to 21 h ' ¹ .
Product analysis is performed using online gas chromatography.
Example 1 (according to the invention)
The catalyst used in this case is a crystalline silicate with the FER structure. HFER has a Si / AI of 33 in the form of powder. The catalyst is calcined with air at 550 ° C
26/29 for 4 hours, before formulation in pellets with 35-45 mesh.
An isobutanol / water mixture having a composition of 95/5% by weight was processed on the catalyst under 2 bars, at temperatures between 350 and 375 ° C, and at a spatial velocity of isobutanol from 7 to 21 h ' ¹ .
In this set of operational conditions, the transformation of isobutanol is almost complete, with a selectivity of butenes greater than 95% by weight, and an isobutene selectivity of about 41-43%. Low amounts of C ₄ ⁺ compounds are generated.
FOODTACTION iButOH / H2O (95/5)% by weight P (bars) 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 Transformation (% inCH2 weight) 100.0 99.4 89.7 99.8 99.2 C-based oxygenates (wt% CH2) - 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 + 0.1 0.1 0.1 0.1 0.1 ketone Yield based on C (wt% CH2) - 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 Olef C5 + 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 C-based selectivity (wt% CH2) - 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 98.0 98.8 97.9 98.3 Olef C5 + 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
27/29
Unknown 0.1 0.0 0.0 0.0 0.0 Distribution of C4 = (% by weight of 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 cylindrical gamma-alumina formulated from Sasol®. The catalyst has a specific surface area of 182 m ² / g and a pore volume of 0.481 ml / g. The impurities present in alumina in small quantities are summarized below:
0.25 wt% Si, 0.02 wt% P, 0.02 wt% fe, 29 ppm Na.
An isobutanol / water mixture having 95/5% by weight of the composition was processed on the catalyst under 2 bars, at temperatures between 350 and 380 ° C, and at a spatial speed of isobutanol from 7 to 12 h ' ¹ .
Under this set of operating conditions, the transformation of isobutanol is almost complete, with a selectivity of butenes greater than 98% by weight, and with an isobutene selectivity of about 90-94%. Thus, very low amounts of nbutenes are produced with this catalyst. Low amounts of Cs ⁺ compounds are generated.
FOOD i-ButOH / H2O (95/5)% by weight P (bars) 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 Transformation (% by weight of CH2) 99.98 99.96 99.93 99.85 Oxygenates (% by weight of CH2) - average Other oxygenates 0.0 0.0 0.0 0.0 Other alcohol 0.0 0.1 0.1 o, 1 C-based selectivity (wt% CH2) - average Paraffins 0.3 0.3 0.1 0.3 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 Olef C5 + 0.7 0.5 0.1 0.3 Dienos 0.1 0.0 0.0 0.1 Aromatic 0.0 0.0 0.0 0.0
28/29
Unknown 0.1 0.1 0.3 0.4 Distribution of C4 = (% by weight) 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 phosphorus-modified zeolite (P-ZSM5), prepared according to the following formula. A sample of the ZSM-5 zeolite (Si / AI = 13) in the form of H was sprayed at 550 ° C for 6 h in 100% H ₂ O. The vaporized solid was contacted with an aqueous solution of H ₃ PO ₄ (85% by weight) for 2 h under reflux conditions (4 ml / 1 g of zeolite). Then, 69.9 h of CaCO3 was introduced maintaining a pH value of 2.52. Then, the solution was dried by evaporation for 3 days at 80 ° C. 750 g of dry sample were extruded with 401.5 g of Bindzil and 0.01% by weight of extrusion additives. The extruded solid was dried at 110 ° C for 16 h and calcined at 600 ° C for 10 h.
An isobutanol / water mixture having a composition of 95/5% by weight was processed on the catalyst under 1.5 bars, at temperatures between 280 and 350 ° C, and at a spatial velocity of isobutanol of about 7 h ' ¹ .
In this set of operating conditions, the transformation of isobutanol is almost complete, with a selectivity of butenes greater than 90% by weight, and with an isobutene selectivity of about 66-67%. Thus, approximately 90% or more of butenes are produced, of which a significant amount is isomerized from the backbone into n-butenes. The production of heavy hydrocarbons is limited to 10% or less.
FOOD: i-ButOH / H2O (95/5)% by weight
P (bars) 1.5 1.5 T (° C) 300 280 WHSV (H-1) 7.4 7.4 Transformation (% by weight of CH2) 100.0 83.5 Oxygenates (% by weight of CH2) - average Other alcohols 0.01 0.00 Other oxygenates 0.03 0.08 C-based selectivity (wt% CH2) - average
29/29
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 Olef C5 + 4.8 2.7 Paraf C5 + 1.9 1.1 Dienos 0.5 0.4 Aromatic 0.5 0.2 Unknown 1.6 1.1 uisuiuiçao of G4 = - average - i-Duteno --— 67.1 65.9 n-butenes 32.9 34.1 1-butene 5.5 6.5 2-butene 27.4 27.7
1/4

权利要求:
Claims (4)
[1]
1. Process for the production of propylene, characterized in that, in a first stage, isobutanol is subjected to simultaneous dehydration and isomerization of the skeleton, to obtain corresponding olefins with the same number of carbons and consisting of
5 a mixture of n-butenes and isobutene and, in a second step, subjecting the n-butenes to metathesis, comprising the said process:
a) to introduce into a reactor a stream (A) comprising isobutanol, optionally water, optionally an inert component,
b) contacting said stream with a catalyst in said reactor, under conditions effective to dehydrate and isomerize the backbone of at least a portion of the isobutanol, to produce a mixture of n-butenes and isobutene,
c) recover, from said reactor, a current (B), remove water, the inert component, if any, and unprocessed isobutanol, if any, in order to obtain a mixture of n-butenes and isobutene,
D) fractionating said mixture to produce a stream of n-butenes (N) and to remove the essential part of isobutene optionally recycled with the stream (A) for the dehydration / isomerization reactor of step b),
e) transfer the current (N) to a metathesis reactor and make the current (N) contact with a catalyst in said metathesis reactor, optionally in the presence of
20 ethylene, under conditions effective to produce propylene,
f) recover, from said metathesis reactor, a stream (P) containing propylene, unreacted nbutenes, heavy hydrocarbons, optionally unreacted ethylene,
g) fractionate the current (P) to recover propylene and optionally recycle unreacted n-butenes and unreacted ethylene to a metathesis reactor.
wherein the catalyst is a crystalline silicate with Si / Al greater than 10 or a molecular sieve of group AEL silicoaluminophosphate, or a silica, zirconate or titanated or fluorinated alumina.
Process according to claim 1, characterized in that the mass space velocity (WHSV) of the isobutanol is at least 1 h ^-1 and the catalyst in the dehydration / isomerization reactor is able to simultaneously dehydrate and isomerize the butene skeleton.
Process according to claim 1, characterized in that the temperature is between 200 ° C and 600 ° C and in that the catalyst in the dehydration / isomerization reactor is simultaneously able to dehydrate and isomerize the skeleton
Petition 870180056157, of 06/28/2018, p. 7/10
[2]
2/4 of the butene.
Process according to claim 2, characterized in that the temperature is between 200 ° C and 600 ° C.
Process according to any one of claims 1 - 4, characterized in that the n-butene stream (N) of step d) comprises less than 10% by weight of isobutene and, preferably, less than 5% by weight.
Process according to any one of claims 1 - 5, characterized in that, in the fractionation of step d), isobutene is removed by means of selective isobutene oligomerization.
Process according to any one of claims 1 - 5, characterized
15 because, in the fractionation of step d), isobutene is removed through selective etherification with methanol or ethanol.
Process according to any one of claims 1 - 5, characterized in that, in the fractionation of step d), isobutene is removed through selective hydration in
20 t-butanol.
Process according to claim 8, characterized in that said t-butanol is recycled to the dehydration / isomerization reactor of step b).
10. Process according to any one of claims 1 - 9, characterized in that the metathesis is performed as an auto-metathesis using only butenes as raw material.
Process according to any one of claims 1 - 9, characterized in that the current of n-butenes (N), recovered in step d), is transferred to a unit
30 isomerization to produce a stream of n-butenes, having a reduced content of 1butene and an increased content of 2-butene, said stream being transferred to the metathesis reactor.
Process according to any one of claims 1 - 6, characterized
35 because the fractionation of Step d) is carried out through a catalytic distillation column, where the essential part of 1-butene is isomerized in 2-butene, the isobutene is recovered as a head product and the 2-butene is recovered in the fractions end of
Petition 870180056157, of 06/28/2018, p. 8/10
[3]
3/4 distillation of said column.
Process according to claim 12, characterized in that the isobutene is recycled to the dehydration / isomerization reactor of Step b).
Process according to any one of claims 11 - 13, characterized in that metathesis is carried out by adding ethylene to butenes.
Process according to any one of claims 1 - 14, characterized in that the pressure of the simultaneous dehydration and isomerization reactor of the isobutanol backbone ranges from 0.5 to 10 bar absolute.
Process according to any one of claims 1 - 15, characterized in that the temperature of the simultaneous dehydration and isomerization of the skeleton of
15 isobutanol is between 250 ° C to 500 ° C.
Process according to any one of claims 1 - 16, characterized in that the temperature of the simultaneous dehydration and isomerization of the isobutanol backbone is between 300 ° C and 450 ° C.
Process according to any one of claims 1 - 17, characterized in that the metathesis catalyst is a metal oxide dispersed on a support, the metal oxide being selected from molybdenum, optionally mixed with cobalt and rhenium, tungsten or rhenium, and being the holder selected from a holder containing alumina or
25 silica.
Process according to any one of claims 1 - 18, characterized in that, during the metathesis, hydrogen is added to the combined raw material of olefin (butene and optionally ethylene) in an amount comprised between 0.1 and 10% of vol ..
Process according to any one of claims 1 - 19, characterized in that, among the butenes produced in Step c), the proportion of n-butenes is greater than 20%.
21. Process according to claim 20, characterized in that, among the butenes 35 produced in Step c), the proportion of n-butenes is greater than 30%.
22. Process according to claim 21, characterized in that, among butenes
Petition 870180056157, of 06/28/2018, p. 9/10
[4]
4/4 produced in Step c), the proportion of n-butenes is greater than 40%.
Process according to Claim 22, characterized in that, among the butenes produced in Step c), the proportion of n-butenes is greater than 50%.
Petition 870180056157, of 06/28/2018, p. 10/10
1/5

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CN113543879A|2019-03-29|2021-10-22|埃克森美孚化学专利公司|MEL-type zeolite for the conversion of aromatic hydrocarbons, method for preparing said zeolite and catalytic composition comprising said zeolite|

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CN112679295A|2019-10-18|2021-04-20|中国石油化工股份有限公司|Method for producing propylene by converting tert-butyl alcohol|

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WO2021099551A1|2019-11-22|2021-05-27|Total Se|Process for converting one or more methyl halides into c3-c5 alpha olefins|

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WO2021198479A1|2020-04-03|2021-10-07|Total Se|Production of light olefins via oxychlorination|

法律状态:
2018-04-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2018-07-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-09-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/03/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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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. |

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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:

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申请号 | 申请日 | 专利标题

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EP10156537A|EP2366682A1|2010-03-15|2010-03-15|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|

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EP10159463A|EP2374781A1|2010-04-09|2010-04-09|Simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts|

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EP10159461A|EP2374780A1|2010-04-09|2010-04-09|Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis|

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EP10160840|2010-04-23|

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EP10161125|2010-04-27|

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PCT/EP2011/053905|WO2011113836A1|2010-03-15|2011-03-15|Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis|

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