 PROCESSES FOR BUTADIENE PRODUCTION
专利摘要:
公开号:BR112012003615B1 申请号:R112012003615-7 申请日:2010-08-05 公开日:2018-05-22 发明作者:Craig Arnold Stephen；Mae Gaffney Anne；John Karas Lawrence；Jay Angevine Philip；Yuan Yeh Chuen；Song Ruozhi 申请人:Lummus Technology Inc.； IPC主号:
专利说明:
(54) Title: PROCESSES FOR THE PRODUCTION OF BUTADIENE (51) Int.CI .: C07C 5/25; C07C 11/167 (30) Unionist Priority: 08/17/2009 US 12 / 542,565 (73) Holder (s): LUMMUS TECHNOLOGY INC. (72) Inventor (s): STEPHEN CRAIG ARNOLD; ANNE MAE GAFFNEY; LAWRENCE JOHN KARAS; PHILIP JAY ANGEVINE; CHUEN YUAN YEH; RUOZHI SONG 1/40 Descriptive Report of the Invention Patent for PROCESSES FOR THE PRODUCTION OF BUTADIENE. Field of the Invention The present invention relates to improved processes for the production of butadiene. Processes are described for the production of butadiene from C 4 feed charges that contain a significant amount of isobutene and / or isobutane in addition to n-butene (s) and / or n-butane. Butadiene is produced by dehydrogenation of n-butenes which incorporates the use of oxydehydrogenation, after highly effective separation of isobutane (plus any isobutane) from all n-butenes (plus any nbutane) using a combination of isomerization reaction of butenes and distillation tower. The process incorporates conversion of 1-butene to 2-butenes to achieve substantially total iso / normal separation. The processes can be supplemented by isomerization and / or dehydrogenation steps for the bottom and top currents of the tower and with additional supply currents. Background Butadiene is a versatile raw material used in the production of a wide variety of synthetic rubbers, polymer resins and chemical intermediates. The most widespread uses for butadiene are the production of styrene butadiene rubber and polybutadiene rubber, which are mainly used in tire products. Butadiene is also one of the components used in the manufacture of acrylonitrile-butadiene-styrene, styrene-butadiene copolymer latex, styrene-butadiene block copolymers25 and nitrile rubbers. There is a developing demand for butadiene caused by the growth in tire demand as well as reduced natural rubber production. The consumption of butadiene worldwide is expected to develop at an average rate of about 2% + per year. The main source of butadiene is as a by-product in the steam cracking of naphtha and gas oil to produce ethylene and propylene. Steam cracking is a process by which hydroPetition molecules 870180019781, of 12/03/2018, p. 5/17 2/40 carbides are exposed to very hot steam, causing them to break into small molecules. Separation of butadiene from the other products of the steam cracking process typically includes the use of extractive distillation. Other potential sources for the production of butadiene include conversion of feed loads comprising butene and butane compounds and mixtures thereof with butadiene. Isobutene was used for the synthesis of TBK. The market for MTBE, however, is declining, especially in the United States. Thus, a relative abundance of isobutene emerges. The various C4 currents represent alternative feed loads for the production of butadiene. Unfortunately, industrial processes have not been developed or designed to effect efficient conversion and selectivity of butadiene from these sources, particularly when they contain a significant amount of isobutene and / or isobutane. Various processes for the isomerization of butene are described in US patents Nos 3.5.31.545; 4,132,745; 5,157,194; and 6,743,958. The processes described in these patents refer to isomerization reactions rather than the production of butadiene. Reverse isomerization of isobutene in n-butenes is described in Japanese patent applications Nos. 2004-0091 36 and 2004-009138, and literature references Gon Seo et al., The Reversible Skeletal Isomerization between n-Butenes and Iso-butene over Solid Acid Catalysts Today 44 (1998) 215-222, and Lucia M. Petkovic and Gustavo Larsen, Linear Butenos from isobutene over H-Ferrierite: In Situ Studies Using an Oscillating Balance Reactor, J. of Catalysis 191, 1 - 1 1 (2000). These processes refer to the production of butadiene. U.S. Patent No. 6,743,958 by Commereuc et al., Describes an integrated process including the separate steps of: (1) selective hydrogenation of butadiene with isomerization of 1butene to 2-butenes; (2) the isomerization of the (reverse) skeleton of isobuene teno in n-butenes; and (3) the inversion of a fraction rich in 2-butene with ethylene. US patent No. 5,157,194 by Rahmim and others describes a method for the high level conversion of hydrocarbon streams con3 / 40 having n-olefin into iso-olefin-rich product streams using a catalyst composition comprising ZSM-22 microcrystalline. Japanese Patent Application No. 2004-009136 describes isomerization of isobutene into n-butenes using ferrierite or gamma-alumina. Japanese Patent Application No. 2004-009138 describes isomerization of isobutene in n-butenes using gamma-alumina with water coalimentation. US Patents Nos 6242661 and 6849773 and others by Podrebarac incorporated by reference in its entirety, the use of a combination of isomerization reaction of butenes and distillation tower 110 for converting butene into 2-butenes while fractionating to separate isobutene (and isobutane) from 2 ; butenes (and n-butane). All of these references in general refer to isomerization reactions or the use of products for metathesis. None of these references include the dehydrogenation of C4 compounds such as n15 butenes to butadiene. Hydrocarbon Processing, Nov. 1978, pages 131 - 136 by PetroTex, describes the oxideshydrogenation of n-butenes to butadiene. However, that reference does not describe butene isomerization, reverse isomerization, or methods to reduce or eliminate the disadvantageous impacts of isobutene by removing it. Furthermore, this reference does not describe the transformation of the unwanted isobutene into additional productive n-butenes and obtaining production of supplementary butadiene by adding the isobutene conversion. Furthermore, the oxideshydrogenation process described in this article has high costs due to the use of a very large amount of steam to dilute the mixture and limit the rise in the reaction temperature in an adiabatic packed bed reactor. US patents Nos 3,668,147; 4,547,615; and 7,034,195, describe the general production of butadiene. US patent No. 7,034,195 by Schindler and others describes an integrated process for the preparation of butadiene from n-butane via (1) feeding n-butane in a first dehydrogenation zone, autothermally (that is, with some exothermic oxygen reaction, eg combustion, to balance heat demand, but not as a direct oxidative dehydrogenation reaction) conversion n-butane to 1-butene, 2-butenes and optionally butadiene, (2) feed of the first product gas stream in a second dehydrogenation, which non-oxidatively converts 1-butene and 2-butenes to butadiene. US patent No. 4,547,615 by Yamamolo describes oxidative dehydrogenation of monoolefin in a C 4 diolefin conjugated via a mixed metal oxide, with primary metals such as Mo, Bi, Cr, Ni, etc. US patent No. 3,668,147 by Yoshino and others describes various reactions including production of butadiene via mixed metal oxides, mainly Fe / Sb / V or Mo or W7 Te / etc. These references, however, do not describe industrial processes for effectively and selectively producing butadiene from C4 feed charges that contain a significant amount of isobutene and / or isobutane. Processes for the production of butadiene from these feed charges should address, among other issues, the undesirable mode of isobutene in the dehydrogenation step to give butadiene and the almost identical volatilities of isobutene and 1-butene making them essentially impossible to separate by standard distillation. . Of the four species of butene (cis2-butene, trans-2-butene, 1-butene and isobutene), isobutene does not substantially form butadiene via dehydrogenation and in oxohydrogenation is reactive in relation to direct combustion and the formation of some amount of undesirable oxygenated by-products and other by-products. This also results in increased oxygen consumption. In addition, it causes catalyst deactivation. Consequently, it is undesirable to have a significant amount of isobutene in the dehydrogenation feed. If present at a substantial level, isobutene in feed charges must be separated from n-butenes and n-butane. However, it is very difficult to totally separate isobutene from all 11-butenes by distillation, in particular, isobutene and 1-butene are considered to be cocalde because they differ by less than 1 ° C at boiling points, at about -6 ° C at atmospheric pressure. The boiler 5/40 of 2-butenes at 1-4 ° C. Correspondingly, elimination of 1-butene by isomerizing it to 2-butenes allows separation of increased isobutene from n-butenes by distillation according to the processes of the present invention. In addition to obtaining a benefit by excluding isobutene from the nC4 dehydrogenation unit feed, an additional benefit can be obtained by converting the isobutene to additional n-butenes by reverse isomerization to increase the feed to the nC 4 dehydrogenation unit t. Isobutene / n-butene isomerization has historically focused on the formation of isobutene because of the demand for MTBE. Since n-butenes are not typically sold commercially, there was little incentive to research the conversion of reverse isobutene to nbutenes. Isobutane also does not form butadiene via its direct dehydrogenation, although this is not harmful in terms of reacting significantly to unwanted by-products. On the other hand, extra butadiene production can be obtained from isobutane if it is dehydrogenated to give isobutene and then the isobutene undergoes the reverse isomerization described above, creating additional n-butenes that can finally be converted to butadiene. Thus, a unit for dehydrogenating isobutane to give isobutene can be added for that purpose according to that invention. A different dehydrogenation unit for converting nbutane to n-butenes and possibly some amount of butadiene can also be added to the overall process installation according to the present invention. While many industrial processes have been tested for, and are related to, butadiene production, nine have been developed and designed for the conversion of C 4 feed loads containing a significant amount of isobutene and / or isobutane. As such, there is a current and unmet need in the industry for economical and efficient methods for the production of butadiene from these feed loads. 6/40 Summary of the Invention The present invention generally relates to a method for the production of butadiene from mixed C 4 feed charges after removal of isobutene. Isobutene removal is performed using a combination of butenes isomerization reaction and distillation tower. The isomerization reaction inside the tower converts 1-butene to 2butenes while fractionating to separate isobutene from 2-butenes. Any isobutane accompanies the isobutene at the top of the tower, while n-butane accompanies the 2-butenes at the bottom of the tower. The conversion of 1-butene to 2butenes prevents 1-butene from entering the top of the tower and allows it to be transferred in a productive form into the bottom of the tower, where it is used in the production of butadiene without being accompanied by isobutene. An example of a combination of butene isomerization reaction and distillation tower is the CDdclB (R) system by CDTECH, part of its CDHydro (R) technologies described in US patents No. 6,242,661 and 6,849,773 referenced above . The catalyst used for the isomerization reaction of n-butenes in the tower is preferably 0.3-0.4% by weight of Pd on alumina type catalyst. The top from the combination (CDdefB (R)) of the butene isomerization reaction and distillation tower contains mainly isobutene and / or isobutane with only small amounts of n-butenes. The bottom from the combination of butenes isomerization reaction and distillation tower comprises mainly 2-butenes and any n-butane, with only small amounts of isobutene. The bottom of the tower is fed to one or more dehydrogenation reactor units for the conversion of 2-butenes, and if desired, nbutane, to butadiene. An oxydehydrogenation system is used for the conversion of n-butenes to butadiene. If a substantial amount of nbutane is present at the bottom of the tower, or if n-butane is supplied in a separate stream, an additional dehydrogenation unit can be added to convert it to n-butene by methods known to those skilled in the art, such as as (i) by non-oxidative dehydrogenation u7 / 40 using the Lummus CATADIENE® process, (ii) by dehydrogenation processes including oxidatively autothermal dehydrogenation (where oxygen is typically added to burn some (s) compound (s), for example, hydrocarbon or preferably hydrogen generated by the dehydrogenation reaction, in sufficient quantity by its heat generation to satisfy the heat requirement of the endothermic dehydrogenation reaction which is the main reaction), or (iii) by its own oxydehydrogenation. In all these cases in combination with the present invention, dehydrogenation of u-butane is used to produce mainly n-butenes which are then used in the final dehydrogenation reaction unit (s) to produce butadiene. Thus, there are two reaction steps from n-butane to n-butenes to butadiene instead of a single step directly from n-butane to give butadiene. Depending on the amount of nbutane and other considerations, the system for dehydrogenation of nbutane may be upstream of the n-butene oxideshydrogenation unit or downstream in the effluent C4 of the n-butene oxideshydrogenation unit after removal of the butadiene and any of your own recycling chain (s). The CATADIENE® process is capable of being used as a single reaction step on its own, carrying out conversion of partial n-butane to n-butenes and another partial conversion to butadiene, with n-butane and n-butenes effluents both recycled afterwards removal of butadiene product. However, due to the large recycles required, and the total costs, it is more cost effective and to use a 2-step approach with CATADIENE®, and feed the n-butenes produced there for the oxideshydrogenation process of the present invention. As yet another option, and depending on the amount of n-butane and other factors, the additional dehydrogenation unit for converting n-butane to n-butenes or butadiene can be omitted to stop using that portion of the production process of butadiene. The top from the combination of butenes isomerization reaction and distillation tower comprises mainly isobutene and possibly isobutane, plus any light compounds that are present. As an option for added value, the top stream can be fed to a reverse isomerization unit where the isobutene is partially converted to n-butenes, producing a mixed butene stream. The mixed butene stream can be fed back to the combination of the butene isomerization reaction and the distillation tower for the conversion of its 1-butene to newly created 2-butenes and recovery of all the newly created 2-butenes at the bottom, as described above. Conversion of isobutene and recycling of its products in the same way increases the total yield of the process and reduces or eliminates the discharge of the isobutene distillate. When a substantial amount of isobutane is present, the isobutane will enter the top of the butene isomerization reaction and distillation tower combination. In one embodiment, a dehydrogenation unit can be added to convert isobutane to isobutene by methods known to those skilled in the art, for example, by non-reactive dehydrogenation using the Lummus CATOFfN® process, or by other types of dehydrogenation processes. This increases the isobutene content in the tower top stream, which can be exported as desired, or can be sent to the reverse isomerization unit as described above for converting the isobutene to n-butenes. The resulting mixed butenes can be fed to the combination of butenes isomerization reaction and distillation tower, where 1-butene is converted to 2-butenes, the 2-butenes are recovered at the bottom of the tower, and the n-butenes are then converted in the oxideshydrogenation unit of n-butenes. As noted above, both the n-butene oxideshydrogenation unit and, if present, the n-butane dehydrogenation unit can utilize recycle chains. In addition, recycling stream (s) and / or effluent stream from each can be sent to the other. Also, recycle stream (s) and / or effluent stream (s) from dehydrogenation units can be recycled for the combination of butene isomerization reaction and distillation tower. 9/40 Butadiene and other effluent compounds can be recovered separately from the effluent of each of the dehydrogenation units or there may be recovery systems that are shared. Depending on the composition of the effluent streams, the effluent streams can be fed from a distance upstream, for example, to a butadiene extraction unit for the original C stream and its source (current cracker, FCC). In one embodiment, the process of the present invention comprises feeding a mixture predominantly containing only n-butenes and isobutene in a combination of butenes isomerization reaction and a distillation tower capable of converting 1-butene to butenes and distillation to separate isobutene from 2 -butenes. The isomerization of 1 - butene to give 2-butenes allows for better separation of the total amount of nbutenes in the isobutene feed due to (i) sufficient boiling point difference between 2-butenes and isobutene and (ii) conversion of 1-butene to 2-butenes to overcome the lack of a boiling point difference between 1-butene and isobutene. The top stream from the combination of the butene isomerization reaction and the distillation tower comprises mainly isobutene with only small amounts of n-butenes carried, plus any light compounds that are present, including isobutane if present. The bottom stream from the butene isomerization reaction and distillation tower combination mainly comprises 2butenes, with only small amounts of 1-butene and isobutene, plus any heavy compounds, including n-butane if present. A portion of the top stream from the combination of the butene isomerization reaction and the isobutene-containing distillation tower and any unconverted 1-butene can be used as direct reflux and the network top stream can be sent to store or for further processing. For added value (unless the isobutene product has a higher value), a portion of the network top can be fed to a reverse isomerization unit where the isobutene is partially converted to n-butenes, producing the mixed butene stream. The current of 10/40 mixed butenes is fed back to the combination of butene isomerization reaction and distillation tower for converting its newly created 1-butene to 2-butenes and recovering all recently created 2-butenes at the bottom, as described above. Conversion of isobutene and recycling of its products in this way increases the total yield of the process and reduces or eliminates the discharge of the isobutene distillate. A portion of the bottom from the combination of the butene isomerization reaction and the distillation tower can be directly referenced and part or all of the network bottom is fed to one or more dehydrogenation reactor units for the conversion of 2-butenes to butadiene . The butadiene product is separated and sent for storage or other processing. N-butenes that remain after the dehydrogenation units (s) can be discharged in a pure and / or recycled stream or to the dehydrogenation units (s) and / or the butene isomerization reaction combination and distillation tower, with the preferred arrangement depending on the composition of the n-butene recycling stream, especially its content of compounds other than n-butenes. In another embodiment of the processes of the present invention, a feed stream comprising mixed olefins (including isobutene as well as n-butenes) is fed to a combination of butenes isomerization reaction and a distillation tower capable of converting 1-butene into 2 -butenes and distillation to separate isobutene from 2-butenes. In that embodiment of the invention, the feed stream subsequently comprises a substantial amount of n-butane. The feed may also contain isobutane. The top resulting from the combination of butenes isomerization reaction and distillation tower comprises mainly isobutene and isobutane present in the feed, with only small amounts of other butenes. A portion of the top stream can be used as a direct reflux and the network top stream can be sent for storage or other processing. Optionally, part or all of the network top current can be fed to a reverse isomerization unit to partially convert the isobutene to n-butenes, 11/40 producing the mixed butene stream (but the isobutane at the top), part or all of which can be recycled for the combination of butene isomerization reaction and distillation tower. The bottom from the combination of the butene isomerization reaction and the distillation tower comprises mainly n-butane and 2butenes, with only small amounts of 1-butene and isobutene. In one embodiment, the funds contain less than 1% by weight, and preferably less than 0.5% by weight of isobutene. A portion of the fund can be directly referenced and part or all of the network funds are fed to a first dehydrogenation reactor whose primary function is to partially convert the n-butane to n-butenes, while it can also convert a portion of n- butenes to butadiene. At least a portion of the n-butenes from the first dehydrogenation unit is fed to a second dehydrogenation unit that incorporates oxideshydrogenation of the n-butenes to give butadiene. The first dehydrogenation reactor can be a CATAD1ENR® type reactor, in which case your product would normally include a significant amount of butadiene and the CATAD1ENR® unit could still be used as a simple system to dehydrate both n-butane and n-butenes and finally produce butadiene without requiring a second reaction step. However, it is advantageous to operate the CATADIENE® unit in combination with an oxidehydrogenation unit and to use conditions in the CATADIENE® unit that maximize the generation of n-butenes and minimize butadiene. Butadiene produced in the first dehydrogenation reactor, such as the CATADIENE® customized or moderate unit (which should also be called a CATOF1N® unit), can be separated or fed to the butadiene product line. Hydrogen can also be separated as a by-product for external or internal use, and water can also be condensed and separated. Residual residual N-butane can be recycled to the first dehydrogenation unit (n-butane) and / or fed forward as a diluent to the second oxydehydrogenation unit (n-butenes). Alternatively, to these separations, part or all of the 12/40 effluent from the n-butane dehydrogenation unit can be fed directly to the n-butene oxideshydrogenation unit, if it is advantageous in terms of monitoring the separations between the two units. As an additional option, a combination of both approaches can be used. That is, a portion of the effluent from the n-butane dehydrogenation unit can be fed directly to the n-butene oxideshydrogenation unit, while a different portion may undergo separations before its n-butenes are also fed to the n-butene unit. oxideshydrogenation of n-butenes. As described above, in one mode of operation, the first dehydrogenation unit obtains dehydrogenation from the n-butane content to nbutenes, while the second dehydrogenation unit uses oxideshydrogenation to convert the n-butenes to butadiene. An alternative operating scheme, which is especially useful when there are substantial n-butenes at the bottom, is to reverse the order and dehydrogenate the n-butenes first, followed by dehydrogenation of the n-butane in the effluent hydrocarbon stream of the oxideshydrogenation unit of n-butenes. The presence of nbutane in the oxideshydrogenation units of n-butenes does not reduce the conversion of n-butenes, and can be beneficial in diluting the exothermic reaction and avoiding flammable process mixtures by making the process mixture composition richer in hydrocarbon. It can be advantageous to form the concentration of n-butane per recycle. Removing n-butenes present in the feed to the dehydrogenation units prior to dehydrogenation of the n-butane and creating additional nbutenes, by converting them to the n-butene oxideshydrogenation units first, then removing the butadiene that is created, can be advantageous. The effluent C 4 stream from the n-butene oxidehydrogenation unit contains virtually all of the n-butane since it is essentially inert in the n-butene oxidehydrogenation unit. With this order of the dehydrogenation units, having only a minimum amount of butenes in the feed for the n-butane dehydrogenation unit reduces the interference of n-butenes in the desi13 / 40 hydrogenation of n-butane to give n-butenes. In addition, the total hydrocarbon flow to the n-butone dehydrogenation unit becomes greatly reduced. If the n-butane content in the feed stream and turret bottom is low, it may be desirable to undergo inclusion of the first dehydrogenation unit, and the production of butadiene which corresponds to the conversion of the n-butane content, and revert to the embodiment which uses only the n-butene oxideshydrogenation unit. Depending on the compositions, the separation of butadiene in the effluents of the two dehydrogenation units can be carried out in a shared butadiene separation system (for example, extraction) or in a butadiene extraction unit for the original C 4 stream from its source (chain cracker, FCC). In another embodiment of the invention, a first feed stream comprising C 4 mixed olefins is fed for the combination of butenes isomerization reaction and a distillation tower capable of converting 1-butene to 2-butenes and distillation to separate 2- isobutene. butenes. The feed may also contain n-butane and / or isobutane. A portion of the top can be used as a direct reflux and the network top stream for storage or other processing. For added value (unless isobutene product has a higher value), a portion at the top of the network can be fed into the reverse isomerization unit and converted to a mixed C 4 olefin stream, plus any additional compounds, and partially or fully recycled to give the combination of butenes isomerization reaction and distillation tower as described above for other embodiments. In this embodiment of the invention, a second, separate feed stream comprising n-butane, and without substantial n-butenes, is fed directly to a first dehydrogenation reactor capable of partially converting n-butane to n-butenes, without feeding that n -butane through the combination of butenes isomerization reaction and distillation tower. For this n-butane current to deflect the 14/40 combination of butenes isomerization reaction and distillation tower, needs to be essentially free of isobutene, although the stream may contain some amount of isobutane. The first dehydrogenation reactor can be a CATADI KNK® customized type reactor as described above. Where the bottom stream of the tower does not contain a substantial amount of n-butane, the bottom from the combination of the butene isomerization reaction and the distillation tower can bypass the first dehydrogenation reactor (n-butane) and can be fed directly to the second dehydrogenation reactor system to convert the n-butenes at the bottom of the tower into butadiene. The second dehydrogenation system (nbutenes) incorporates the use of oxideshydrogenation. The effluent from the first dehydrogenation unit (nbutane) can be fed to the second dehydrogenation unit (n-butenes) directly or with some intermediate separations, recycling, etc. Each dehydrogenation unit can have one or more effluent recycle streams, and recycle streams can be recycled to feed the dehydrogenation unit, the other dehydrogenation unit, or the butene and isomerization reaction combination. distillation tower. In an alternative embodiment of the process, the second feed stream, which comprises n-butane and is essentially free of isobutene, can also contain substantial n-butenes. Alternatively, the second (or third) feed stream may comprise n-butenes without substantial n-butane and again be essentially free of isobutene. In this case, as discussed for the previous embodiment, it may be desirable to feed the second (or third) feed stream in the first place to the n-butene oxideshydrogenation system, with the effluent C4 stream from that unit then being fed to the n-butane dehydrogenation unit (ie the second dehydrogenation unit starts followed by the first). In another embodiment, the first supply chain 15/40 may contain a substantial amount of n-butane as well as mixed C4 olefins. In that case, it may be advantageous to feed the mesh bottom of the combination of butenes isomerization reaction and distillation tower to the first dehydrogenation unit (n-butane) together with the second feed stream comprising n-butane and essentially no isobutene. Alternatively, the preferred processing scheme can be sent the network funds to the second oxideshydrogenation unit (n-butenes) followed by the first dehydrogenation unit (n-butane). In addition, there is an option to include the entire n-butane dehydrogenation unit and use only the n-butene oxideshydrogenation unit. As previously described, each dehydrogenation unit can have its own recycle (s), and its recycle stream (s) can be sent to your feed, to the other dehydrogenation unit, or to the reaction combination butomer isomerization and distillation tower. As described above, depending on compositions, the separation of butadiene in the effluents of the two dehydrogenation units can be carried out in a shared butadiene separation system (for example, extraction), or one or more of the effluent and recycle streams can be fed to a butadiene extraction unit for the original C4 stream from its source (stream cracker, FCC). In another embodiment of the present invention, a feed stream comprising both mixed C4 and mixed C4 olefins, thus both isobutane and isobutene as well as nbutane and n-butenes, is fed to the combination of butene isomerization reaction and distillation tower capable of converting 1-butene to 2-butenes, and distillation to separate isobutane and isobutene from n-butane and 2-butenes. A portion of the top from the butene isomerization reaction and the distillation tower can be used as direct reflux and the network top stream for storage or other processing. For added value (unless isoC products have a higher value), a portion of the 16/40 network top can be fed to the reverse isomerization unit where the isobutene is partially converted into n-butenes, producing an isobutane plus mixed butene current. The most common isobutane of mixed butenes is recycled and is fed back to the combination of butenes isomerization reaction and distillation tower for the conversion of the 1butene formed in the 2-butenes reverse isomerization unit and recovery of the 2-butenes at the bottom, as described above. When the feed contains significant isobutane, the isobutane must be purged from the top system. This can be accomplished by simply purging a sufficient amount of the top stream before or after the reverse isomerization unit, although this incorporates losses of isobutene and possibly n-butenes. Alternatively, isobutane can be purged by carrying out another distillation to separate isobutane from isobutene, for example, isobutane as the top chain and isobutene as the side chain. Yet another option is to introduce the dehydrogenation unit at the top, such as a CATOFfN® unit, capable of converting isobutane to isobutene. The outlet of the isobutane dehydrogenation unit comprises a substantially increased level of isobutene, and at least a portion can be fed to the reverse isomerization unit capable of converting isobutene to mixed C4 olefins. If isobutene is a desired product, a portion of the product from the isobutane dehydrogenation unit can be used for that purpose. The output of the reverse isomerization unit is fed back to the combination of butenes isomerization reaction and distillation tower. Conversion of both isobutane and isobutene and recycling of their products thereby obtains several increases in the total yield of the butadiene process (and / or other provisions of n-butenes) and reduces or eliminates the discharge of the isoC4 distillate. The bottom from the combination of the butene isomerization reaction and the distillation tower comprises 2-butenes and n-butane, with only small amounts of 1-butene and isobutene. A portion of the fund can be directly referred and part or all of the network funds 17/40 can be fed to a first dehydrogenation reactor capable of converting n-butanes to n-butenes. As described above, the first dehydrogenation reactor can be a CATADIENE® type reactor customized for use in the process. At least a portion of the n-butenes produced in the first dehydrogenation reactor is fed to the second dehydrogenation reactor system, which incorporates oxideshydrogenation where the nbutenes are converted to butadiene. If produced for a significant amount, as in a CATADIENE® unit, butadiene and / or hydrogen produced in the first dehydrogenation reactor (n-butane), and water in its effluent, can be separated from the n-butenes in the effluent. Butadiene can be fed to the butadiene product line, and other separate compounds can be sent to its relevant provisions before n-butenes are fed to the second dehydrogenation reactor system. Alternatively, the effluent compounds from the n-butane dehydrogenation reactor system can be included, at least in part, in the feed for the nbutene oxideshydrogenation reactor system without separation steps between the two dehydrogenation systems. As discussed above, an alternative processing scheme may be to feed the network bottoms of the combination of butenes isomerization reaction and distillation tower to the second oxideshydrogenation unit (n-butenes), followed by feeding the effluent from the oxideshydrogenation of n-butenes to the first (n-butane) dehydrogenation unit. In addition, there is the option to grant inclusion of the n-butane dehydrogenation unit together using only the n-butene oxideshydrogenation unit. As previously described, each dehydrogenation unit can have its own recycle (s), and its recycle stream (s) can be sent to its feed, to the other dehydrogenation unit, or to the isomerization reaction combination of butenes and distillation tower. As described above, depending on the compositions, the separation of butadiene in the effluents of the two dehydrogenation units 18/40 can be carried out in a shared butadiene separation system (eg extraction), or one or more of the effluent or recycle streams can be fed to a butadiene extraction unit from the original C4 stream from its source (cracker current, FCC). In another embodiment of the processes of the present invention, a feed stream comprising mixed C4 paraffins, with or without substantial C4 olefins, is fed to the distillation tower where isobutane is separated from n-butane. A portion of the top of the distillation tower can be used as a direct reflux and the network top stream can be sent for storage or other processing. At least a portion of the network top stream is fed to a dehydrogenation unit, such as a CATOFIN® unit, capable of converting isobutane to isobutene. At least a portion of the outlet of the isobutane dehydrogenation unit, now comprising substantial isobutene, is fed to the reverse isomerization unit capable of converting isobutene to mixed C4 olefins. At least a portion of the output from the reverse isomerization unit, now comprising substantial newly created n-butanes can be added to the butadiene production, is fed back to the distillation tower, which is now the combination of butene isomerization reaction and tower processing distillation of a complete mixture of mixed paraffins and mixed C4 olefins, which converts 1-butene to 2-butenes and distills to separate isobutane and isobutene from n-butane and 2-butenes. The bottoms of the butene isomerization reaction and distillation tower combination comprise n-butane, plus 2-butenes derived from isobutene dehydrogenation at the top followed by its reverse isomerization and return to the tower. A portion of the fund can be directly referenced and part or all of the network funds can be fed to a first dehydrogenation reactor capable of converting n-butane to n-butenes. As described above, the first dehydrogenation reactor can be a CATADIENE® type reactor customized for use in the process. At least one 19/40 portion of the n-butenes produced in the first dehydrogenation reactor is fed to the second dehydrogenation reactor system, which incorporates oxideshydrogenation where the n-butenes are converted to butadiene. If produced for a significant amount, as in a standard CATADIENE® unit, butadiene and / or hydrogen produced in the first dehydrogenation reactor (n-butane), and water in its effluent, can be separated from the n-butenes in the effluent. Butadiene can be fed to the butadiene product line, and other separate compounds can be sent to its relevant provisions before, n-butenes are fed to the second dehydrogenation reactor system. Alternatively, the effluent compounds from the n-butane dehydrogenation reactor system can be included, at least in part, in the feed to the n-butene oxideshydrogenation reactor systems without separation steps between the two dehydrogenation systems. As discussed above, in an alternative processing scheme, the network bottoms of the combination of butenes isomerization reaction and distillation tower is fed to the second oxideshydrogenation unit (n-butenes), followed by feeding the effluent from the oxideshydrogenation of n-butenes for the first (n-butane) dehydrogenation unit. In addition, there is the option to include the entire n-butane dehydrogenation unit and use only the n-butene oxidehydrogenation units. As previously described, each dehydrogenation unit can have its own recycle (s), and its recycle stream (s) can be sent to its feed, to the other dehydrogenation unit, or to the isomerization reaction combination of butenes and distillation tower. Depending on the compositions, the separation of butadiene in the effluents of two dehydrogenation units can be carried out in a shared butadiene separation system (for example, extraction), or one or more of the effluent or recycle streams can be fed to an extraction unit. butadiene to the original C4 current from its source. 20/40 It would be understood that the initial feed (s) to be processed, and also some recycling streams, may contain additional compounds in addition to the C4 olefins and paraffins that have been discussed. These may include C diolefins and acetylenic compounds, as well as compounds other than C4 hydrocarbons. Additional processing steps can be added, by methods known to those skilled in the art, to convert some of the compounds into additional C4 olefins or paraffins, for example, by selective hydrogenation, or to remove compounds when required for other acceptable processing. An advantage of the present invention is an economical and effective process configuration using a minimum number of steps to effect high butadiene conversion and selectivity from mixed C4 (olefins and / or paraffins) feeds that contain a significant amount of isobutene and / or isobutane. This advantage is given by way of non-limiting examples only, and additional advantages and benefits will be readily apparent to those skilled in the art by virtue of the description given here. Brief Description of Drawings Figure 1 is a flow chart showing an embodiment of the present invention in which butadiene is produced by oxideshydrogenation of n-butenes at the bottom of a combination of butene isomerization reaction and distillation tower which is fed with a mixed C4 olefin feed charge. containing the significant amount of isobutene as well as n-butene (s). Figure 2 is a flowchart showing another embodiment of the present invention in which butadiene is produced by oxideshydrogenation of n-butenes at the bottom of a combination of butenes isomerization reaction and distillation tower which is fed with a feed stream comprising C4 olefins mixed with n-butane. Figure 3 is a flow chart showing another embodiment of the present invention in which a separate stream of n-butane is fed to a dehydrogenation unit for converting n-butanes to 21/40 n-butenes. Alternatively, a separate stream of nC4 can be fed first to the n-butene oxideshydrogenation unit, especially if it comprises substantial content of n-butenes. Figure 4 is a flow chart showing an embodiment of the invention in which all or part of a second feed stream containing n-butenes is fed directly to the oxydehydrogenation unit. Figure 5 is a flowchart showing another embodiment of the present invention in which butadiene is produced by oxideshydrogenation of n-butenes at the bottom of a combination of butene isomerization reaction and distillation tower which is fed with a feed stream comprising both C4 mixed olefins and mixed C4 paraffins. Detailed Description of the Invention The present invention relates to improved processes for the production of butadiene from C4 feed charges that contain a significant amount of isobutene and / or isobutane, via oxydehydrogenation after the first removal of isobutene without loss of 1-butene as feed of high value. A feed stream comprising a mixture of C4 olefins is fed to the combination of butenes isomerization reaction and distillation tower capable of converting 1-butene to 2-butenes and separation of isobutene from 2-butenes by distillation. In some embodiments of the invention, the feed stream may further comprise C4 paraffins. The top from the combination of the butene isomerization reaction and the distillation tower contains mainly isobutene, with only small amounts of n-butenes. Any isobutane would also be present. Optionally, isobutene in a top stream can be partially converted to n-butenes by feeding a top stream to the reverse isomerization unit to convert the isobutene to a mixed C4 stream. The output of the reverse isomerization unit is then fed back to the combination of bu22 / 40 tenos isomerization reaction and distillation tower, as an additional source of n-butenes for the production of butadiene. The funds from the combination of the butene isomerization reaction and the distillation tower comprise mainly 2-butenes with only small amounts of other butenes. Any n-butane would also be present. The funds are fed to an oxideshydrogenation unit, where the n-butenes present in the funds are converted to butadiene. In another embodiment of the invention, as described in detail below, a significant amount of n-butane can be included in the feed for the combination of butenes isomerization reaction and distillation tower, in addition to mixed butenes. The top from the tower is as described in the first embodiment, while the bottom from the combination of butenes isomerization reaction and distillation tower can be fed to a first dehydrogenation unit, such as, for example, the CATADIENE type unit. ®customized, where n-butane is partially converted to n-butenes and some of the n-butenes can be partially converted to butadiene. The outlet from the first dehydrogenation unit can be separated into a stream of butadiene product and an n-butene stream that is fed to a second dehydrogenation unit, which incorporates the use of oxydehydrogenation to convert the n-butenes to butadiene. Hydrogen produced in the first dehydrogenation unit can also be separated, as well as water in its effluent. Optionally, the outlet from the first dehydrogenation unit can be fed directly to the oxideshydrogenation unit without intermediate separations. Alternatively, in one embodiment, the bottom from the combination of butene isomerization reaction and distillation tower can be fed to the second dehydrogenation unit first, and after that a portion of the effluent from the second dehydrogenation unit can be fed to the first dehydrogenation unit Another option with this feed mixture (n-butane 23/40 together with mixed butenes) is to undergo inclusion of the first dehydrogenation unit, and the production of butadiene which corresponds to the conversion of the n-butane content, and use only the n-butene oxideshydrogenation unit. In another embodiment, a stream containing n-butane and essentially no isobutene can be fed into a stream separate from the mixed butene feed that contains significant isobutene and is being processed in a combination of butene isomerization reaction and distillation tower. The separated n-butane stream can be sent directly to a first dehydrogenation unit to convert the n-butanes to n-butenes (and possibly some butadiene). In this case, the bottom from the combination of butenes isomerization reaction and distillation tower can be sent together with the output of the first dehydrogenation unit, to the second dehydrogenation unit to convert the n-butenes to butadiene using oxideshydrogenation. If a separate n-C4 feed stream contains substantial nbutenes, with or without n-butane, but does not yet contain significant isobutene and requires processing in the combination of butenes isomerization reaction and distillation tower, it can be sent to the unit of n-butenes oxideshydrogenation first, and after that a portion of the effluent from the n-butenes oxideshydrogenation unit can be sent to the n-butane dehydrogenation unit. If the mixed butene feed stream containing significant isobutene and being processed in the combination of the butene isomerization reaction and the distillation tower also contains significant n-butane, the bottoms of the tower can be sent first to the second dehydrogenation unit (n oxideshydrogenation) -butenes) as stated, or vice versa, for the first dehydrogenation unit (n-butane dehydrogenation) depending on the composition and other factors. As with the previous embodiment, an additional option with this total feed mixture (n-butane and mixed butenes) is to suffer 24/40 inclusion of the first dehydrogenation unit, and the production of butadiene which corresponds to the conversion of the n-butane content, and uses only the n-butene oxideshydrogenation unit. In yet another embodiment, both the feed stream comprising both mixed C4 paraffins and mixed C4 olefins are fed into the combination of butene isomerization reaction and distillation tower where 1-butene is converted to 2-butenes, and isobutane and isobutene are separated from n-butane and 2-butenes. Optionally, the top isobutene can be partially converted to n-butenes using a reverse isomerization unit. The mixed C4 stream is back recycled for the combination of butenes isomerization reaction and distillation tower. Since the feed has significant isobutane, the isobutane must be purged from the top system. This can be accomplished by simply purging a sufficient amount of the top stream before or after the reverse isomerization unit, although it also results in losses of isobutene and possibly n-butenes. Alternatively the isobutane can be purged by carrying out another distillation to separate isobutane from isobutene, for example, isobutane as a top chain and isobutene as a side chain. Yet another option is to introduce an isobutane dehydrogenation unit at the top to partially convert the isobutane to isobutene, then feed the effluent from that to the reverse isomerization unit. With this combination of units, almost all isoC4s, saturated as well as unsaturated, can be transformed into n-butenes and finally butadiene. In this embodiment, the background from the combination of the butene isomerization reaction and the distillation tower, comprising 2butenes and n-butane, can be processed as in the two previous embodiments. In yet another embodiment of the processes of the present invention, a feed stream comprising C4 mixed paraffins, with or without substantial olefins, is fed into the combination of the butene isomerization reaction and the distillation tower where isobutane is 25/40 separated from n-butane. The top from the butene isomerization reaction combination, and the distillation tower is fed to a dehydrogenation unit to partially convert the isobutane to isobutene and its product is fed to the reverse isomerization unit capable of partially converting isobutene into C4 mixed olefins. The output of the reverse isomerization unit is fed back to the combination of the butene isomerization reaction and the distillation tower, which now contains 2-butenes and also 1-butene to convert to 2-butenes, as well as isobutene to distill back to the top, in addition to the original mixed C4 paraffins. The bottom from the combination of the butene isomerization reaction and the distillation tower comprises n-butane and 2-butenes, and can be processed as in the previous embodiments containing these compounds. Figure 1 shows an embodiment of the present invention in which butadiene is produced from a mixed olefin feed stream (10). The mixed olefin feed stream generally comprises isobutene, 1-butene and 2-butenes, which can be present in the feed stream in any proportions. Isobutene and 1-butene have very similar boiling points called coebulators. Both boil at ~ 6 ° C at atmospheric pressure. Separation of two is difficult by distillation alone. On the other hand, 2-butenes boil at about 1 -4 ° C. To capitalize on this increased difference in relation to isobutene, 1-butene is isomerized to give 2-butenes in the combination of butenes isomerization reaction and distillation tower (15), which allows isobutene separation from all n-butenes by distillation and increases the process yield and selectivity. The mixed olefin C4 feed stream (10) is introduced into the butene isomerization reaction and distillation tower (15) combination to convert 1-butene in the feed stream into 2butenes. An example of this combination of butene isomerization reaction and distillation system is the CDdclB (c) system by CDTKCH, part of its CDHydro® technologies. The 2-butenes in the mixture are separated from the isobutene and residual 1-butene by distillation. The top stream (12) originating from the combination of butenes isomerization reaction and distillation tower (15) contains substantially the entire feed stream, with small amounts of n-butenes. Typically, the top stream comprises 5 wt% or less of nC4s (n-butane plus n-butenes). The bottoms (22) arising from the combination of the butene isomerization reaction and the distillation tower (15) consist substantially of 2-butenes, with only small amounts of 1-butene or isobutene. Typically, the bottom stream comprises 1% by weight or less of iC4s (isobutane plus isobutene) and 1-5% by weight or less of 1-butene. The combination of the butene isomerization reaction and the distillation tower (15) includes a catalyst. The catalyst can be selected from any known catalyst used in the industry for the isomerization of olefin. In some embodiments, the catalyst is Pd. In a particular embodiment, the catalyst is 0.3-0.4% by weight of Pd on alumina. Typically, the combination of butene isomerization reaction and distillation tower 15 is operated at a pressure of between 344.7 kPa (50 psig) (1 psig = 0.07 kg / cm 2 manometer) and 758.4 kPa (110 psig) (1 psig = 0.07 kg / cm 2 gauge). The top stream comes out of the combination of butene isomerization reaction and distillation tower (15) at a temperature between 26.6 ° C (80 ° F) and 82.2 ° C (180 ° F), and the current bottom comes out of the combination of butenes isomerization reaction and distillation tower 15 at a temperature between 37.7 ° C (100 ° F) and 121 ° C (250 ° F). Heat for the distillation process can be provided by any means known to those skilled in the art, such as by using a re-boiler. The top stream 12 is typically condensed in a reflux condenser 17 and a portion is typically returned to the butene isomerization reaction combination and distillation tower 15 as reflux 14, in a ratio of 0.5 to 33. If desired , a portion of the net top 16, i.e. the top stream 12 minus the backflow stream 14, can be discharged from the facility for disposal, storage or other processing via line 18. It would be understood that line 18 can represent a single line or several different lines, possibly with 27/40 different compositions. Optionally, a portion of the network top stream 20 can be further processed and recycled to the combination of butene isomerization reaction and distillation tower 15. In this embodiment, a portion of the network top stream is fed through line 40 for a reverse isomerization unit 45) to convert isobutene to n-butenes, creating a mixed C4 current. The reverse isomerization unit can be of any type known to those skilled in the art. Part or all of the output from the reverse isomerization unit 45 is fed through line 44 back into the butene isomerization reaction combination and distillation tower 15. Optionally, part of the output from the reverse isomerization unit 45 can be sent to other arrangements via line 46), it may represent several lines for various destinations, and some portion of the effluent from the reverse isomerization unit 45 can be recycled via line 42 back to the supply current of the reverse isomerization unit 40. A portion of the bottom stream 22 from the combination of the butene isomerization reaction and the distillation tower 15, comprising 2-butenes, is typically referred directly to a re-boiler 21 and is fed back to the tower. A portion of the network bottoms (bottom chain 22 minus a portion is fed back to tower 24) can be discharged from the facility for storage or other processing 26. Part or all of the network bottoms are fed through line 70 to feed 72 to an oxideshydrogenation unit 75 to convert the 2-butenes to butadiene. The oxidehydrogenation unit 75) can be any type known to those skilled in the art for converting olefins to dienes. The oxidehydrogenation unit 75 includes a catalyst. Any catalyst used for converting olefins to dienes can be used. Catalysts that are particularly suitable for the oxideshydrogenation of n-butenes to 1,3-butadiene are generally based on mixed Mo-Bi metal oxide systems. Their preparations are described, 28/40 for example, in US patent No. 3,911,039 (Moi2BiFe3Co4, 5 NÍ2,5Snoo, 5Ko, iOx), in US patent No. 4,424,141 (Mo 12 BiFe 3 Co4,5NÍ2,5Po, 5Ko o, iO x ), in US patent No. 4,547,615 (M012B1 Feo, iNÍ8ZrCr 3 Ko, 20x), in US patent No. 7,034.95 (Moi2Bo, 6Fe 3 Co 7 Cro, 5Sii, 6Ko, o80 x , in US patent No. 4,423,281 (Mo 12 BiCr 3 NO 8 Li 2 Pbo, 50 x ), and US patent No. 4,336,409 (Moi2BiCr 3 Ni 6 Po, 5Cd2FeO x ). In the process according to the invention, preferred catalyst systems are described, for example, in US Patent No. 3,911,039 (Mo 12 BiFe 3 Co4,5NÍ2,5Sbo, 5Ko, iOx) and in US Patent No. 7,034,195 (Moi2Bio, 6Fe 3 Co7Cro, 5Sii, 6Ko, o80x) · The oxydehydrogenation unit 75 preferably operates at a pressure of between 0 and 689.5 kPa (0 psig and 100 psig) (1 psig = 0.07 kg / cm 2 of marking force), and a temperature of between 287 ° C (550 ° F) and 583 ° C (850 ° F). The butadiene produced in the oxideshydrogenation unit 75 is separated from other effluent compounds by methods known to those skilled in the art, for example, incorporation of extractive distillation. Any residual n-butenes, plus other useful compounds to be recycled, for example, n-butane and other non-reactive paraffins as diluents for the reaction can be recycled to the oxideshydrogenation unit 75. Residual n-butenes can be recycled through line 74 to match the feed to the oxideshydrogenation unit 75 in the feed stream 72 or through line 78 to match the feed stream 10 for the butene isomerization reaction combination and the distillation tower 15. By-products and compounds not reacted, etc., are purged from the system via that discharge line (s) 80, which may constitute a line or several lines, possibly with different compositions. Recycling via line 78 for the combination of butene isomerization reaction and distillation tower 15 instead of or in addition to line 74 may have another path to remove quantities of iC4s and lighter compounds that can accompany desirable recycling compounds. If both lines 74 and 78 are used, they can have different compositions. The butadiene product is fed through line 82 to 29/40 storage or other processing. In another embodiment of the invention shown in figure 2, butadiene is produced from a feed stream (10) comprising n-butane in addition to mixed C4 olefins. The feed stream may also contain isobutane. The feed stream (10) is introduced into a combination of butene isomerization reaction and distillation tower (15) of the type described above. The 1-butene in the feed stream is converted to 2-butenes in an isomerization reaction inside the tower's catalyst. The top stream (12) from the combination of the butene isomerization reaction and the distillation tower (15) contains substantially all of the isobutene from the feed stream, but any isobutane that is present, with only small amounts of n-butenes and n-butane. Typically, the top stream comprises 5 wt% or less of cC4 (n-butane plus n-butenes). The bottoms (22) from the combination of the butene isomerization reaction and the distillation tower (15) consist substantially of 2-butenes and n-butane, with only small amounts of 1-butene or isobutene. Typically, the bottom stream comprises 1 wt% or less of iC4s (isobutene plus isobutene) and 1 -55 wt or less of 1-butene. A portion of the top stream is typically returned for the combination of butene isomerization reaction and distillation tower 15 as reflux 14. A portion of the network top 16, i.e., top stream 12 minus the reflux stream 14, can be discharged from the facility for disposal, storage or other processing via line (s) 18. Optionally, all or a portion of the network top stream 20 can be further processed and recycled to the combination of butene isomerization reaction and distillation tower as described above and as follows. The portion of the network top stream 20 being recycled is fed through line 40 to the reverse isomerization unit 45 to convert isobutene to nbutenes. Part or all of the output from the reverse isomerization unit 45 can be fed via line 44 back to the butene isomerization reaction combi30 / 40 and distillation tower 15. If desired, part of the output from the isomerization unit Reverse can be sent to other arrangements via line (s) 46, and some portion of the effluent from the reverse isomerization unit 45 can be recycled back to the feed stream 40 to the reverse isomerization unit via line 42. The bottoms 22 arising from the combination of the butene isomerization reaction and the distillation tower 15 comprise 2-butenes and n-butane. A portion of the bottom is typically referenced to a re-boiler 21 and is fed back to the tower 15 via line 24. A portion of the bottom mesh can be discharged from the facility for storage or other processing via line 26. Part or a all of the network bottoms can be fed via line 50 to feed 54 to a first dehydrogenation unit 55 capable of partially converting n-butane to n-butenes. Optionally, dehydrogenation unit 55 can be configured to also convert n-butenes to butadiene. The first dehydrogenation unit 55 can incorporate a CATADIENO (c) type reactor, in which case your product would normally include a significant amount of butadiene, but the CATADIENO® unit can be operated to use conditions that maximize n- butenes and minimize butadiene. In such an operating mode, it can be called a CATOKIN® unit or it can also be called a CATADIENO® (moderate) unit. At least a portion of the n-butenes produced in the n-butane dehydrogenation reactor 55 is fed via line 64 to an oxideshydrogenation reactor 75 of the type described above, where the n-butenes are converted to butadiene. Butadiene produced in the first dehydrogenation unit 55 can be separated and fed through line 60 to the butadiene product line 84. Hydrogen can also be separated and removed as a by-product through 62 for external or internal use. Water can be condensed, separated and removed via line 62. Some portion of the n-butenes can be discharged 62 if desired for use other than 31/40 conversion to butadiene. It would be understood that line 62 can represent a single line or several different lines, possibly with different compositions, for the removal of any unreacted product, by-products or feed components. Residual n-Butane and other compounds can be separated and recycled to the first dehydrogenation unit 55 via line 56. Alternatively or in addition, a portion of the residual nbutane can be recycled by combining it with the feed stream 10 for the combination of isomerization reaction of butenes and distillation tower 15 through line 58, especially if there are any iC4s or lighter compounds to purge via that route. In another embodiment, some portion of the residual n-butane is fed forward through line 64, together with or separately from the n-butenes, to the second dehydrogenation unit 75. In another embodiment, part or all of the effluent from the first dehydrogenation unit can be fed, without the separation of by-products and n-butane described above, directly through line (64) to the second dehydrogenation unit 75, if advantageous regarding the separation between the two units. As an additional option, a combination of both approaches can be used. That is, a portion of the entire effluent from the first dehydrogenation unit can be fed directly through line (64) to the second dehydrogenation unit 75, while a different portion may undergo separations before its n-butenes are also fed through the line 64 for the second dehydrogenation unit 75. In the embodiments described above, the first dehydrogenation unit 55 obtains dehydrogenation of the n-butane content at the bottom of the tower in n-butenes, while the second (n-butenes) dehydrogenation unit 75 converts the n-butenes with butadiene using oxideshydrogenation. In other embodiments of the process shown in figure 2, which are especially useful when there are substantial n-butenes in the tower bottom stream, the order described above is reversed and at least a portion of the network bottoms of the butene isomerization reaction combination and tower 32/40 distillation 15 is fed through line 70 to dehydrogenate the nbutenes first in the oxideshydrogenation unit 75, followed by sending the n-butane portion of the effluent from the n-butenes oxideshydrogenation unit 75 to the n dehydrogenation unit -butane 55 via line 76 and / or possibly for the combination of butenes isomerization reaction and distillation tower 15 via line 78. In this embodiment, feed 72 for the n-butene oxideshydrogenation unit 75 is a combination of direct bottoms of the combination of butene isomerization reaction and distillation tower 15 provided via line 70 together with n-butene stream (s) 64 from the n-butane dehydrogenation unit 55. The total feed to the oxideshydrogenation unit of nbutenes 75 may also include recycling 74 of its own effluents. Alternatively, a first portion of the bottoms from the butene isomerization reaction combination and distillation tower 15 can be fed to the n-butane dehydrogenation unit 55 via line 50 and and the second portion of the bottom from the butane reaction combination. butenes isomerization and distillation tower 15 can be fed to the n-butenes oxideshydrogenation unit 75 via line 70. In yet another embodiment (not shown in figure 2, but with the same configuration as shown in figure 1), the n-butane dehydrogenation unit 55 and the butadiene production that corresponds to the conversion of the n-butane content may have left to use, and the n-butene oxideshydrogenation unit 75 can be used alone to convert n-butenes to butadiene, while n-butane is purged via line 80. Although not shown in figure 2, the separation of butadiene in the effluents of the two dehydrogenation units 55 and 75 can be carried out in a shared butadiene separation system (for example, extraction), if desired, one or more effluent or recycle streams upstream, for example, to a butadiene extraction unit for the original C4 stream from its source ( 33/40 current, FCC). In another embodiment of the present invention shown in figure 3, a first feed stream 10 comprising a mixed C4 olefin stream is fed to the butene isomerization reaction combination and distillation tower 15 of the type described above, and a second stream feed 52 comprising n-butane and essentially isobutene free is fed to an n-butane dehydrogenation unit 55 via line 54. As described above, in the combination of butenes isomerization reaction and distillation tower 15, 1butene in the first supply current is converted to 2-butenes. The 2-butenes in the mixture are separated from the isobutene and residual 1-butene by distillation. The top stream 12 from the combination of the butene isomerization reaction and the distillation tower 15 contains substantially all of the isobutene, plus any isobutane that is present in the first feed stream, with only small amounts of n-butenes. The top stream is cooled in the cooler 12. The bottoms 22 from the combination of the butene isomerization reaction and the distillation tower 15 are substantially 2-butenes, plus any n-butane that may be contained in the first feed stream, with only small amounts of 1-butene or isobutene. A portion of the top stream 12 is typically returned for the combination of butene isomerization reaction and distillation tower 15 as reflux 14. A portion of the top net 16 can be discharged from the facility for disposal, for storage or other purposes. processing via line (s) 18. Optionally, All or a portion of the network top stream 20 may undergo further processing and be recycled to the butene isomerization reaction combination and distillation tower 15 as described above and as follows. The portion of the network top stream to be recycled is fed through line 40 to the reverse isomerization unit 5 to convert isobutene to n-butenes. Part or all of the output from the reverse isomerization unit 45 is fed through line 44 back to the combination of isome reaction34 / 40 butene rization and distillation tower 15. Part or all of the output can be sent to other arrangements 46, and some portion of the effluent from the reverse isomerization unit 45 can be recycled 42 back to the unit via the feed line 40. The bottoms 22 arising from the combination of butenes isomerization reaction and distillation tower 15 comprise 2-butenes and any n-butane that is present. A portion of the bottom is typically referenced to the re-boiler 21 and is fed back to the tower 15 via line 24. A portion of the bottom of the net can be discharged from the facility for storage or other processing 26. Part or all The network funds from the combination of butenes isomerization reaction and distillation tower 15 can be fed through line 70 to the oxidehydrogenation unit 75 for the conversion of 2-butenes to butadiene. The second feed stream 52 comprising nbutanes can be fed through line 54 to the first dehydrogenation unit 55 capable of partially converting n-butane to n-butenes. Optionally, the first dehydrogenation unit 55 can be configured to also convert n-butenes to butadiene. The first dehydrogenation unit 55 can incorporate a CATADIENO® type reactor, in which case its product would normally include a significant amount of butadiene but the CATADIENO® unit can be operated to use conditions that maximize generation of n-butenes and minimize butadiene . In such a mode of operation, the unit can be considered a CATOFTN® unit or it can also be considered a CATADIENO® unit (moderate). At least a portion of the output of the n-butane dehydrogenation unit 55 is fed through line 64, along with network bottoms 70 of the butene isomerization reaction combination and distillation tower 15, in the combined stream 72 with the oxideshydrogenação 75 where n-butenes are converted to butadiene. Effluents from dehydrogenation units 55 and 75 can undergo alternative processing approaches as described above 35/40 ma for the embodiments illustrated in figure 2. butadiene produced in the first dehydrogenation unit 55 can be separated and fed through line 60 to line of butadiene product 84. Hydrogen can also be separated and removed as a by-product via 62 for external or internal use. Water can be condensed, separated and removed via line 62. Some of the n-butenes can be discharged 62 if desired for use other than conversion to butadiene. It would be understood that line 62 can represent a single line or several different lines, possibly with different compositions, for the removal of some unreacted n-butenes, by-products or feed components. Residual N-butane and other compounds can be separated or recycled to the first dehydrogenation unit 55 via line 56. Alternatively or in addition, a portion of the residual n-butane can be recycled by combining it with the feed stream 10 with the combination of butene isomerization reaction and distillation tower 15 via line 58. In another embodiment, some portion of the residual nbutane is fed forward through line 64, together with or separately from the n-butenes, to the second unit of dehydrogenation 75. In another embodiment, part or all of the effluent from the first dehydrogenation unit can be fed, without the separation of by-products and n-butane described above, directly through line (64) to the second dehydrogenation unit 75, if advantageous regarding the separation between the two units. As an additional option, a combination of both approaches can be used. That is, a portion of the total effluent from the first dehydrogenation unit can be fed directly through line 64 to the second dehydrogenation unit 75 while a different portion can undergo separations before its n-butenes are also fed through line 64 to the second dehydrogenation unit 75. In the embodiments described above, the first dehydrogenation unit 55 obtains dehydrogenation of the n-butane content in the second cor36 / 40 feed side 52 for n-butenes, while the second oxideshydrogenation unit (n-butenes) 75 converts the n-butenes in butadiene using oxideshydrogenação. In another embodiment of the process shown in figure 4, which is especially useful when there are substantial n-butenes in the second feed stream 52, the order described above is reversed and at least a portion of the second feed stream 52 is fed through the line 53 for the feed line 72 for the oxideshydrogenation unit 75 to dehydrate the n-butenes in the feed stream 52 in the oxideshydrogenation unit 75, followed by sending the n-butane portion of the effluent from the nbutene oxideshydrogenation unit 75 to the n-butane dehydrogenation unit 55 via line 76 as described above. In this embodiment, the feed to the n-butene oxideshydrogenation unit 75 can be a combination of direct bottoms of the butene isomerization reaction combination and distillation tower 1 provided through line 70 together with all or a portion of the second feed stream. feed 52 and also n-butene stream (s) 64 of the n-butane dehydrogenation unit (55). The total feed 72 for the n-butene oxideshydrogenation unit 75 may also include recycle 74 of its own effluent as described above. Alternatively, a first portion of the second feed stream 52 can be fed to the n-butane dehydrogenation unit 55 via line 54 and a second portion of the second feed stream52 can be fed to the n-butene oxideshydrogenation unit 75 via line 72. These two portions can have different compositions and be considered as a second and third feed stream. In yet another embodiment (not shown), the n-butane dehydrogenation unit 55 and the production of butadiene which corresponds to the conversion of the n-butane content can be discontinued altogether, and the n-butene oxideshydrogenation unit 75 can be used alone to convert n-butenes to butadiene, with the second feed stream37 / 40 tion (52 sent directly to the nbutene oxideshydrogenation unit 75. As described above, the separation of butadiene in the effluents of the two dehydrogenation units 55 and 75 can be carried out in a shared butadiene separation system (for example, extraction). If desired, one or more of the current or recycle effluents can be fed far upstream, for example, to a butadiene extraction unit for the original C4 current from its source (current cracker, FCC). In another embodiment of the invention shown in figure 5, butadiene is produced from the feed load comprising both mixed butanes and mixed butanes. The mixed C4 feed stream is carried through line 10 for the combination of butenes isomerization reaction and distillation tower 15 where 1-butene is converted to 2-butenes, and isobutane and isobutene are separated from n-butane and 2butenes . A portion of the top stream 12 comprising isobutane and isobutene is typically returned to the combination of the butene isomerization reaction and distillation tower 15 as reflux 14 after cooling in the cooler 17. A portion of the network top 16, that is, the top stream 12 minus the reflux stream 14, can be discharged from the facility for disposal, storage or other processing 18. Optionally, all or a portion of the network top chain 20 can be further processed and recycled to the combination of butenes isomerization reaction and distillation tower 15. In this embodiment, both isobutane and isobutene in the network top chain are transformed into compounds that can be converted to butadiene and recycled, by feeding a portion of the network top stream 20 through line 30 to a dehydrogenation unit 35, such as a CATOFIN® unit, capable of converting isobutane to isobutene . Some portion of the outlet of the dehydrogenation unit 35 can be discarded 32 and a second portion can be recycled to inlet 30 of the isobutane dehydrogenation unit 35 via line 34. It would be understood that line 32 can represent a single line or several different lines, possibly with different compositions, for the removal of any unreacted product, by-products or food components. At least a portion of the outlet 36 from the dehydrogenation unit 35 comprising substantially increased isobutene, is fed through line 40 to the reverse isomerization unit 45 capable of converting isobutene to n-butenes. Part or all of the output from the reverse isomerization unit 45 is fed through line 44 back to the butene isomerization reaction combination and distillation tower 15. Part can be sent to other arrangements 46, and some portion of the effluent of the reverse isomerization unit 45 can be recycled 42 back to the unit via the feed line 40. The bottom from the combination of butenes isomerization reaction and distillation tower 15 comprises 2-butenes and n-butane and can undergo any of the processing alternatives of the embodiments described above. Also, a second (or third) feed stream 52 comprising n-butane and / or n-butenes and essentially free of isobutene can be fed directly to an n-butane dehydrogenation unit 55 or the n-butene oxideshydrogenation unit 75, as described above for figure 3 and using one of the processing alternatives described above. In another embodiment of the processes of the present invention using the process equipment as illustrated in figure 5, a feed stream 10 comprising only mixed paraffins (ie without C4 = substantial) is fed into the butene isomerization reaction combination and distillation tower 15 where isobutane is separated from nbutane. A portion of the top stream 12 is typically returned for the combination of the butene isomerization reaction and distillation tower 15 as reflux 14 after cooling in the chiller (17. A portion of the top net 16, i.e. the top stream 12 minus the reflux current 14, can be discharged from the installation for disposal, for ar39 / 40 storing or other processing 18. In this embodiment, at least a portion of the mesh top 20 is transformed into compounds that can be converted into butadiene and recycled back to the butene isomerization reaction combination and distillation tower 15. A portion of the network top stream 20 is fed through line 30 to a dehydrogenation unit 35, such as a CATOFVN® unit , capable of converting isobutane to isobutene. At least a portion of the outlet 36 from dehydrogenation unit 35, comprising substantially increased isobutene, is fed through line 40 to the unit reverse isomerization 45 capable of converting isobutene to n-butenes. At least a portion of the output of the reverse isomerization unit is fed back to the combination of butenes isomerization reaction and distillation tower 15 via line 44. Since chain 44 now contains some isobutene as well as n-butenes and some isobutane, the combination of butene isomerization reaction and distillation tower 15 now operates with a mixture of both mixed butanes and mixed butenes as in the previous embodiments and can undergo any of the processing alternatives of the embodiments described above. The bottom from the combination of butene isomerization reaction and distillation tower 15 comprises 2-butenes and n-butane and can undergo any of the processing alternatives of the embodiments described above. One skilled in the art will recognize that numerous variations or changes can be made to the process described above without departing from the scope of the present invention. Correspondingly, the above description of preferred embodiments is intended to describe the invention in an exemplary sense, rather than a limiting sense. Subsequently, when an amount, concentration or other value or parameter is given as either a range, preferred range or a list of upper preferable values and lower preferable values, this should be understood as specifically revealing all ranges formed from any pair of any upper range limit or preferred value 40/40 and any lower range limit or preferred value, regardless of whether ranges are revealed separately. Where a range of numerical values is reported here, unless otherwise stated, the range is intended to include its end points, and all integers and fractions within the range. It is intended that the scope of the invention is limited to the specific values reported when defining a range. 1/7
权利要求:
Claims (7) [1] 1. Process for the production of butadiene, characterized by the fact that it comprises the steps of: (a) feeding a feed stream (10) comprising a mixture of C4 olefins for a combination of butenes isomerization reaction and distillation tower (15) to produce a top stream (12) comprising isobutene and a stream of bottom (22) comprising 2-butene; (b) feeding at least a portion (70) of the bottom 10 stream (22) to an oxidehydrogenation unit (75) to convert the 2butenes to butadiene; (c) separation of butadiene (82) in the effluent from the oxideshydrogenation unit (75) from unreacted compounds and by-products (80); (d) feeding at least a portion (20) of the top 15 stream (12) to a reverse isomerization unit (45) to convert isobutene to n-butene; and (e) feeding at least a portion (44) of the effluent from the reverse isomerization unit (45) for the combination of butenes isomerization reaction and distillation tower (15). 20 2. Process according to claim 1, characterized by the fact that it subsequently comprises the step of: (d) recycling at least a portion (74) of the effluent from the oxideshydrogenation unit (75) for feeding to the oxideshydrogenation unit (75). 25 3. Process according to claim 1, characterized by the fact that it subsequently comprises the step of: (d) feeding at least a portion (78) of the effluent from the oxideshydrogenation unit (75) for the combination of butenes isomerization reaction and distillation tower (15). 30 4. Process for the production of butadiene, characterized by the fact that it comprises the steps of: (a) supplying a supply chain (10) comprising Petition 870180019781, of 12/03/2018, p. 6/17 [2] 2/7 giving a mixture of C4 olefins and n-butane for a combination of butene isomerization reaction and distillation tower (15) to produce a top stream (12) and a bottom stream (22); (b) feeding at least a portion of the bottom current 5 (22) to a dehydrogenation unit (35) for converting n-butanes to n-butenes; (c) feeding at least a portion (70) of the effluent from the dehydrogenation unit (35) to an oxideshydrogenation unit (75) to convert n-butenes to butadiene; (D) separation of the butadiene (82) in the effluent of the oxideshydrogenation unit (75) from the unreacted compounds and by-products (80); (e) feeding at least a portion (20) of the top stream (12) to a reverse isomerization unit (45) to convert isobutene to n-butene; and 15 (f) feeding at least a portion (44) of the effluent from the reverse isomerization unit (45) for the combination of butenes isomerization reaction and distillation tower (15). 5. Process according to claim 4, characterized by the fact that it subsequently comprises the step of: (G) recycling at least a portion (34) of the effluent from the dehydrogenation unit (35) for feeding to the dehydrogenation unit (35). 6. Process according to claim 4, characterized by the fact that it subsequently comprises the step of: 25 (g) recycling at least a portion (78) of the effluent from the dehydrogenation unit (75) for the combination of butenes isomerization reaction and distillation tower (15). 7. Process according to claim 4, characterized by the fact that it subsequently comprises the step of: (G) recycling at least a portion (76) of the effluent from the oxideshydrogenation unit (75) to feed to the dehydrogenation unit (35). Petition 870180019781, of 03/12/2018, p. 7/17 [3] 3/7 8. Process according to claim 4, characterized by the fact that it subsequently comprises the step of: (g) feeding at least a portion (78) of the effluent from the oxideshydrogenation unit (75) for the reaction combination 5 of butenes isomerization and distillation tower (15). 9. Process for the production of butadiene, characterized by the fact that it comprises the steps of: (a) feeding a first feed stream (10) comprising a mixture of C4 olefins for a combination of butene isomerization reaction and distillation tower (15) to produce a top stream (12) and a bottom stream (22); (b) feeding a second feed stream (52) comprising n-butanes to a dehydrogenation unit (55) to convert n-butanes to n-butenes; (C) feeding at least a portion (64) of the bottom stream to an oxideshydrogenation unit (75) to convert the 2butenes to butadiene; (d) feeding the effluent from the dehydrogenation unit (55) to the oxideshydrogenation unit (75); and 20 (e) separation of the butadiene (82) in the effluent of the oxideshydrogenation unit (75) from unreacted compounds and by-products (80). 10. Process according to claim 9, characterized by the fact that it subsequently comprises the steps of: (E) supplying at least a portion (20) of the top stream (12) to a reverse isomerization unit (45) to convert isobutene to n-butene: and (f) supplying the effluent (44) from the unit reverse isomerization (45) for the combination of bute30 nos isomerization reaction and distillation tower (15). 11. Process according to claim 10, characterized by the fact that it subsequently comprises the step of: Petition 870180019781, of 03/12/2018, p. 8/17 [4] 4/7 (e) feeding at least a portion of the bottom stream (22) directly to the oxideshydrogenation unit (75). 12. Process according to claim 10, characterized by the fact that it subsequently comprises the step of: [5] 5 (g) recycling at least a portion (78) of the effluent from the oxideshydrogenation unit (75) for feeding to the oxideshydrogenation unit (75). 13. Process according to claim 10, characterized by the fact that it subsequently comprises the step of: 10 (g) feeding at least a portion (58) of the effluent from the dehydrogenation unit (55) for the combination of butenes isomerization reaction and distillation tower (15). 14. Process according to claim 10, characterized by the fact that it subsequently comprises the step of: (G) recycling at least a portion (56) of the effluent from the dehydrogenation unit (55) to feed to the dehydrogenation unit (55). 15. Process according to claim 10, characterized by the fact that it subsequently comprises the step of: 20 (g) feeding at least a portion (58) of the effluent from the dehydrogenation unit (55) for the combination of butenes isomerization reaction and distillation tower (15). 16. Process for the production of butadiene, characterized by the fact that it comprises the steps of: 25 (a) feeding a first feed stream (10) comprising a mixture of C4 olefins for a combination of butenes isomerization reaction and distillation tower (15) to convert ibutene to 2-butenes and produce a top stream ( 12) and a bottom chain (22); (B) feeding a second feed stream (52) comprising n-butanes to a first dehydrogenation unit (35) to convert n-butanes to n-butenes; Petition 870180019781, of 03/12/2018, p. 9/17 5/7 (c) feeding at least a portion (70) of the bottom stream to an oxideshydrogenation unit (75) to convert the 2butenes to butadiene; (d) feeding the effluent from the first dehydrogenation unit (35) to the oxidehydrogenation unit (75); (e) feeding at least a portion of the top stream (12) to a second dehydrogenation unit (55) to convert isobutane to isobutene; (f) feeding at least a portion of the effluent from the second dehydrogenation unit (55) to a reverse isomerization unit (45) to convert isobutene to n-butenes; (g) feeding at least a portion (58) of the effluent from the second dehydrogenation unit (55) for the combination of butenes isomerization reaction and distillation tower (15); 15 (h) separation of the butadiene (80) in the effluent from the oxideshydrogenation unit from other compounds. 17. Process according to claim 16, characterized by the fact that it subsequently comprises the steps of: (i) feeding at least a portion (20) of the top 20 stream (12) to a reverse isomerization unit (45) to convert isobutene to n-butenes; and (j) feeding at least a portion (44) of the effluent from the reverse isomerization unit (45) for the combination of butenes isomerization reaction and distillation tower (15). 18. Process according to claim 16, characterized by the fact that it subsequently comprises the step of: (i) feeding at least a portion (70) of the bottom stream (22) directly to the oxideshydrogenation unit (75). 19. Process according to claim 17, characterized by the fact that it subsequently comprises the step of: (k) recycling of at least a portion (74) of the effluent from the oxideshydrogenation unit (75) for feeding to the uniPetition 870180019781, of 12/03/2018, p. 10/17 [6] 6/7 oxydehydrogenation (75). 20. Process according to claim 17, characterized by the fact that it subsequently comprises the step of: (k) feeding at least a portion of the effluent from the first dehydrogenation unit (35) to the butene isomerization reaction combination and the distillation tower (15). 21. Process according to claim 17, characterized by the fact that it subsequently comprises the step of: (k) recycling at least a portion (34) of the effluent from the first dehydrogenation unit (35) into the feed for the first dehydrogenation unit (35). 22. Process according to claim 16, characterized by the fact that it subsequently comprises the step of: (g) feeding at least a portion of the effluent from 15 of the first dehydrogenation unit (35) for the combination of butenes isomerization reaction and distillation tower (15). 23. Process for the production of butadiene, characterized by the fact that it comprises the steps of: (a) feeding a first feed stream (10) 20 comprising a mixture of C4 olefins for a combination of butene isomerization reaction and distillation tower (15) to produce a top stream (12) and a bottom stream (22); (b) feeding at least a portion of a second feed stream (52) comprising n-butanes and n-butenes to 25 an oxideshydrogenation unit (75) for converting n-butenes to butadiene; (c) feeding at least a portion of the effluent from the oxideshydrogenation unit (75) to a dehydrogenation unit (35) to convert the 2-butanes to 2-butenes; (D) feeding the effluent from the dehydrogenation unit (35) to the oxideshydrogenation unit (75); and (e) separation of the butadiene (80) in the effluent of the oxydePetition unit 870180019781, of 03/12/2018, p. 11/17 [7] 7/7 dehydrogenation (75) of unreacted compounds and by-products (82). Petition 870180019781, of 03/12/2018, p. 12/17 V5 2/5 CM Ο IL · 3/5 4/5 5/5
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公开号 | 公开日 CA2770311A1|2011-02-24| WO2011022038A8|2012-03-08| CN102712555A|2012-10-03| PL2467352T3|2018-02-28| CA2770311C|2017-09-12| JP6039630B2|2016-12-07| JP5940449B2|2016-06-29| US20110040134A1|2011-02-17| MX2012001919A|2012-04-30| CN102712555B|2015-10-07| TWI475001B|2015-03-01| WO2011022038A1|2011-02-24| ZA201201874B|2012-12-27| BR112012003615A2|2016-02-23| SG10201404372WA|2014-09-26| TW201113249A|2011-04-16| JP2013502414A|2013-01-24| MY160648A|2017-03-15| SG178341A1|2012-03-29| MY169109A|2019-02-18| US20130102822A1|2013-04-25| KR20120103759A|2012-09-19| AR079405A1|2012-01-25| JP2015061859A|2015-04-02| EP2467352B1|2017-10-04| EP2467352A1|2012-06-27| KR101882173B1|2018-07-26| US8933284B2|2015-01-13| KR20150046373A|2015-04-29| US8293960B2|2012-10-23| CL2012000358A1|2012-08-24|
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法律状态:
2017-12-12| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]| 2018-04-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2018-05-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]| 2020-09-29| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 10A ANUIDADE. | 2021-01-12| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2595 DE 29-09-2020 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
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申请号 | 申请日 | 专利标题 US12/542,565|US8293960B2|2009-08-17|2009-08-17|Process for the production of butadiene| US12/542,565|2009-08-17| PCT/US2010/002176|WO2011022038A1|2009-08-17|2010-08-05|Process for the production of butadiene| 相关专利
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