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    • 专利摘要:
    PROPYLENE VIA METATHESIS WITH LOW, OR WITHOUT ETHYLENE CONTENT The present invention relates to a process to produce propylene, which includes: fractionating a stream of mixed C4 hydrocarbons to recover a first fraction, comprising isobutene, and a second fraction comprising 2 -butene; placing the first fraction in contact with a first metathesis catalyst in a first metathesis reaction zone; recover an effluent from the first metathesis reaction zone, comprising at least one among ethylene, propylene, unreacted isobutene, C5 olefins and C6 olefins; contacting the second fraction and ethylene in the effluent with a second metathesis catalyst in a second metathesis reaction zone; recover an effluent from the second reaction zone, which comprises at least one among ethylene that has not reacted, propylene, 2-butene that has not reacted, fractionate the effluent from the first metathesis reaction zone and the effluent from the second metathesis reaction zone to recovering a fraction of ethylene, a fraction of propylene, one or more C4 fractions and a fraction comprising at least one of the C5 and C6 olefins.
    公开号:BR112015005606B1
    申请号:R112015005606-7
    申请日:2013-09-11
    公开日:2021-03-09
    发明作者:Stephen J. Stanley；Robert J. Gartside；Thulusidas Chellppannair
    申请人:Lummus Technology Inc；
    IPC主号:
    专利说明:

    [001] The modalities disclosed in the present invention refer, in general, to the production of propylene via metathesis without using or using a low content of fresh ethylene. BACKGROUND OF THE INVENTION
    [002] In typical olefin plants, as illustrated in U.S. Patent No. 7,223,895, there is a demethanizer at the front end for removing methane and hydrogen, followed by a deethanizer for removing ethane, ethylene and acetylene C2. The lower part of this desetanizing tower consists of a mixture of compounds that vary, in number of carbon, from C3 to C6. This mixture can be separated into different carbon numbers, usually by fractionation.
    [003] The C3 cut, mainly of propylene, is removed as a product and is finally used for the production of polypropylene or for chemical synthesis, such as propylene oxide, cumene or acrylonitrile. Impurities of methyl acetylene and propadiene (MAPD) must be removed by fractionation or hydrogenation. Hydrogenation is preferred, as some of these highly unsaturated C3 compounds are ultimately transformed into propylene, increasing yield.
    [004] The C4 cut, consisting of C4 acetylenes, butadiene, iso and n-butenes and iso and n-butane, can be processed in several ways. A typical steam C4 cracker contains the following components in% by weight: Table 1. Components of the typical C4 cut and percentages by weight.

    [005] The components in a refinery or C4 cut based on FCC are similar, except that the percentage of paraffins is considerably higher.
    [006] Typically, butadiene and C4 acetylenes are removed first. This can be accomplished by hydrogenation or extraction. The product of the removal of butadiene and acetylene C4 is called rafinate I. If the extraction is used, the remaining 1-butene and 2-butene remain essentially the same ratio as that of the initial raw material. If hydrogenation is used, the initial product of hydrogenation of butadiene is 1-butene. Subsequently, hydroisomerization occurs in the same reaction system, changing 1-butene to 2-butene. The extent of this reaction depends on the conditions of the reaction and the catalyst in the hydrogenation system. However, it is common practice to limit the extent of hydroisomerization to avoid "excessive hydrogenation" and the production of butanes from butenes. This would represent a loss of raw material for butene for downstream operations. The remaining butenes in the mixture consist of normal olefins (1-butene, 2-butene) and iso-olefins (isobutylene). The rest of the mixture consists of iso and n-butanes from the original supply, plus what was produced in the hydrogenation steps and any small amount of unconverted or not recovered butadiene.
    [007] A refine flow I can be further processed in several ways. A stream of raffinate II is, by definition, a stream after removal of the isobutylene. Isobutylene can be removed in several ways. It can be removed by fractionation. In fractionation, isobutane will be removed together with isobutylene. In addition, a fraction of the 1-butene will also be lost. The resulting raffinate II will mainly contain normal paraffins and olefins, and a minimal amount of iso-olefins and isoparaffins. Isobutylene can also be removed by reaction. The reactions include: reaction with methanol to form MTBE, reaction with water to form tertiary butyl alcohol or reaction with itself to form a component of gasoline C. In all reaction cases, the paraffin is not removed and thus the mixture will contain ne isoparaffins. The paraffin content and composition of rafinate II impact downstream processing options.
    [008] Butenes have many uses. One of these uses is for the production of propylene through metathesis. Another is for the production of ethylene and hexene through metathesis. Conventional metathesis involves the reaction of normal butenes (1-butene and 2-butene) with ethylene (mainly the reaction of 2-butene with ethylene to form propylene). These reactions occur in the presence of a metal oxide catalyst group of the VIA or VIIA group, whether supported or not. The paraffin components of the reaction supply are essentially inert and do not react and are normally removed from the process through a purge flow in the separation system that comes after the metathesis reactor. Typical catalysts for metathesis are tungsten oxide supported on silica or rhenium oxide supported on alumina. Examples of suitable catalysts for metathesis of olefins are described in U.S. Patent No. 6,683,019, for example. Isobutylene (isobutene) can be removed from the raw material before the metathesis reaction step. The reaction of isobutylene with ethylene is not productive, and the reaction with itself and / or with other C4s is limited in the presence of excess ethylene. Non-productive reactions essentially occupy catalytic sites, but do not produce product. If left to remain in the supply for the metathesis unit, the concentration of this non-reactive species would accumulate, causing capacity limitations. The reaction of 1-butene with ethylene is also non-productive. However, it is common to use a double bonded isomerization catalyst within the metathesis reactor to modify 1-butene to 2-butene and allow the reaction to continue. Typical double bonded isomerization catalysts include basic metal oxides (group II), with or without support. Magnesium oxide and calcium oxide are examples of such double bonded isomerization catalysts that can be physically mixed with the metathesis catalyst. No equivalent cocatalyst exists for the isomerization of the isobutylene backbone to normal butene. In the case of a conventional metathesis system that uses both a metathesis catalyst and a mixed double bond isomerization catalyst, the butadiene must be removed to less than 500 ppm to prevent fouling of the double bond isomerization catalyst. The metathesis catalyst itself can tolerate butadiene levels of up to 10,000 ppm.
    [009] In some cases, an isobutylene removal step is employed prior to metathesis. Options include reacting it with methanol to produce tert-butyl methyl ether (MTBE) or to separate isobutylene from butenes by fractionation. U.S. Patent No. 6,358,482 discloses the removal of isobutylene from the C4 mixture prior to metathesis. This scheme is also reflected in US Patent Nos. 6,075,173 and 5,898,091. United States Patent No. 6,580,009 discloses a process for the production of propylene and hexene from a limited fraction of ethylene. For molar ratios of ethylene to butenes (expressed as n-butenes) from 0.05 to 0.60, the inventors use a stream of raffinate II as the raw material for C4.
    [010] The typical metathesis process uses raffinate I and removes most of the isobutylene by fractionation, as described above, to form a raffinate II. In this step, the isobutene is also removed, in addition to some amounts of normal butenes, depending on the fractionation conditions. The rafinate II is then mixed with ethylene, passes through the guard beds to remove poisons, is vaporized, preheated and fed to the metathesis reactors. Operating conditions are typically 300 ° C and 2,000 kPA to 3,000 kPa (20 to 30 bar) pressure. The effluent from the reactor after heat recovery is then separated in a fractionation system. First, ethylene is recovered in the airspace in a first tower and recycled to the reactor system. The back of the tower is then sent to a second tower, where the propylene is recovered in the air space. A side suction is made, containing most of the unconverted C4 components and is recycled to the reactor. The bottoms of the tower containing C5 and heavier products, in addition to C4 paraffins and olefins, are sent for purging. The purge rate is usually fixed to contain enough C4 paraffins to prevent their accumulation in the reactor's recycling stream. In some cases, a third tower is used at the bottom of the tower to separate the C4 components in the airspace and the C5 and heavier components, as a flow from the inside.
    [011] United States Patent No. 6,271,430 discloses a two-step process for the production of propylene. The first step consists in the reaction of 1-butene with 2-butene in a stream of raffinate II in an auto-synthesis reaction, to form propene and 2-pentene. The products are then separated in the second step. The third step specifically reacts 2-pentene with ethylene to form propylene and 1-butene. This process uses the isobutylene-free raffinate II stream. The pentenes recycled and reacted with ethylene are normal pentenes (2-pentene).
    [012] The removal of isobutylene from the C stream can also be carried out using a combined catalytic distillation hydroisomerisation deisobutylenator system, to remove isobutylene and recover the n-butenes with high efficiency, isomerizing the 1-butene in 2-butene with known isomerization catalysts and thereby increasing the difference in volatility. This technology combines conventional fractionation for the removal of isobutylene with hydroisomerization in a catalytic distillation tower. In US patent No. 5,087,780, to Arganbright, 2-butene is hydroisomerized to 1-butene, as fractionation occurs. This allows quantities greater than those found in the 1-butene equilibrium to be formed as the mixture is separated. Likewise, 1-butene can be hydroisomerized to 2-butene in a catalytic distillation tower. When separating a stream of C4 containing isobutylene, 1-butene and 2-butene (in addition to paraffins), it is difficult to separate isobutylene from 1-butene, since their boiling points are very close. By using the simultaneous hydroisomerization of 1-butene to 2-butene with isobutylene fractionation, isobutylene can be separated from normal butenes with high efficiency.
    [013] The metathesis reaction described above is equimolar, that is, one mole of ethylene reacts with 1 mole of 2-butene to produce 2 moles of propylene. However, commercially, in many cases, the amount of ethylene available is limited in relation to the amount of butenes available. In addition, ethylene is an expensive raw material and it is desired to limit the quantities of ethylene used. As the ratio of ethylene to butenes is decreased, there is a greater tendency for butenes to react with themselves, which reduces the global selectivity of propylene.
    [014] Metathesis catalysts and double bond isomerization catalysts are very sensitive to poisons. Poisons include water, CO2, oxygen compounds (such as MTBE), sulfur compounds, nitrogen compounds and heavy metals. It is common practice to use guard beds upstream of the metathesis reaction system to ensure the removal of these poisons. It does not matter whether these guard beds are directly before the metathesis reaction system or, upstream, as long as the poisons are removed and no new poisons are subsequently introduced.
    [015] Metathesis reactions are very sensitive to the olefin double bond site and the stereostructure of individual molecules. During the reaction, the double bond on each pair of olefins adsorb on the surface and exchange double bond positions with the carbon groups on either side of the double bonds. Metathesis reactions can be classified as productive, semi-productive or non-productive. As described above, non-productive reactions result, essentially, in the absence of any reaction. When the double bonds move with the metathesis reaction, the new molecules are the same as the molecules originally adsorbed, and thus, no productive reaction occurs. This is typical for reactions between symmetric olefins or reactions between ethylene and alpha olefins. If fully productive reactions occur, new products are generated, regardless of the orientation that the molecules occupy at the sites. The reaction between ethylene and 2-butene to form two propylene molecules is a fully productive reaction. Semi-productive reactions are sterically inhibited. If the pair of olefins adsorb in an orientation (usually in the cis position in relation to the linked R groups) when the double bonds move, new products are formed. Alternatively, if they adsorb to a different steric configuration (trans position), when the bonds move, identical olefins are formed and, thus, new products are not formed. The various metathesis reactions occurred at different rates (a fully productive reaction is generally faster than a semi-productive reaction). Table 2 summarizes the reactions between ethylene and various butenes, and the reactions between butenes themselves.
    [016] The reactions listed in table 2 represent the basic reaction with ethylene (reaction 1, 4 and 5), as well as the reactions between the various C4 olefins. It is especially important to make a distinction between the propylene selectivity of total C4 olefins (including isobutylene) and the propylene selectivity of the normal C4 olefins involved in the reaction. The reaction of isobutylene with 2-butene (reaction 6) produces propylene and a branched C5 molecule. For this reaction, propylene is produced with a selectivity equal to 50 molar% of the total C4s (similar to reaction 2), but with a selectivity equal to 100 molar compared to normal C4s (2-butene). For the purposes of definitions, conventional metathesis is defined as the reaction of the flow of C4 olefin with ethylene. However, the C4 flux can also react in the absence of ethylene as a raw material. This reaction is called self-synthesis. In this case, reactions 2, 3, 6 and 7 are the only possible reactions and will occur at rates dependent on the composition of the raw material.


    [017] In conventional metathesis, the focus is on maximizing reaction 1 to produce propylene. This will maximize selectivity for propylene. As such, excess ethylene is used to reduce the group of reactions of butenes with themselves (reactions 2, 3, 6 and 7). The theoretical ratio is equal to 1/1 molar or weight ratio equal to 0.5 ethylene in relation to n-butenes, but it is common, in conventional metathesis, to use significantly higher ratios, typically equal to 1.3 or more , to minimize reactions 2, 3, 6 and 7. Under conditions of excess ethylene, and due to the fact that both isobutylene and 1-butene do not react with ethylene (see reactions 4 and 5), two sequences of the process are used. First, the isobutylene is removed before metathesis. If isobutylene is not removed, it will accumulate as n-butenes are recycled to achieve high yield. Second, 1-butene is isomerized to 2-butene, including a double bonded isomerization catalyst, such as magnesium oxide mixed with the metathesis catalyst. Note that this catalyst will not cause skeletal isomerization (isobutylene to normal butenes), but will only shift the double bond from position 1 to position 2, for normal butenes. Thus, when operating with excess ethylene, eliminating isobutylene from the supply of the metathesis before the reaction, and using a double bonded isomerization catalyst, reaction 1 is maximized. However, note that when removing isobutylene, the potential production of propylene or other products is lost.
    [018] When there is no or only a limited amount of fresh ethylene (or butenes in excess of the available ethylene), there are currently two options available for the production of propylene. In such cases, the first option will first remove the isobutylene and then process the normal butenes with whatever ethylene is available. The entire mixture of only n-butenes is metathesis with the available ethylene. Finally, if fresh ethylene is not available, the C4s react with themselves (self-synthesis). Under conditions of low ethylene concentration, reactions 2, 3, 6 and 7 will occur, leading to a low selectivity of propylene (50% or less compared to 100% for reaction 1). Less selectivity results in less propylene production. Note that reactions 6 and 7 will be minimized as a result of removing isobutylene (up to low levels, but not necessarily zero). Alternatively, the molar flows of ethylene and butenes can be equated by limiting the flow of butenes to produce conditions where there is a high selectivity of normal butenes to propylene in the reaction of lane 1. By limiting the flow of n-butenes to equate with for ethylene, propylene production is limited by the reduced flux of butenes.
    [019] Pentenes and some hexenes are formed, to a certain extent, in the case of conventional metathesis, with low ethylene content through reactions 2 and 3. The volume of these components will depend on the ratio of ethylene / n-butenes with a lower rate of slower production of more C5 and C6 components. In the conventional case of the prior art, where isobutylene is removed before any metathesis, these C5 and C6 olefins are normal olefins, since there is no isomerization in the skeleton. It is possible to recycle these olefins back to the metathesis stage where, for example, the reaction with ethylene and 2-pentene will occur, producing propylene and 1-butene. 1-butene is recovered and recycled. Note, however, with limited ethylene, that reaction 1 can occur only up to the ethylene availability limit. Finally, these non-selective by-products, pentenes and hexenes must be purged from the system.
    [020] United States Patent No. 6,777,582 discloses a process for the self-synthesis of olefins, to produce propylene and hexene. In it, the self-synthesis of a mixture of normal butenes fed in the presence of a metathesis catalyst operates without any ethylene in the feed mixture for the metathesis reactor. Some fractions of the 2-butene fed can be isomerized into 1-butene, and the 1-butene formed together with the 1-butene in the supply reacts quickly with the 2-butene to form propylene and 2-pentene. The supply to the reactor also includes recycling the 2-pentene formed in the reactor with the butenes that did not react to simultaneously form more hexene and propylene. The 3-hexene formed in the reaction can be isomerized to 1-hexene.
    [021] In US Patent No. 6,727,396, ethylene and 1-hexene are produced from 1-butene through the methesis of 1-butene and by the isomerization of the 3-hexene produced therein, to 1-hexene. The initial starting material is a mixed butene stream, in which the 1-butene is isomerized to 2-butene, with the isobutylene being separated from it, followed by the isomerization of the 2-butene to 1-butene, with the 1-butene being the supply for the metathesis.
    [022] In US Patent No. 7,214,841, the C4 cut of a hydrocarbon cracking process is first subjected to self-synthesis before any isobutylene removal and without any addition of ethylene, favoring the reactions that produce propylene and pentenes. The ethylene and propylene produced are then removed, leaving a stream of C4s and heavier components. The C5 and heavier components are then removed, leaving a mixture of 1-butene, 2-butene, isobutylene and iso and n-butanes. The isobutylene is then removed, preferably, by a catalytic distillation hydroisomerisation deisobutylizer. The isobutylene-free flow of C4 is then mixed with the ethylene product removed from the self-synthesis product, together with any necessary fresh external ethylene and subjected to conventional metathesis, producing more propylene.
    [023] The processes for producing propylene using little or no ethylene are interesting due to the limited commercial availability of ethylene, especially in relation to the amount of commercially available butenes. In addition, ethylene is an expensive raw material, and limiting the amounts of ethylene used can result in significant cost savings. However, as the ratio of ethylene to butenes is decreased, there is a greater tendency for butenes to react with themselves, which reduces the overall selectivity of propylene. SUMMARY OF THE INVENTION
    [024] The modalities disclosed in the present invention refer to the production of propylene when processing a C4 cut of a hydrocarbon cracking process, when the supply of ethylene is limited. The C4 cut has typically had butadiene removed to a level where the inlet concentration is less than 10,000 ppm (a stream of raffinate I).
    [025] In one aspect, the embodiments disclosed in the present invention relate to a process for producing propylene, which includes: fractionating a stream of mixed C4 hydrocarbons to recover a first fraction, comprising isobutene, and a second fraction comprising 2- butene; contacting at least a portion of the first fraction with a first metathesis catalyst in a first metathesis reaction zone; recovering an effluent from the first metathesis reaction zone, comprising at least one among ethylene, propylene, unreacted isobutene, C5 olefins and C6 olefins; contacting at least a portion of the second fraction and at least a portion of ethylene with a second metathesis catalyst in a second metathesis reaction zone; recover an effluent from the second reaction zone, which comprises at least one unreacted ethylene, propylene, 2-butene which has not reacted, fractionate the effluent from the first metathesis reaction zone and the effluent from the second metathesis reaction zone to recover a fraction of ethylene, a fraction of propylene, one or more C4 fractions and a fraction comprising at least one of the C5 and C6 olefins.
    [026] In another aspect, the modalities disclosed in the present invention refer to a process for the production of propylene, which includes: fractionating a stream of mixed C4 hydrocarbons to recover a first fraction comprising isobutene and 1-butene and a second fraction comprising 2-butene; contacting at least a portion of the first fraction with a first metathesis catalyst in a first metathesis reaction zone; recovering an effluent from the first metathesis reaction zone comprising at least one of ethylene, propylene, unreacted isobutene, unreacted 1-butene, C5 olefins and C6 olefins; fractionating the effluent from the first metathesis reaction zone to recover a fraction comprising ethylene and propylene, a fraction comprising any unreacted isobutene and any unreacted 1-butene, and a fraction comprising any C5 and C6 olefins; contacting at least a portion of the second fraction and ethylene with a second metathesis catalyst in a second metathesis reaction zone; recovering an effluent from the second reaction zone comprising at least one of unreacted ethylene, propylene and 2-butene which has not reacted, fractionating the effluent from the second metathesis reaction zone and the fraction comprising ethylene and propylene to recover a fraction of ethylene, a propylene fraction, a C4 fraction and a fraction comprising at least one of the C5 and C6 olefins; feeding at least a portion of the ethylene fraction to the second metathesis reaction zone such as ethylene; feeding at least a portion of the C4 fraction to the second metathesis reaction zone; and feeding at least a portion of the fraction comprising any unreacted isobutene and any unreacted 1-butene to the first metathesis reaction zone.
    [027] In another aspect, the embodiments disclosed in the present invention relate to a process for the production of propylene, including: feeding a stream of mixed C4 hydrocarbons comprising 1-butene, 2-butene and isobutene to a distillation reactor system catalytic; at the same time in the catalytic distillation reactor system: isomerizing at least a portion of the 2-butene to form 1-butene; fractionating the flow of mixed C4 hydrocarbons to recover a first fraction comprising isobutene and 1-butene, and a second fraction comprising 2-butene; and contacting at least a portion of the first fraction with a first metathesis catalyst in a first metathesis reaction zone; recovering an effluent from the first metathesis reaction zone, which comprises at least one among ethylene, propylene, unreacted isobutene, C5 olefins and C6 olefins; contacting at least a portion of the second fraction and at least a portion of the ethylene in the effluent, with a second metathesis catalyst in a second metathesis reaction zone; recover an effluent from the second reaction zone, which comprises at least one of unreacted ethylene, propylene and 2-butene which has not reacted, fractionate the effluent from the first metathesis reaction zone and effluent from the second metathesis reaction zone to recover a ethylene fraction, propylene fraction, one or more C4 fractions and a fraction comprising at least one of the C5 and C6 olefins.
    [028] Other aspects and advantages will be evident from the description below and the attached claims. BRIEF DESCRIPTION OF THE DRAWINGS
    [029] Figure 1 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [030] Figure 2 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [031] Figure 3 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [032] Figure 4 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [033] Figure 5 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [034] Figure 6 is a simplified process flow chart of a process for the production of propylene, according to the modalities disclosed in the present invention.
    [035] Figure 7 is a simplified process flow chart of a comparative process for the production of propylene. DETAILED DESCRIPTION
    [036] The modalities disclosed in the present invention refer, in general, to the production of propylene through the methesis of C4 olefins, using little or no fresh ethylene. In cases where the molar ratio of ethylene to the C4 flux is zero or less than the weight ratio of 0.5 or the molar ratio of 1.0, the C flux is processed more efficiently and the total propylene produced from a catalytic fluid-cracking C4 flow containing isobutylene and isobutane can increase according to the modalities disclosed in the present invention, first, by fractioning the supply of C4 to produce a fraction of isobutylene and a fraction of 2-butene, using an auto-metastasis step to react isobutylene to form ethylene (for example, reaction 5). The ethylene produced can therefore be used in a second conventional metathesis reaction system to react ethylene with the 2-butene flow. Depending on the relative concentration of C4 paraffins and olefins (n-butane, isobutane), several separation schemes can be used to fractionate the respective metathesis products, to result in a fraction of ethylene, a fraction of the propylene product, in one or more fractions of recycled C4 and in one or more fractions of product C5 and / or C6.
    [037] The processes according to the modalities disclosed in the present invention advantageously produce ethylene from isobutylene, according to the following reaction (reaction 8): Isobutylene + Isobutylene ^ Ethylene + 2,3-dimethyl-2-butene (8). In addition to reaction 8, other modalities disclosed in the present invention can produce ethylene by means of reaction 2 (1-butene + isobutylene ^ ethylene + 2-methyl-2-pentene). The performance of self-synthesis may vary, depending on the relative compositions of isobutylene, 1-butene and 2-butene in the C4 flow.
    [038] In other embodiments, the ratio of isobutylene, 1-butene or 2-butene in the C4 flow can be adjusted using structural isomerization (1-butene ^ isobutylene) or positional isomerization (1-butene ^ 2-butene) , where the type of isomerization or preferred product may depend on the particular C4 flow used. Structural isomerization or isomerization can be performed using a fixed bed or a catalytic distillation reactor system. In other embodiments, the concentration (ratio) of isobutylene can be adjusted using an isobutylene flow, as it may be readily available in some hydrocarbon processing plants.
    [039] In some embodiments, the hydrocarbon supply to the processes disclosed in the present invention can be supplied as a mixed C4 stream. The flow of C4 mixed with the processes disclosed in the present invention can include hydrocarbons from C3 to C6 + including cracked effluents C3, C4 to C5 and C4 to C6, as from a steam cracker or a fluid catalytic cracking unit (FCC) . Other hydrocarbon streams from the refinery containing a mixture of C olefins can also be used. When components C3, C5 and / or C6 are present in the supply, the flow can be pre-fractionated to result in a primary C4 cut, a C4 to C5 cut or a C4 to C6 cut.
    [040] The C4 components contained in the feed stream may include n-butane, isobutane, isobutene, 1-butene, 2-butene and butadiene. In some embodiments, the mixed C4 supply is pretreated to provide a supply of 1-butene for the metathesis reaction. For example, when butadiene is present in a C4 supply, butadiene can be removed by hydrogenation or extraction. In other embodiments, the supply of mixed butenes after or together with the hydrogenation of the butadiene can be subjected to hydroisomerization conditions to convert the 1-butene to 2-butene, with the isobutylene being separated from a 2-butene stream by fractionation. The 2-butene stream can then be isomerized back to 1-butene in a subsequent step for use as a supply for the metathesis portion of the processes disclosed in the present invention.
    [041] Referring now to figure 1, a simplified process flow chart of a process according to the modalities disclosed in the present invention is illustrated. A C4 cut, such as a stream of raffinate I containing isobutylene, 1-butene and 2-butene can be fed through flow line 2 to a separation system 4, which may include one or more distillation columns and / or systems catalytic distillation reactors. The C4 cut can then be fractionated to result in a fraction of isobutylene, recovered through flow line 6, and a fraction of 2-butene, recovered through flow line 8. Depending on the separation requirements and the equipment used in the separation zone 4, the isobutylene fraction can include isobutylene, isobutane and / or 1-butene, as well as trace amounts of 2-butene.
    [042] The isobutylene fraction can then be fed into the reaction zone of self-synthesis 14 containing a metathesis catalyst. If desirable or available, a supply of fresh isobutylene 9 can be combined with the isobutylene fraction 6, to adjust a ratio of isobutylene to 1-butene and 2-butene in the system. The isobutylene can be brought into contact with the metathesis catalyst under suitable operating conditions, for the conversion of at least a portion of the isobutylene to ethylene and 2,3-dimethyl-2-butene. When present, 1-butene can also react with each other or with isobutylene to produce ethylene via reactions 3 and 7. Likewise, when trace amounts of 2-butene are present, ethylene can react with 2-butene to produce a certain amount of propylene. Other reactions may also occur.
    [043] The effluent from the self-synthesis can be recovered through the flow line 15 and fed to a separation system 18, which can include a depropanizer, for example, to recover a fraction comprising ethylene and propylene, and a desbutanizer, to recover a C4 fraction (composed of isobutylene, 1-butene, trace amounts of 2-butene and also isobutane, when present). Ethylene and propylene can be recovered from the depropanizer via a flow line 16, the C4 fraction can be recovered through flow line 20 and the C5s and C6s produced can be recovered through flow line 22.
    [044] The C4 fraction can be recycled to the metathesis reaction zone 14 via flow line 20, a part of which can be purged, if necessary, to prevent the accumulation of isobutane within the system. C5s and C6s recovered from flow line 22 can be used, for example, as a fraction of gasoline, or can be further processed to produce desired end products (such as the production of ethylene and / or propylene through a cracking process (not shown)).
    [045] The fraction of ethylene and propylene recovered through flow line 16 can be fed to a separation zone 28, which can include, for example, a de-tanner, a de-propanizer and a de-butcher. A fraction of ethylene can be recovered from the desetanizer through flow 26, and propylene can be recovered through flow 32.
    [046] The ethylene produced in the metathesis reaction zone 14 and recovered in separation zones 18 and 28 via flow 26 can then be combined with the 2-butene fraction in flow 8 and fed to a reaction zone of conventional metathesis 24 containing a metathesis catalyst. If desired and available, fresh ethylene can be fed to the metathesis reaction zone 24 via flow line 27. The 2-butene and ethylene can then be brought into contact with the metathesis catalyst under operating conditions suitable for convert at least a portion of 2-butene and ethylene to form propylene.
    [047] The effluent from the conventional metathesis reaction zone 24 can be recovered through flow 30, which can then be fed to the separation zone 28 together with the ethylene fraction 26 for the separation of the metathesis products. As mentioned above, the separation zone 28 can include, for example, a desetanizer, a depropanizer and a desbutanizer. The ethylene that did not react in the conventional metathesis effluent and the ethylene produced in the reaction zone of self-synthesis 14 can be recovered from the desetanizer through the flow line 26 for recycling / feeding, to the reaction zone of conventional metathesis 24. Propylene, in the effluents from conventional metathesis and self-synthesis can be recovered from the depropanizer via flow line 32. A fraction of C4 can be recovered from the de-butcher via flow line 36, including 2-butene, to recycle to the reaction zone conventional metathesis 24. If necessary, a portion of the C4 fraction can be purged to prevent the build-up of n-butanes in the system. A C5 + fraction can also be recovered from the desbutanizer through flow line 34.
    [048] As mentioned above, it may be desired to adjust the relative amounts of isobutylene, 1-butene or 2-butene in the system. For example, it may be desirable to limit the amount of 1-butene in the isobutylene fraction. This can be accomplished, for example, by adjusting the fractionation conditions in the fractionation zone 4. Alternatively, the amount of 1-butene in the isobutylene fraction can be reduced by the isomerization of 1-butene to 2-butene before or during fractionation in the separation zone 4. As another example, it may be desirable to increase an amount of isobutylene, while decreasing the amount of 1-butene in the isobutylene fraction, which can be accomplished through the structural isomerization of 1-butene and / or 2-butene to form the isobutylene. Isomerization catalysts and reaction conditions are disclosed in U.S. Patent No. 5,087,780, for example. Structural isomerization catalysts and reaction conditions are disclosed in U.S. Patent Nos. 4,410,753, 5,321,193, 5,321,194, 5,382,743 and 6,136,289, among others. Each of these patents is incorporated into the present invention by reference.
    [049] Referring now to figure 2, a simplified process flowchart for the production of propylene, according to the modalities disclosed in the present invention, is illustrated, where similar numbers indicate similar parts. In that embodiment, the separation zone 4 includes a catalytic distillation reaction zone 7, including an isomerization or structural isomerization catalyst. In addition, or alternatively, a fixed bed isomerization reactor (not shown) can be used upstream of the reaction zone of catalytic distillation 7.
    [050] Referring now to figure 3, a simplified process flowchart for the production of propylene, according to the modalities disclosed in the present invention, is illustrated, where similar numbers indicate similar parts. In that embodiment, a reaction zone 11 of isomerization can be used to isomerize a portion of 2-butene, to form additional isobutylene and / or 1-butene.
    [051] Referring now to figure 4, a simplified process flowchart for the production of propylene, according to the modalities disclosed in the present invention, is illustrated, where similar numbers indicate similar parts. In that embodiment, the separation zone 4 includes a deisobutylizer 40 to separate 1-butene, isobutylene and isobutane from 2-butene and n-butane, when present. The 2-butene fraction is recovered via flow 8 and processed as described above. The aerial parts of the desisobutylizer 40 can be recovered by means of flow 42 and, later, fractionated in a deisobutanizer 44 to separate the isobutane from the remaining olefins, isobutylene and 1-butene if they are present. Isobutane can be recovered via flow 46. The isobutylene fraction can be recovered via flow line 6 and processed as described above. The use of a deisobutanizer 44 can encompass a more concentrated olefin stream 6 fed to the self-synthesis reactor 14, as well as reduced separation and purging rates for downstream processes.
    [052] Referring now to figure 5, a simplified process flowchart for the production of propylene, according to the modalities disclosed in the present invention, is illustrated, where similar numbers indicate similar parts. In this modality, the fractionation zone 4 includes a catalytic distillation reactor system 7 and a deisobutanizer 44.
    [053] Referring now to figure 6, a simplified process flowchart for the production of propylene, according to the modalities disclosed in the present invention, is illustrated, where similar numbers indicate similar parts. In that embodiment, the separation zone 4 includes a deisobutanizer 40 and a deisobutanizer 44, as well as a reaction zone of isomerization 11.
    [054] Although only a limited number of possible flow, reaction, and separation schemes have been illustrated, a person skilled in the art could note that other schemes are possible to similarly produce propylene through the metathesis of a C4 flow, with the use of little or no ethylene. The particular flow, reaction or separation scheme used may depend on available supplies, such as the relative amounts of isobutane, isobutylene, 1-butene and 2-butene.
    [055] In the above modes, the self-synthesis and conventional metathesis reactors can be operated at a pressure between 2 and 40 atmospheres in some modalities, and between 5 and 15 atmospheres in other modalities. Metathesis reactors can be operated, so that the reaction temperature is within the range of about 50 ° C to about 600 ° C; in the range of about 200 ° C to about 450 ° C, in other modalities; and from about 250 ° C to about 400 ° C, in other additional embodiments. Metathesis reactions can be performed at an hourly space speed in weight (WHSV) in the range of about 3 to about 200 in some modalities, and from about 6 to about 40 in other modalities.
    [056] The reactions can be carried out by contacting the olefin (s) with the respective metathesis catalysts in the liquid or gas phase, depending on the structure and molecular weight of the olefin (s). If the reaction is carried out in the liquid phase, solvents or diluents for the reaction can be used. Aliphatic saturated hydrocarbons, for example, pentanes, hexanes, cyclohexanes, dodecanes and aromatic hydrocarbons, such as benzene and toluene, are suitable. If the reaction is carried out in the gas phase, diluents such as saturated aliphatic hydrocarbons, for example, methane, ethane, and / or substantially inert gases, such as nitrogen and argon, may be present. For high product yield, the reaction can be carried out in the absence of significant amounts of deactivation materials, such as water and oxygen.
    [057] The contact time required to obtain a desirable yield of products from the metathesis reaction depends on several factors, such as the activity of the catalyst, temperature, pressure and the structure of the olefin (s) to be subjected metathesis. The period of time during which the olefin (s) comes into contact with the catalyst can conveniently vary between 0.1 second and 4 hours, preferably from about 0.5 sec to about 0 , 5 hour. Metathesis reactions can be carried out in batch or continuously, with fixed catalyst beds, with fluidized catalyst, fluidized beds or using any other conventional contact techniques.
    [058] The catalyst contained in metathesis reactors can be any known conventional self-metathesis or metathesis catalysts, which may be the same or different, and which include metal oxides of the VIA group and the VIIA group, in supports. The catalyst supports can be of any type and could include alumina, silica, mixtures thereof, zirconia and zeolites. In addition to the metathesis catalyst, the catalyst contained in the metathesis reactor can include a double bonded isomerization catalyst, such as magnesium oxide or calcium oxide. In some embodiments, the catalyst may include a promoter to reduce acidity; for example, an alkali metal (sodium, potassium or lithium), cesium, a rare earth, etc.
    [059] The processes described above cover the efficient production of propylene from C4 olefins. The processes disclosed in the present invention can be advantageously used where there is little or no ethylene available, or where there is an excess of C4 olefins over the available ethylene. EXAMPLES
    [060] The following examples are derived from modeling techniques. Although the work has been done, these examples are presented in the present to comply with the applicable rules.
    [061] In the following examples and comparative examples, the process for producing propylene according to the modalities disclosed in the present invention is compared to the process as disclosed in United States Patent No. 7,214,841 ('841) . A simplified process flowchart, of the process as disclosed in the '841 patent, is illustrated in figure 7. In this process, the entire cut of C4 (raffinate I) is fed through the flow line 101 to the auto-synthesis reactor 103. The effluent from the self-synthesis reactor 103 is recovered through the flow line 105 and fed to the separation zone 107, to recover a fraction of propylene 109, a fraction of C5 / C6 111, a fraction of ethylene 113 and a fraction of C4 115, which includes 1-butene, 2-butene, etc. The C4 fraction in the flow line 115 is then fed to the catalytic distillation reactor 117 for the simultaneous isomerization of the 1-butene, to form more 2-butene and separate the 2-butene from the isobutylene. The 2-butene fraction is recovered via flow line 121, and the isobutylene fraction can be recovered via flow line 127. The 2-butene fraction 121 and ethylene fraction 113 are then placed in contact with a metathesis catalyst in a conventional metathesis reaction zone 123. The effluent from reaction zone 123 can be recovered through flow line 125 and fed to the separation zone 107, for separation and recovery of the respective fractions. To prevent the accumulation of n-butanes, for example, a C4 purge can be removed via flow line 122. Comparative Example 1
    [062] The process, as illustrated in figure 7, is simulated. The details and results of the simulation are provided in tables 2 and 4. The flow numbers in table 2 correspond to those shown in figure 7. The supply 101 to the process includes a total flow of isobutylene of 142 thousand tons per year (kta), 1-butene of 178 kta and 2-butene of 357 kta, for a total olefin flow of 677 kta. The ratio of isobutylene to n-butenes in the supply is about 0.26. There are a total of 4 fractionation towers.

    [063] The simulation is performed to meet several convergence criteria, and the "steady state" simulation results indicate the following. The feed rate of ethylene to butene in the conventional metathesis reactor is equal to 0.18. The analysis of product flows indicates that the use of nC4 is equal to about 90.4%; the use of iC4 is equal to about 67.8%; and the general use of olefin is equal to about 85.8%, for both olefins in the range of propylene as well as gasoline. C3 production, as a percentage of total olefin, is about 36.9%. The total flow of isopentenes and isohexenes is equal to 127 kta, and the flow of n-pentenes and n-hexenes is equal to 196 for a ratio of iC5-6 to nC5-6 of 60.5%, indicating the extent of reactions 2 and 3 that form, n-olefins C5-6. Comparative Example 2
    [064] Comparative example 2 is also based on figure 1, with a greater need for isobutane concentration in the aerial part of tower 117 (retention of more olefins in flow 121). The supply for the process is the same as that used in Comparative Example 1, with an isobutylene to n-butenes ratio of 0.26. The details and results of the simulation are provided in Tables 3 and 4.


    [065] The simulation is performed to meet several convergence criteria, and the "steady state" simulation results indicate the following. The feed rate of ethylene to butene in the conventional metathesis reactor is 0.2. The analysis of product flows indicates that the use of nC4 is equal to about 91.2%; the use of iC4 is equal to about 85.1%; and the general use of olefin is equal to about 90.2%, for both olefins in the range of both propylene and gasoline. The production of C3, as a percentage of the total olefin supply, is equal to about 38.9%. The total flow of isopentenes and isohexenes is equal to 160 kta, and the flow of n-pentenes and n-hexenes is equal to 179 for a ratio of iC5-6 to nC5-6 of 52.8%, indicating the extent of reactions 2 and 3 that form C5-6 n-olefins.
    [066] Compared to comparative example 1, increasing the amount of isobutylene in the lower parts of tower 117 improves the general use of olefins and the yield of propylene, but requires more utilities to carry out the necessary separations.

    Example 1
    [067] A process similar to that illustrated in figure 4 is simulated, with the separation zone 4 including a desisobutyener 40 and a desisobutanizer 44. The details and results of the simulation are provided in tables 5 and 7. The flow numbers in the table 5 correspond to those shown in figure 4. The supply for the system (flows 2 and 9) includes a total flow of isobutylene of 251 thousand tons per year (kta) (78 + 173), 1-butene of 97 kta and 2 -butene of 196 kta for a total olefin flow of 371 kta. The ratio of isobutylene to n-butenes in supply 2 is about 0.26. There are a total of 6 fractionation towers.

    [068] The simulation is performed to meet several convergence criteria, and the "steady state" simulation results indicate the following. The feed rate of ethylene to butene in the conventional metathesis reactor is 1.7. The analysis of product flows indicates that the use of nC4 is equal to about 93%; the use of iC4 is equal to about 91.4%; and the general use of olefin is equal to about 92.8%, for both olefins in the range of propylene and gasoline. C3 production, as a percentage of total olefin, is about 46.1%. The total flow of isopentenes and total isohexenes is equal to 235 kta, and the flow of n-pentenes and n-hexenes is equal to 6 kta, for a ratio of iC5-6 to nC5-6 equal to 2.5 %. This process results in a very high efficiency of C4 n-olefins for propylene, and the use of olefins is high. Example 2
    [069] A process similar to that illustrated in figure 5 is simulated, with the separation zone 4, including a catalytic distillation reactor system 7 (countercurrent isomerization + fractionation in a deisobutery user) and a deisobutanizer 44. Details and results of the simulation are provided in tables 6 and 7. The flow numbers in table 6 correspond to those shown in figure 5. The supply for the system (flows 2 and 9) includes a total isobutylene flow of 344 thousand tons per year (kta) (53 + 290), 1- 68butene, kta and 2-butene 135 kta for a total olefin flow of 546 kta. The ratio of isobutylene to n-butenes in supply 2 is about 0.26. There are a total of 6 fractionation towers.


    [070] The simulation is performed to meet several convergence criteria, and the "steady state" simulation results indicate the following. The feed rate of ethylene to butene in the conventional metathesis reactor is 1.7. The analysis of product flows indicates that the use of nC4 is equal to about 90.7%; the use of iC4 is about 94.9; and the general use of olefin is equal to about 93.3%, for both olefins in the range of propylene and gasoline. The production of C3, as a percentage of the total olefin supply, is equal to about 45.9%. This process results in a very high efficiency of C4 n-olefins for propylene, and the use of olefins is high.



    [071] As shown by the examples above, the embodiments disclosed in the present invention provide an efficient process for converting C4 olefins to propylene.
    [072] As described above, the embodiments disclosed in the present invention encompass the production of propylene from C olefins, where there is little or no fresh ethylene, or an excess of C4 olefins over the available ethylene. In comparison, the embodiments disclosed in the present invention can produce propene with a very high use of C4 olefins for propylene. In some embodiments, where 1-butene is converted to 2-butene, for example, processes according to the modalities disclosed in the present invention can produce propylene with percentage yields that approximate the theoretical amount of propylene from nC4s in a process of conventional metathesis (with ethylene).
    [073] While possibly requiring more capital for equipment and utilities, namely, additional fractionation towers compared to the process in the comparative examples (6 towers compared to 4 towers in the comparative examples), the greater selectivity for propylene provided by processes disclosed in the present invention can offset the increased capital and operating expense. As such, the embodiments disclosed in the present invention provide a new alternative process for the production of propylene from C4 olefins, where there is little or no fresh ethylene, or an excess of C4 olefins over the available ethylene.
    [074] Although the disclosure includes a limited number of modalities, people skilled in the art, with the advantage of this disclosure, will notice that other modalities can be designed, which do not deviate from the scope of the present disclosure. Therefore, the scope should be limited only by the appended claims.
    权利要求:
    Claims (13)
    [0001]
    1. Process for the production of propylene, CHARACTERIZED by the fact that it comprises: fractionating a stream of C4 hydrocarbons (2) mixed to recover a first fraction (6), which comprises isobutene, and a second fraction (8) which comprises 2-butene ; contacting at least a portion of the first fraction (6) with a first metathesis catalyst in a first metathesis reaction zone (14); recovering an effluent (15) from the first metathesis reaction zone (14) comprising at least one of ethylene, propylene, unreacted isobutene, C5 olefins and C6 olefins; contacting at least a portion of the second fraction (8) and at least a portion of ethylene in the effluent (15) with a second metathesis catalyst in a second metathesis reaction zone (24); recover an effluent (30) from the second reaction zone of the metathesis, which comprises at least one of unreacted ethylene, propylene or unreacted 2-butene, fractionate the effluent (15) from the first metathesis reaction zone (14) and the effluent (30) from the second metathesis reaction zone (24) to recover a fraction of ethylene (26), a fraction of propylene (32), one or more C4 fractions (36) and a fraction (34) comprising at least one of the C5 and C6 olefins.
    [0002]
    2. Process, according to claim 1, CHARACTERIZED by the fact that it also comprises feeding the ethylene fraction (26) to the second metathesis reaction zone (24) as at least a portion of the ethylene in the effluent (15) of the first metathesis reaction zone (14).
    [0003]
    3. Process, according to claim 1, CHARACTERIZED by the fact that it also comprises recycling one or more fractions of C4 (36) to at least one of the first metathesis reaction zone (14) and the second reaction zone of metathesis (24).
    [0004]
    4. Process according to claim 1, CHARACTERIZED by the fact that the first fraction (6) comprises isobutene and 1-butene.
    [0005]
    5. Process according to claim 4, CHARACTERIZED by the fact that the first fraction (6) further comprises isobutane, the process further comprising: fractionating the first fraction (6) to recover a fraction of isobutane (20) and a fraction which comprises isobutene and 1-butene (20); and feeding the fraction comprising isobutene and 1-butene (20) to the first metathesis reaction zone (14) as at least a portion of the first fraction (6).
    [0006]
    6. Process according to claim 1, CHARACTERIZED by the fact that it further comprises isomerizing at least a portion of the 2-butene to form 1-butene.
    [0007]
    7. Process, according to claim 6, CHARACTERIZED by the fact that the isomerization is carried out simultaneously with the fractionation of a mixed C4 hydrocarbon flow (2).
    [0008]
    8. Process according to claim 6, CHARACTERIZED by the fact that the isomerization comprises feeding a portion of the second fraction (8) to a reaction zone of isomerization (11), recovering an effluent from the reaction zone of isomerization (11) and feed the effluent from the reaction isomerization zone (11) to the fractionation of a mixed C4 hydrocarbon flow.
    [0009]
    9. Process, according to claim 1, CHARACTERIZED by the fact that: the first fraction (6) further comprises 1-butene; the effluent (15) recovered from the first reaction zone of the metathesis (14) optionally further comprises unreacted isobutene; fractionating the effluent (15) from the first metathesis reaction zone (14) and the effluent (30) from the second metathesis reaction zone (24) comprising: fractioning the effluent (15) from the first metathesis reaction zone (14 ) to recover a fraction comprising ethylene and propylene (16), a fraction comprising any unreacted isobutene and any unreacted 1-butene (20), and a fraction comprising any C5 and C6 olefins (22); and fractionate the effluent (30) from the second metathesis reaction zone (24) and the fraction comprising ethylene and propylene to recover a fraction of ethylene (26), a fraction of propylene (32), a fraction of C4 (36), and a fraction comprising at least one of the C5 and C6 olefins (34); and the process further comprising: feeding at least a portion of the ethylene fraction (26) to the second metathesis reaction zone (24) such as ethylene; feeding at least a portion of the C4 fraction (36) to the second metathesis reaction zone (24); and feeding at least a portion of the fraction comprising any unreacted isobutene and any unreacted 1-butene (20) to the first metathesis reaction zone (14).
    [0010]
    10. Process according to claim 9, CHARACTERIZED by the fact that it further comprises: feeding a portion of the second fraction (8) to a reaction isomerization zone (11) containing an isomerization catalyst; contacting the 2-butene with the isomerization catalyst to convert at least a portion of the 2-butene to 1-butene; recovering an effluent from the reaction isomerization zone (11) comprising 1-butene and any portion of unreacted 2-butene; and feeding the effluent from the reaction isomerization zone (11) to the fractionation of a mixed C4 flow.
    [0011]
    11. Process according to claim 9, CHARACTERIZED by the fact that the first fraction (8) further comprises isobutane, the process further comprising: fractionating the first fraction (8) to recover an isobutane fraction and a isobutene fraction and 1-butene; and feeding the fraction comprising isobutene and 1-butene to the first metathesis reaction zone (14) as at least a portion of the first fraction (8).
    [0012]
    12. Process according to claim 7, CHARACTERIZED by the fact that it further comprises: feeding a mixed C4 hydrocarbon stream (2) to a catalytic distillation reactor system (7); the mixed C4 hydrocarbon stream (2) comprising 1-butene, 2-butene and isobutene; the first fraction (6) further comprises 1-butene; and the isomerization and fractionation of the mixed C4 hydrocarbon flow (2) are carried out in the catalytic distillation reactor system (7).
    [0013]
    13. Process according to claim 12, CHARACTERIZED by the fact that the first fraction (6) further comprises isobutane, the process further comprising: fractionating the first fraction to recover an isobutane fraction (46) and an isobutene fraction and 1-butene (6); and feeding the fraction comprising isobutene and 1-butene (6) to the first metathesis reaction zone (14) as at least a portion of the first fraction.
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    同族专利:
    公开号 | 公开日
    KR20150056606A|2015-05-26|
    PH12015500512B1|2015-04-27|
    CL2015000635A1|2015-11-20|
    CA2885002C|2016-11-29|
    JP2017160246A|2017-09-14|
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    PH12015500512A1|2015-04-27|
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    TW201418205A|2014-05-16|
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    EP2895445A4|2016-04-13|
    ZA201501433B|2016-01-27|
    JP6366587B2|2018-08-01|
    TWI586642B|2017-06-11|
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    CN104684873A|2015-06-03|
    SG11201501890YA|2015-04-29|
    US9422209B2|2016-08-23|
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-09| 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 11/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261701144P| true| 2012-09-14|2012-09-14|
    US61/701,144|2012-09-14|
    PCT/US2013/059260|WO2014043232A1|2012-09-14|2013-09-11|Propylene via metathesis with low or no ethylene|
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