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  • 专利说明
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    • 专利摘要:
    ETHYLENE SEPARATION PROCESS. Ethylene separation processes are described here. Ethylene separation processes generally include the introduction of a feed stream including ethylene and butene in a de-ethylenizer; and separating ethylene from butene through fractional distillation within the de-ethylene maker to form an upstream including separate ethylene and a bottom stream including separate butene, wherein the de-ethylene maker operates at a pressure below 350 psig (2.41 MPa).
    公开号:BR112015015460B1
    申请号:R112015015460-3
    申请日:2014-01-08
    公开日:2021-01-12
    发明作者:Allen David Hood Jr.；Robert S. Bridges；Gary A. Sawyer；Steven T. Coleman
    申请人:Lyondell Chemical Technology, L.P.；Equistar Chemicals, Lp；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDERS
    [001] This application claims benefit and priority from United States Patent Application No. 13 / 738,685 filed on January 10, 2014, which is incorporated herein by reference, in its entirety. BACKGROUND FIELD OF THE INVENTION
    [002] The present invention generally relates to ethylene separation processes. More particularly, the present invention generally relates to the separation of ethylene within a propylene production process. RELATED TECHNIQUE
    [003] This section presents information about the technique that may be related to or provide context for some aspects of the techniques described here and / or claimed below. This information represents a history to facilitate a better understanding of what is disclosed here. This is a discussion of the "related" technique. The fact that such a technique is related in any way implies that it is also a "prior" technique. The related technique may or may not be prior art. The discussion should be read in this light and not as an admission of prior art.
    [004] Ethylene separation processes within propylene production processes often exchange fresh ethylene with the feed for the ethylene separation process before introducing fresh ethylene for a metathesis reaction. However, efforts are continuously underway to improve ethylene separation processes, including reducing energy requirements and other costs in propylene production processes.
    [005] The present invention is aimed at solving, or at least reducing, one or all of the problems mentioned above. SUMMARY
    [006] Various embodiments of the present invention include processes for separating ethylene. Ethylene separation processes generally include introducing a feed stream including ethylene and butene into a de-ethenizer; and separating the ethylene from the butene by fractional distillation within the de-ethylenizer to form an upper stream including separate ethylene and a back stream including separate butene, where the de-ethylene operates at a pressure of less than 2.41 MPaG (350 psig).
    [007] Various embodiments of the present invention further include processes for the production of propylene. The processes generally include reacting a metathesis feed stream including butene with ethylene in the presence of a metathesis catalyst through a metathesis reaction to form a metathesis product stream including propylene, ethylene and butene; separating ethylene from propylene by fractional distillation within a de-ethylenizer to form a top stream including separate ethylene and a back stream including separate butene and propylene; and recycle the upper chain of the de-ethenizer for the reaction of metathesis in the form of steam.
    [008] One or more modalities include the process of any previous paragraph, including compressing the upper current from a first pressure to a second pressure.
    [009] One or more modalities include the process of any previous paragraph, in which the first pressure ranges from 1.72 MPaG to 2.24 MPaG (250 psig to 325 psig) and the second pressure range varies from 2.07 MPaG to 2.26 MPaG (300 psig to 400 psig).
    [0010] One or more modalities include the process of any previous paragraph, where the difference between the second pressure and the first pressure is 0.34 MPaG to 0.69 MPaG (50 psig to 100 psig).
    [0011] One or more embodiments include the process of any preceding paragraph including further condensing a portion of the upper stream to form a recycling ethylene stream and introducing the recycling ethylene stream to the de-ethenizer, where the upper stream is compressed before condensing.
    [0012] One or more modalities include the process of any previous paragraph, also including the introduction of fresh ethylene in the de-ethylenizer as a recurrent supplement.
    [0013] One or more modalities include the process of any previous paragraph, in which the de-ethenizer operates at a pressure below 2.41 MPaG (350 psig).
    [0014] One or more modalities include the process of any previous paragraph, in which the feed stream also includes propylene.
    [0015] One or more embodiments include the process of any preceding paragraph, further including condensing a portion of the upper stream to form a recycling ethylene stream and introducing the recycling ethylene stream to the de-ethenizer.
    [0016] One or more modalities include the process of any previous paragraph, in which fresh ethylene is introduced into the de-ether at a temperature of -28.88 ° C to -12.22 ° C (-20 ° F to 10 ° F ).
    [0017] One or more modalities include the process of any previous paragraph, in which the current of the metathesis product is introduced into the de-ethenizer at a temperature of 10 ° C to 32.22 ° C (50 ° F to 90 ° F ).
    [0018] One or more modalities include the process of any previous paragraph, in which the flow of metathesis product is introduced into the de-ethenizer at a pressure of 1.72 MPaG to 2.41 MPaG (250 psig to 350 psig).
    [0019] The above paragraphs present a simplified summary of the object currently disclosed in order to provide a basic understanding of some aspects of it. The summary is not an exhaustive view, nor is it intended to identify key or critical elements to delimit the scope of the object claimed below. Its sole purpose is to present some concepts in a simplified way as an introduction to the more detailed description presented below. BRIEF DESCRIPTION OF THE DRAWINGS
    [0020] The object claimed can be understood by reference to the following description taken in conjunction with the attached drawings, in which the same reference numbers identify the same elements, and in which:
    [0021] Figure 1 illustrates an application of a propylene production process.
    [0022] Figure 2 illustrates an alternative application of a propylene production process.
    [0023] Although the invention is susceptible to several modifications and alternative forms, the drawings illustrate specific applications described in detail here by way of example. It should be understood, however, that the description here of specific applications is not intended to limit the invention to particular disclosed forms, but rather the intention is to cover all modifications, equivalents and alternatives that belong to the spirit and scope of the invention as defined by the attached claims. DETAILED DESCRIPTION
    [0024] Modalities illustrating the object claimed below will now be disclosed. For the sake of clarity, not all features of an actual implementation are described in this report. It will be noted that in the development of any such real application, numerous implementation-specific decisions must be made to target the specific objects of the developers, such as compliance with system-related and business-related restrictions, which will vary from one implementation to another . Furthermore, it will be noted that such a development effort, even if complex and laborious, would be a routine task for those skilled in the art having the benefit of this description.
    [0025] In the description below, unless otherwise specified, all compounds described here may be substituted or unsubstituted and the list of compounds includes derivatives thereof. In addition, various ranges and / or numerical limitations can be expressly indicated below. It must be recognized that unless otherwise stated, the parameters are intended to be interchangeable. In addition, any ranges include iterative ranges of similar magnitudes covered within the ranges or limitations expressly indicated.
    [0026] Applications described herein include ethylene separation processes. Ethylene separation processes are discussed primarily here with reference to separating a metathesis product stream within a propylene production process. However, it is envisaged that the ethylene separation processes described herein can be used within any process that requires the separation of ethylene from butene.
    [0027] Propylene production processes generally include reacting a metathesis feed stream including n-butene with ethylene in the presence of a metathesis catalyst to form a metathesis product stream including propylene, ethylene, butene and C5 + olefins. As used herein, the term "metathesis" refers to an equilibrium reaction between two olefins where the double bond of each olefin is broken to form intermediate reagents. These intermediates recombine to form new olefin products. In one or more specific applications discussed here, the two olefins include ethylene and butene and the new olefin product is propylene.
    [0028] As discussed above, n-butene is fed into the metathesis reaction through the metathesis feed stream. Ethylene can be fed into the reaction by any suitable method known to a person skilled in the art. For example, ethylene can be fed into the metathesis reaction through an input separate from an input used to feed the metathesis feed stream. Alternatively, ethylene can be combined with the metathesis supply stream before the metathesis supply stream passes through such an inlet.
    [0029] Metathesis catalysts are well known in the art (see, for example, US Patent No. 4,513,099 and US Patent No. 5,120,894). Generally, the metathesis catalyst includes a transition metal oxide, for example, the transition metal oxides of cobalt, molybdenum, rhenium, tungsten and combinations thereof, for example. In one or more specific embodiments, the metathesis catalyst includes tungsten oxide. The metathesis catalyst can be supported on a support, such as silica, alumina, titanium, zirconia, zeolites, clays and their mixtures, for example. In one or more modalities, the support is selected from silica, alumina and their combinations. The catalyst can be supported on a support by methods known in the art, such as, for example, adsorption, ion exchange, impregnation or sublimation, for example. The metathesis catalyst can include from 1% by weight to 30% by weight or from 5% by weight to 20% by weight of transition metal oxide, for example.
    [0030] The metathesis reaction may also include the contact of butene with ethylene in the presence of an isomerization catalyst (either sequentially or simultaneously with the metathesis catalyst). The isomerization catalyst is generally adapted to convert 1-butene present in the metathesis feed stream into 2butene for subsequent reaction to propylene. Isomerization catalysts can include zeolites, metal oxides (for example, magnesium oxide, tungsten oxide, calcium oxide, barium oxide, lithium oxide and combinations thereof), mixed metal oxides (for example, silica-alumina, zirconia -silica), acid clays (see, for example, US Patent No. 5,153,165; US Patent No. 4,992,613; US Patent No. 2004/0249229 and US Patent No. 2006 / 0084831) and their combinations, for example. In one or more specific applications, the catalyst is magnesium oxide. Magnesium oxide can have a surface area of at least 1 m2 / g or at least 5 m2 / g, for example.
    [0031] The isomerization catalyst can be supported on a support material. Suitable support materials include silica, alumina, titania, silica-alumina and combinations thereof, for example.
    [0032] The metathesis reaction can occur at a pressure of 1.03 MPaG to 4.1 MPaG or from 1.38 MPaG to 3.45 MPaG or from 1.65 MPaG to 3.10 MPaG (150 psig to 600 psig , or 200 psig to 500 psig or 240 psig to 450 psig), for example. Metathesis reactions can occur at a temperature of 100 ° C to 500 ° C, or from 200 ° C to 400 ° C or from 300 ° C to 350 ° C, for example. Metathesis reactions can occur at an hourly space weight velocity (WHSV) of 3 h-1 to 200 h-1, or from 20 h-1 to 40 h-1, for example.
    [0033] The contact time required to obtain a desirable yield of metathesis reaction products depends on several factors, such as the activity of the catalyst, temperature and pressure, for example. However, in one or more embodiments, the period of time during which the metathesis supply current and ethylene are in contact with the catalyst can vary from 0.1 second to 4 hours or from 0.5 second to 0, 5 hours, for example. The metathesis reaction can be conducted in batches or continuously with fixed catalyst beds, paste catalyst, fluidized beds, or using any other conventional contact techniques, for example.
    [0034] The metathesis product stream generally includes ethylene, propylene, C4 olefins, and C5 + olefins (including pentene and hexene, for example). Therefore, the propylene production process often includes separating chain components from metathesis product. An example of a separation method is shown in U.S. Patent Letter No. 7,214,841, which is hereby incorporated by reference, and such a method generally includes separation within a fractionation system. As used herein, the term "fractionation" refers to processes for the separation of components based on the relative volatility and / or boiling point of the components. Fractionation processes can include those known in the art, and the term "fractionation" can be used interchangeably here with the terms "distillation" and "fractional distillation".
    [0035] The fractionation system usually includes a deetizer. The de-ethenizer receives and separates the metathesis product stream to form an upper stream and a bottom stream. The upper stream is mainly composed of recovered ethylene and at least a portion of the upper stream can be recycled for the metathesis reaction (discussed in more detail below). The bottom stream generally includes propylene, butene and C5 + olefins.
    [0036] The applicant is a distillation technique that involves condensing vapors and returning this condensate to the system from which it originated. Within the distillation column, the downward flowing liquid provides cooling and condensation of the upward flowing vapors, thus increasing the efficiency of the distillation column. Typically, the recurrent liquid is the portion of the upper stream of a distillation column that is returned to the top of the column. Often, the entire upper stream of the dehizer is condensed to form a stream of condensate, which can then be divided into a recurrent liquid stream and a recycle ethylene stream. In such processes, the recycling ethylene stream is returned to the metathesis reaction in liquid form.
    [0037] One or more modalities include partially condensing the upper stream to form a recurring liquid stream and a recycling ethylene stream, which can then be returned to the steam metathesis reaction. Alternatively, when no portion of the above product will be used as a recurring liquid, it is contemplated that the upper stream can be recycled (ie returned to the metathesis reaction) without going through a condenser.
    [0038] When recycling ethylene as steam for the metathesis reaction, the ethylene vapor can be compressed through a first pressure compressor to a second pressure sufficient to supply the ethylene vapor stream for the metathesis reaction. In one or more embodiments, the first pressure can range from 1.72 MPaG to 2.24 MPaG (250 psig to 325 psig) and the second pressure can range from 2.07 MPaG to 2.76 MPaG (300 psig to 400 psig) ), for example. Alternatively, the difference between the first pressure and the second pressure can be from 0.34 MPaG to 0.69 MPaG (50 psig to 100 psig), for example. A specific embodiment includes compressing the above product to raise the condensation temperature used in a subsequent partial condenser.
    [0039] One or more modalities include introducing fresh ethylene to the upper portion of the de-ethenizer, either as an addition, or as a substitute for the recurrent liquid stream. Consequently, fresh ethylene introduced in the de-ethenizer is referred to here as a recurrent complement. As known in the art, "fresh" ethylene refers to ethylene that has not been processed in the system being referred to here as the propylene production process. In one or more modalities, fresh ethylene is introduced into the de-ethylenizer as a recurrent supplement at a rate that is lower than that of the recurrent current liquid.
    [0040] In one or more applications, the complement of fresh / recurring ethylene is introduced into the de-ethenizer at a temperature of -28.88 ° C to 37.77 ° C (-20 ° F to 100 ° F), or -23.33 ° C to 10 ° C (-10 ° F to 50 ° F) or -23.33 ° C to -12.22 ° C (-10 ° F to 10 ° F) and a pressure of 2.07 MPaG to 6.89 MPaG (300 psig to 1000 psig), or 2.76 MPaG to 6.20 MPaG (400 psig to 900 psig) or 4.14 MPaG to 5.51 MPaG (600 psig up to 800 psig), for example.
    [0041] Generally, a de-ethenizer within a propylene production process operates at a pressure of 2.41 MPaG to 4.48 MPaG (350 psig to 650 psig). However, one or more applications of the present invention include operating the de-ethenizer at a pressure below that. For example, one or more modalities include operating the de-ethenizer at a pressure less than 2.41 MPaG (350 psig), or a pressure less than 2.07 MPaG (300 psig), or a pressure less than 1.72 MPaG (250 psig).
    [0042] The fractionation system, in one or more modalities, may also include a de-propanizer and a de-butenizer as known in the art. The de-propanizer can receive and separate the bottom stream (from the de-ethnizer) to form a top stream from the de-propanizer and a bottom stream from the de-propanizer. The top stream of the de-propanizer is composed primarily of the propylene product. The de-propanizer bottom stream generally includes butene and C5 + olefins.
    [0043] The de-butenizer can receive and separate at least a portion of the de-propanizer back stream to form a top de-butenizer back and a debugger back stream. The top stream of the de-butenizer is composed primarily of recovered butene and the bottom stream of the debugger usually includes C5 + olefins. Optionally, at least a portion of the top stream of the de-butenizer can be recycled back to the metathesis reaction.
    [0044] The processes described herein can advantageously reduce the heating requirements in the metathesis reactor and / or in the dehumanizer, possibly by half the heating requirements for similar systems absent in the modalities of the invention. For example, modalities described here provide for a stream of metathesis product entering the de-ethenizer to have a temperature of 10 ° C to -32.22 ° C (50 ° F to 90 ° F) and a pressure of 1.72 MPaG to 2.41 MPaG (250 psig-350 psig), which can eliminate the need for heat exchange from the metathesis product stream.
    [0045] It is noted, however, that, while the addition of a pressor to the ethylene recycling stream can add the capital cost to the process, the low pressure system in the metathesis reaction and the de-ethenizer can offset the compressor's capital cost.
    [0046] Referring now to Figure 1, a simplified process current diagram of a process 100 for the production of propylene according to applications disclosed here is illustrated. Figure 1 illustrates a process 100 including introducing a metathesis feed stream 102 into a metathesis reactor 104 containing metathesis catalyst 105 (and an optional isomerization catalyst not shown) arranged to form the metathesis product stream 106 including propylene, ethylene, butene and C5 + olefins. Figure 1 illustrates a specific application in which ethylene is mixed with the metathesis feed stream 102 through line 108; however, it is anticipated that ethylene may have contact with the metathesis feed stream through processes known in the art.
    [0047] The chain of the metathesis product 106 is passed to a de-ethenizer 110 to separate at least a portion of the ethylene from the chain of the metathesis product 106 to form an upper chain 112 and a bottom chain 114 including propylene and C4 + olefins. .
    [0048] Fresh ethylene is introduced in the de-ethenizer 110 as a recurrent complement (in the same way as the liquid ethylene recurrent is introduced in the de-ethenizer 110) via line 116. In the specific application illustrated in Figure 1, the upper current 112 is passed through a partial condenser 118 to form a recycle ethylene stream 120 and a recurring liquid stream 122. The recycle ethylene stream 120 is removed from the partial condenser 118 as a vapor and is compressed in compressor 128 and then recycled to metathesis reactor 104 via line 130. Recurrent liquid stream 122 is returned to deetherizer 110.
    [0049] On the other hand, as shown in Figure 2, the upper current 112 can be compressed inside the compressor 128 before passing through the partial condenser 118, resulting in a higher condensing temperature than shown in Figure 1.
    [0050] As known in the art, the backflow stream from deetherizer 114 can be passed through a reheater (not shown) and the de-ethenizer 110 is stopped or further separated into additional separation columns (not shown).
    [0051] Therefore, the present invention is well adapted to achieve the purposes and advantages mentioned as well as those that are inherent to them. The particular modalities disclosed above are illustrative only, as the present invention can be modified and practiced in different ways, but apparent equivalents for those skilled in the art having the benefit of the principles contained herein. In addition, no limitation is intended as to the details of construction or design shown here, in addition to those described in the claims below. It is, therefore, evident that the particular illustrative modalities disclosed above can be altered, combined, or modified and all such variations are considered within the scope and spirit of the present invention.
    [0052] The invention illustratively disclosed here may duly be practiced in the absence of any element that is not specifically disclosed here and / or any optional element disclosed here. Although compositions and methods are described in terms of "comprising", "containing", or "including" various components or steps, the compositions and methods can also "consist essentially of" or "consist of" various components and steps. All numbers and ranges disclosed above may vary by a certain amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range that belongs to the range are specifically disclosed. In particular, each range of values (of the form, "from about (a) to about (b)" or, equivalently, "from approximately (a) to (b)" or, equivalently, "from approximately ab") disclosed here must be understood as established for each number and range encompassed within a broader range of values.
    [0053] This concludes the detailed description. The particular applications disclosed above are illustrative only, as the invention can be modified and practiced in different ways, but apparent equivalents to those skilled in the art having the benefit of the principles disclosed herein. In addition, no limitation is intended as to the details of construction or design shown here, other than those described in the claims below. It is, therefore, evident that the particular illustrative applications disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. Consequently, the protection sought here is established in the claims below.
    权利要求:
    Claims (13)
    [0001]
    1. Ethylene separation process, characterized by the fact that it comprises the following steps: introducing a feed stream (108) comprising ethylene and butene in a de-ethylenizer (110); separating ethylene from butene by fractional distillation inside the de-ethylene maker (110) to form a top stream (112) comprising separate ethylene and a bottom stream (114) comprising separate butene, wherein the de-ethylene maker operates at a pressure of less than 2.41 MPaG (350 psig); and introducing fresh ethylene into the de-ethylenizer as a recurrent supplement (116).
    [0002]
    2. Ethylene separation process according to claim 1, characterized by the fact that it still comprises the stage of compression of the upper stream (112) from a first pressure to a second pressure.
    [0003]
    3. Ethylene separation process according to king-vindication 2, characterized by the fact that the first pressure ranges from 1.72 MPaG (250 psig) to 2.24 MPaG (325 psig) and the second pressure varies from 2 .7 MPaG (300 psig) to 2.76 MPaG (400 psig).
    [0004]
    4. Ethylene separation process according to king-vindication 2, characterized by the fact that the difference between the second pressure and the first pressure varies from 0.34 MPaG (50 psig) to 0.69 MPaG (100 psig) ).
    [0005]
    5. Ethylene separation process according to king-vindication 2, characterized by the fact that it still comprises the step of condensing a portion of the upper stream (112) to form a recycling ethylene stream (122) and introducing the stream of recycling ethylene in the de-ethylenizer (110), in which the upper stream is compressed before condensation.
    [0006]
    6. Ethylene separation process according to king-vindication 1, characterized by the fact that the de-ethylenizer operates at a pressure lower than 2.41 MPaG (350 psig).
    [0007]
    7. Ethylene separation process according to king-vindication 1, characterized by the fact that the feed stream still comprises propylene.
    [0008]
    8. Ethylene separation process according to king-vindication 1, characterized by the fact that it still comprises the steps of condensing a portion of the upper stream to form a recycling ethylene stream (122) and introducing the ethylene stream of recycling in the de-ethylenizer (110).
    [0009]
    9. Ethylene separation process according to king-vindication 1, characterized by the fact that fresh ethylene (116) is introduced into the de-ethylenizer at a temperature of -28.8 ° C (-20 ° F) to 12, 2 ° C (10 ° F).
    [0010]
    10. Ethylene separation process according to king-vindication 1, characterized by the fact that the chain of the metathesis product (106) is introduced into the de-ethylene maker (110) at a temperature of 10 ° C (50 ° F) at 32 ° C (90 ° F).
    [0011]
    11. Ethylene separation process according to king-vindication 1, characterized by the fact that the current of the metathesis product (106) is introduced into the de-ethylene maker (110) at a pressure of 1.72 MPaG (250 psig) at 2.41 MPaG (350 psig).
    [0012]
    12. Process for producing propylene, characterized by the fact that it comprises the following steps: reacting a metathesis feed stream (102) comprising: butene with ethylene in the presence of a metathesis catalyst through a metathesis reaction to form a methane stream metathesis product (106) comprising propylene, ethylene and butene; introducing the chain of the metathesis product (106) into the de-ethylenizer (110); and separating ethylene from propylene by fractional distillation within the de-ethylenizer (110) to form a top stream (112) comprising separate ethylene and a bottom stream (114) comprising butene and separate propylene, wherein the de-ethylenizer (110) operates at a pressure less than 2.41 MPaG (350 psig); and also introducing fresh ethylene (116) into the de-ethylene maker (110) as a recurrent supplement; and recycle (130) the upper stream (112) from the de-ethylenizer (130) for the metathesis reaction in the form of steam.
    [0013]
    Process according to claim 12, characterized by the fact that it still comprises the stages of compression (128) of the upper stream (112) from a first pressure to a second pressure; condensing (118) a portion of the upper stream comprising the second pressure to form a recycle ethylene stream (130); and introducing the recycle ethylene stream into the feed metathesis stream (102).
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    法律状态:
    2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| 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 08/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/738,685|2013-01-10|
    US13/738,685|US9688591B2|2013-01-10|2013-01-10|Ethylene separation process|
    PCT/US2014/010631|WO2014110102A1|2013-01-10|2014-01-08|Ethylene separation process|
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