• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the production of ethylene by pyrolytically cracking one or more C2-6-paraffins in a pyrolytic cracking furnace having a plurality of elongated serpentine-situated thermal cracking tubes which have a 20-50% longer run life as a result of the selective cracking of a hydrocarbon feed having more carbon atoms per molecule than the C2-6-paraffins at conditions sufficient to selectively place a coat of amorphous, relatively smooth coat of coke on the interior walls of the thermal cracking tubes and thereby mask the catalytic effect of iron, nickel, both iron and nickel, or other metal catalytic sites indigenous to the walls of the tubes.
    公开号:SU1621812A3
    申请号:SU864027821
    申请日:1986-07-10
    公开日:1991-01-15
    发明作者:Линн Бадделл Робин；Мари Освальд Одри；Алберт Лагард Вилльям
    申请人:Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a method for producing ethylene by the pyrolytic cracking of paraffinic hydrocarbons having no more than six carbon atoms per molecule in a pyrolytic cracking furnace having a series of elongated thermal cracking pipes located therein.
    The aim of the invention is to create a method for cracking a lower paraffinic hydrocarbon into a low olefinic hydrocarbon in a thermal cracking scheme with a longer service life of the thermal cracking reactor - a tube furnace.
    The process is carried out in a cracking furnace, usually consisting of a large compartment, lined up or lined with high.
    refractory material, with tools. to allow direct heat by direct combustion of methane or fossil fuels. Within the scope of the invention, it is also assumed that the furnace is heated by other means (coal furnace or energy turf). In the preheating zone, the feed material is heated, passes through a conductive shaft, and is cracked in the combustion sector of the furnace. The first hydrocarbon feed (gasoline fraction) and the second hydrocarbon feed (ethane) are kept inside a row of cracked-kinging pipes that extend almost from the top to the bottom of the furnace.

    ABOUT
    Furnace cracking pipes may be one long joint engine pipe, a pair or more of interconnected pipes located in a substantial pipe.
    middle section of the cracking furnace. It is desirable that the hydrocarbon materials pass very quickly through the coil circuit of the heating tubes. Dp this, they are calculated with the bandwidth JQ
    the ability with respect to the second hydrocarbon feed at a specific temperature to ensure the cracking of paraffin (ethane) into the olefin product (ethylene) to produce as much as possible 15 coke.
    The method is carried out as follows.
    Ethane is loaded in a mixture with dilute steam at a ratio of ethane to py preferably from 1: 0.3 to 1: 0.6. Ethane is cracked under ethylene cracking conditions, which preferably include a temperature of 315 -, a pressure of 0.5 - 10 bar (a lower pressure of 25 is actually desirable), preferably 1-10 bar, and a gas hourly space velocity of 0.2 -, 2 s. . It is inevitable that the cracking of ethane will produce uncatalyzed gas phase 30 tar, which is then deposited on. the inner side walls of the chimneys and the cooling zone form coke. However, the amount of coke produced in the gas phase for a certain 35 period of time is less than the amount that is produced catalytically in the absence of a selected precoat. Selective coating of the inner walls of the cracking tubes to a layer of coke from the first cracking of hydrocarbons inhibits metallic coke formation.
    The catalytic sites of iron, nio, kel, and other catalytically active metals are masked by a selective coating layer of amorphous coke on the inner walls of the cracking tubes. Uncoated catalytic metal sites catalyze the cracking of at least a portion of ethane to unwanted coke deposits. Since then, the conversion of ethane to pyrolysis into ethylene has been carried out almost in the complete absence of the catalytic composition of the substance added to the raw material, or existing as an ion inherent in the material
    55
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    Secondly made tank walls
    tube furnace.
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    After the formation of ethylene, the effluent stream of the product is withdrawn from the pipes of the cracking furnace and is passed to the cooling and separation zone. The cooling zone, which rapidly cools ethylene, can be of any known type. The preferred cooling means comprises a shell-and-tube heat exchanger with a large number of tubes sufficient to pass the hot ethylene effluent stream directed upwards in heat exchange through the wall with liquid material, such as boiler water. having a temperature below the ethylene effluent temperature. The temperature of the ethylene effluent is lowered to a value no higher than 482 ° C, at least by, preferably, from a temperature of 982 or 1093 ° C existing during emission from the final stage of the process in a tubular thermal cracking unit. Lowering the temperature of ethylene ensures that no further conversion or cracking will occur in the future to form coke or other less desirable hydrocarbons.
    The cooled reaction product directed downstream of the cooling zone passes through a series of fractionation units to further lower the temperature and fractionate the ethylene to a pure state. It is possible that some impurities in ethane will be present in ethylene and therefore will create a need for further rectification. Any recovery of uncracked ethane or paraffin by-product can be recycled to the cracking zone, with or without using a purification technique to protect against unwanted accumulation of impurities in the cracking tubes.
    The drawing graphically presents data comparing the service life of kiln tubes in days for experiments conducted with initial cracking of ethane and subsequent cracking of liquids, only with cracking of ethane, as well as with cracking of ethane, which was preceded by a selective cracking process for coating chimney tubes from
    m, as expected, a layer of ethane coke is deposited on the walls of the cracking furnace and in the injection heat exchanger. Then, after stopping the passage of ethane, a liquid feed containing material with a boiling range of gasoline is added to the cracking furnace. Immediately, the ethane-derived coke begins to crack and immediately clogs the pipes of the pressure heat exchanger. The process time is 25 days for ethane and less than one day for a liquid feed material. This is shown on the curve A and in the table. In the drawing, the pressure drop through the heat exchanger is plotted in bars along the vertical axis and the service life in days along the horizontal axis.
    Comparative experiment B.
    In this experiment, ethane is again cracked again, followed by the cracking in the vapor phase of a dry gas containing evaporated C $ / C $ fractions. The total cycle time with ethane is 26 days and the pressure immediately rises low in the heat exchanger after the start of cracking the second hydrocarbon feed. It is determined that an immediate increase in pressure in the injection heat exchanger precludes the continuation of the cracking of the second hydrocarbon feed.
    Comparative experiment C.
    In this experiment, only ethane is cracked into ethylene without any other material. The pressure drop through the heat exchanger reaches a hard-to-control level after 35 days of the full operating cycle; This indicator can be achieved without a pre-selected coating of the cracking tubes. This is shown in the drawing of curve C.
    Examples 1-2. This shows the pre-selected coating of the cracking furnace of the invention. Liquid gasoline feedstock is passed through the system for 11 days at an outlet temperature of 804-815 ° C from the coil to selectively apply a relatively even layer of amorphous coke to the pipe walls of the cracking furnace.
    3.18 - 1.59 mm. After this cracking, ethane is charged and the reactor is in working condition until the pressure at the exit of the heat exchanger becomes unacceptable. Delta
    15
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    5 jq
    40
    dg
    35
    50
    55
    Flow through the heat exchanger as a function of the duration of the working cycle is shown in the drawing using curves 1 and 2, respectively for examples 1 and 2.
    Comparative experiments D - C.
    The cracking of a liquid hydrocarbon was first used in comparative experiments for a period of time insufficient to form the necessary coke layer in the pipes. Duration of working cycles with ethane is 21,20,48 and 35 days respectively. The results of these experiments are summarized in the table.
    It can be seen that a certain amount of coke resulting from the supply of liquid hydrocarbon must be deposited on the inner surfaces of the cracking furnace tubes in order to achieve longer periods for the transmission of ethane, as shown in Example 1. The exact duration of these cycles may vary in depending on the conditions and the particular supply of hydrocarbon, which should be cracked first. The duration of the operating cycle of the first stage of the preferred coating should be sufficient to apply a layer of coke formed by cracking hydrocarbons containing more than two carbon atoms with a depth of more than 1.59 mm but less than 3.18 mm.
    The length of the operating cycle of the cracking furnace, indicated by the pressure at the inlet of the heat exchanger, is the end of the operating cycle. This exact pressure may vary for different cracking processes; however, as soon as this pressure starts to rise above 1.4 bar, there comes a point when, during the continuous operation of the furnace, the pressure rises sharply and exponentially. A rapid increase in pressure is indicated by ordinate in the drawing.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing ethylene, including the preliminary thermal cracking of the gasoline fraction in the coils of a tubular furnace to produce a hydrocarbon product and coke, followed by thermal cracking of ethane in the same coils of the tubular furnace, about l and
    relatively even layer of amorphous coke.
    Example. Ethane is cracked to ethylene in the presence of diluted steam. Ethane is loaded into the heating sector of the furnace through the pipeline and the suction inlet. Steam through the pipeline and the pipe is mixed with ethane. Any of these components may be pre-mixed before loading into the nozzle using a pipeline and a movable valve. The nozzle communicates with elements of a tubular cracking reactor, which is made to pass through a furnace containing a preheating zone, a charge, and a furnace. In the kiln preheating sector, a series of burners for direct fired heating of the feed ethane can be located. If necessary, direct preheaters to maintain the endothermic conditions of pyrolytic cracking in the furnace can be used for heating when ethane is fed into the pipeline (even in the heating sector), in which case there is no need to install direct firing burners. Ethane flows very quickly through pipes into the heating sector through the mine space to the firebox. It is assumed (but not necessary) that the preheating sector and the mining sector can be eliminated to eliminate capital costs, since a certain type of preheating means is provided to transfer the heated ethane to the furnace. It is also contemplated that the combustion unit may preferably be divided into three parts in order to more fully utilize the calculated temperature distribution profiles for the cracking of ethane.
    The temperature in the lower part of the pipes can drop to 315 ° C, while the temperature in the upper part of the pipes can reach 1093 ° C, for this reason, constant cooling and heating of ethane during the passage through the tubular cracking reactors create a significant stress, which may cause the pipes to bend in such a way that they will not be placed in a strictly linear order one above the other. Ethane is cracked to ethylene in pipes. Ethylene exits the combustion unit through pyrolytic cracking pipes through a pipeline and passes through
    0
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    A discharge pipe (not shown) in a plurality of tubular sections for upward movement to the top of the heat exchanger. Heat exchanging fluid (water or water vapor) is supplied to the case of the shell-like heat exchanger using inlet and outlet means. The temperature of ethylene in the pipeline is much higher than the temperature of ethylene in the cooling zone (heat exchanger) of the effluent, the temperature of the fluid in the pipeline is much higher than the temperature of the fluid in the pipeline.
    Coke samples taken either from the cooling injection sections or from the tube furnaces have different visible substrates. For example, one of these substrates is a glossy black substrate — a typical representative of a coke-formed cracking derivative of hydrocarbons containing more than two carbon atoms per molecule, while ethane-produced coke is very porous and brittle.
    The following examples are given to illustrate the unpredictable increase in the service life achieved by selectively coating the coke derivative of the cracking of hydrocarbons containing more than two carbon atoms per molecule before injecting ethane. Unexpected results were found during the actual operation of the cracking furnace, modified to accommodate both liquid and gaseous feed materials, and these examples do not limit the claims. Comparative experiments are not in accordance with the invention.
    Comparative experiment A.
    In this experiment, the sequential hydrocracking system is carried out in such a way that ethane is first cracked to precipitate the ethane-derived coke layer on the walls of the cracking furnace before introducing a liquid feed that has a gasoline boiling point. Ethane is added to the preheating section of the furnace when it is discharged from the preheating section at 593-643 ° C and fed to the combustion section, maintaining the last temperature at 1121dC. Ethane is continuously cracked for 25 days of continuous kiln operation and is prompted by the fact that, in order to increase the duration of operation of the tube furnace, the preliminary thermal cracking of the gasoline fraction is a disease under conditions that ensure the deposition of an amorphous coke layer on the inner surface of the tube furnace coils thickness of 1.59-3.18 mm.
    F CC gas is a catalytic cracking exhaust gas in a fluidized bed that contains up to 10 wt.% Cg / Cf material.
    1,380 1,240
    f, f04 0, W 0.828 0.690 0.552. 0, W 0, Z76
    o, m
    0 5 Ю 15 W 25 30 35 W ft 50 55 60 65 70 75 80 85 30 35 W
    类似技术:
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    同族专利:
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    ES2000271A6|1988-02-01|
    KR940001846B1|1994-03-09|
    CA1263967A|1989-12-19|
    EP0208359A3|1987-07-01|
    CN86104303A|1987-02-18|
    EP0208359B1|1990-08-08|
    AU589655B2|1989-10-19|
    CN1006704B|1990-02-07|
    JPS6219538A|1987-01-28|
    EP0208359A2|1987-01-14|
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    BR8603226A|1987-02-24|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US2111900A|1936-02-08|1938-03-22|Nagel Theodore|Process for the manufacture of ethylene from oil|
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    US5733438A|1995-10-24|1998-03-31|Nalco/Exxon Energy Chemicals, L.P.|Coke inhibitors for pyrolysis furnaces|
    US5863416A|1996-10-18|1999-01-26|Nalco/Exxon Energy Chemicals, L.P.|Method to vapor-phase deliver heater antifoulants|
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    KR100419621B1|1998-12-21|2004-04-17|주식회사 포스코|Manufacturing method of concrete aggregate having excellent compressive strength|
    DE10344801A1|2003-09-26|2005-05-04|Celanese Emulsions Gmbh|High solids aqueous polymer dispersions, process for their preparation and their use|
    US8057707B2|2008-03-17|2011-11-15|Arkems Inc.|Compositions to mitigate coke formation in steam cracking of hydrocarbons|
    WO2010021909A2|2008-08-19|2010-02-25|Shell Oil Company|Process for the conversion of lower alkanes to ethylene and aromatic hydrocarbons|
    US8835706B2|2009-11-02|2014-09-16|Shell Oil Company|Process for the conversion of mixed lower alkanes to aromatic hydrocarbons|
    ES2714870T3|2011-06-13|2019-05-30|Eco Environmental Energy Res Institute Limited|Method for preparing fuel using oils and biological fats|
    WO2015000944A1|2013-07-02|2015-01-08|Shell Internationale Research Maatschappij B.V.|A process of converting oxygenates to olefins and a reactor for that process|
    WO2015000948A1|2013-07-02|2015-01-08|Shell Internationale Research Maatschappij B.V.|A method of converting oxygenates to olefins in a reactor having a protective layer of carbonaceous material|
    WO2015000950A1|2013-07-02|2015-01-08|Shell Internationale Research Maatschappij B.V.|A process of converting oxygenates to olefins and a reactor comprising a inner surface coated with a protective layer of carbonaceous material|
    DE102014007470A1|2013-11-15|2015-05-21|Linde Aktiengesellschaft|Process and apparatus for steam reforming and steam cracking of hydrocarbons|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/755,035|US4599480A|1985-07-12|1985-07-12|Sequential cracking of hydrocarbons|
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