![]() Method of separating hydrocarbons
专利摘要:
The invention relates to the production of hydrocarbons, in particular their separation from a raw oxygen-containing gas, and can be used to separate waste gases from installations for the production of ethylene oxide. Allocation leads to adsorption from a feed gas containing methane, ethylene, CO-g, nitrogen, argon, and oxygen. 公开号:SU1433407A3 申请号:SU833607162 申请日:1983-06-14 公开日:1988-10-23 发明作者:Бенкманн Христиан 申请人:Линде Аг (Фирма);Хемише Верке Хюльс Аг (Фирма); IPC主号:
专利说明:
Sl1 The invention relates to a pulse pressure adsorption process for producing a hydrocarbon from a gaseous stream containing hydrocarbons and a small amount of oxygen, and can be used, for example, to separate waste gases from installations for the production of ethylene oxide, these exhaust gases can contain a substantial amount of ethylene, less significant amounts of methane, small amounts of oxygen and additionally inert gases, such as argon, nitrogen, carbon dioxide. The purpose of the invention is to increase the safety of the process by reducing the risk of an explosion due to the fact that gas with a low oxygen content is used to increase the pressure in the adsorbers, and also before the completion of the pressure buildup stage, the gas flow is removed from the outlet end of the adsorber. a mixture of gas or this mixture and methane. Fig. I shows the scheme implementing the proposed method; figure 2 is a graph of the installation time. The process is carried out at the facility, switching on four adsorbers 1-4 connected to the syroto gas pipeline 5 from the inlet side, from the exhaust side to the residual gas pipeline 6 having a pressure reducing valve 7. In addition, the outlet ends of the adsorbers are connected to the pipeline 8, which is connected to the pipeline 6 by means of the valve 9. The expansion gases, obtained by reducing the pressure of the first phase and rich in non-adsorbed components, are released into the residual gas through this pipeline. From the inlet side, the adsorbers are connected to the pipeline 10 leading to the buffer or surge tank 11 connected to the pipeline 12 through the valve 13. The gaseous product obtained during the countercurrent depressurization, as well as the cleaning gas and desorbate obtained during the cleaning phase, are introduced into the tank 11 through the pipeline 10. . On the inlet side, the adsorbers have valves 14 - 17 connecting them to the pipeline 5, and on the outlet side 0 five 0 five 0 five 0 five 0 five - not to the pipeline 6, the adsorbers are connected by means of valves 18 - 21, to the pipeline 8 - by means of valves 22 - 25, to the pipelines 10 - by means of valves 26 - 29. Valves 30-33 installed on the inlet side of the adsorbers are connected via pipeline 34 and control valve 35 to pipeline 5 of raw gas. Increased pressure in purified adsorbers using raw gas is carried through this pipeline. Four adsorbers go through identical cycles chronologically shifted relative to each other so that one adsorber is always in the adsorption phase, thus ensuring uninterrupted operation. The adsorption phase of ADS, carried out at constant pressure, is followed by a first E1 pressure release in continuous flow mode. The pressure gas thus obtained is discharged to the residual gas. In the second phase of the flow-through depressurization, E2, the additional gas is removed through the outlet end of the adsorber. This gas passes through the open valves 22 and 25 to the outlet end of the adsorber 4 and.-Flows through the adsorber 4, which is in the purification phase S before it passes through the valve 29 and the pipeline 10 to the buffer tank 11. Following the second continuous flow pressure relief is the phase EZ of the countercurrent pressure relief, during which the flow of desorbate passes through the open valve 26 and the pipeline 10 to the surge tank 11. After the countercurrent pressure drop of the EZ in the adsorber is completed, the cleaning phase S is performed. enny of phase ramjet E2 depressurising the adsorber 2 is supplied via open valves 22 23rd pro- tivotochno direction through adsorption .adsorber 1. Cleaning gas performs a displacement of the adsorbed product component which includes still a high concentration through the outlet end of the adsorber. The cleaning phase is kept relatively short in order to avoid unnecessary dilution of the target gas supplied to the surge tank 11 with cleaning gas. In another embodiment, 3 It is also possible for the process to carry out desorption steps S together with the use of pressure below atmospheric. The product quality improvement achieved in this way, however, is achieved due to ps of the increased energy consumption of the vacuum pump. After the purification phase S is completed, the pressure in the adsorber can be increased to the adsorption pressure. This takes place during the pressure increase phase B, during which the raw gas is supplied to the adsorber 1 through the open valves 35 and 30. After the pressure of the raw gas in the adsorber 1 is increased, the latter completes the full cycle. The remaining adsorbers go through the same cycle, but in a shifted timeline (Fig 2). Example 1. P {) hydrate of ethylene from purge gas - coming out of the ethylene-oxygen conversion unit to produce ethylene oxide. The purge gas exits the installation in the amount of 500 r. At a pressure of 10 bar and a temperature of 40 C. This gas has the following composition, vol. %: Methane50 Ethylene28 Ethane1 Oxygen 5 Carbon dioxide 6 Inert gases IO To restore the ethylene content in this gas, it is fed to the adsorption unit. Silica gel is used as an adsorbent, the cycle time is 16 minutes. The cycle consists of an adsorption phase, during which the gas at a pressure of 9.9 bar flows through the adsorber, the time is 240 seconds, the first continuous phase of the E1 pressure reduction, which lasts 160 seconds and during which the pressure decreases from 9.9 to 6.0 bar, the second continuous phase of pressure reduction E2, which lasts 70 seconds and during which the pressure decreases from 6.0 to 3.0 bar, the countercurrent phase of pressure reduction EZ, which lasts 160 seconds and during which the pressure decreases at a pressure of 1.6 bar from 3.0 bar to the lowest m pressure followed in for 80 seconds of the washing phase S and, finally, the pressure phase B, 0 five 0 five 3407 gQ gg 0 35 40 four which lasts for 240 s and during which the pressure in the adsorber is again increased from 1.6 to 9.9 bar by supplying the source gas. The residual gas in the amount of 222 at 40 ° C is withdrawn from the outlet end of the adsorption unit and, after reducing the pressure in valve 7 to 6 bar, it is discharged. The residual gas has the following composition,%: Methane Ethylene Ethane Oxygen Inert gases 69.9 1.7 .1.4 9.0 18.0 During the regeneration of the loaded adsorbers, a gas is obtained - a product with a higher ethylene content in the amount of 278 nm / h at a pressure of 1.5 bar and temperature. This gas has the following composition, vol.%: Methane34.1 Ethylene49.0 Ethan0.7 Oxygen1,8 Carbon dioxide 10.8 Inert gases 3.6 PRI mme R 2. Source gas of the same composition as in njJHMepe 1. Activated carbon is used as an adsorbent. To prevent an undesired increase in the oxygen concentration in stage B, the residual gas is vented through valves 18 and 19, 20, 2 and 7 to a pressure in the adsorber of 6 bar. The duration of stage B is increased to -300 s due to the fact that the duration of the adsorption stage is reduced to 180 s. Table 1 presents the composition of the material flows, namely the composition of the raw gas, the residual gas at stage B, the residual gas at the stage ADSM grocery gas. I -, Froze The process is carried out analogously to example 2, when using sipikegel as an adsorbent, the original is separated. gas with an oxygen concentration of 8 vol.%. No undesirable oxygen concentration is observed. The composition of the material flows are given in table 2. EXAMPLE 4 The process is carried out analogously to example 1. At an oxygen concentration of 10% by volume and the use of silica gel as an adsorbent, the process is carried out with the addition of oxygen-free methane at the first stage of stage B to a pressure of 3 bar. For further pressurization, feed gas is used. The composition of the material flows is given in table 3. i Sample The process is conducted Nitrogen, argon, and oxygen with an oxygen content of 5–12 vol.% during the adsorption phase at elevated pressure adsorb ethylene to silica gel or activated carbon from the outlet side of the adsorber during the adsorption phase –i. The subsequent phase of the direct flow is similar to Example 1, but when pressure is applied, the gas stream with a reduced scientific research institute of activated coal, with ethylene content, desorbs 10% by volume of the adsorbed ethylene with oxygen, and when using silica from the outlet the adsorber of the gel, and in the source gas of an ethylene-enriched content is displaced by 12% by volume of oxygen, the first stage of the 5th phase of the countercurrent depressurization of pressure; stage I is carried out at a pressure of 4 bar; can not contain oxygen until adsorption pressure during the methane phase. To further increase the pressure of the feed gas, the feed gas is used. or raw gas and methane from star-Tables .. 4 and 5 show the compositions before the completion of this phase of the respective material flows. gaseous flow with reduced ethylene content through the adsorbent outlet, and the cycle is repeated. 2. A method according to claim 1, characterized in that a raw gas is used which contains 5-10% by volume of oxygen. 3. The method according to Claim 1 is also distinguished by the fact that a raw gas containing 5-8% by volume of oxygen is used.
权利要求:
Claims (1) [1] Claim 1. The method of introducing hydrocarbons 25 from a raw oxygen-containing | Gas by adsorption with a pulsating pressure, carried out in several cyclically interconnected adsorb-Ipax, characterized in that to increase the safety of the process, from a raw gas containing methane, ethylene, carbon dioxide, nitrogen, argon and oxygen when containing Activated carbon, 5 bb.% Oi in commodity gas 50,00250,0054,3716,50 28,00140,00,2,720,83 1,005,000,890,27 5,0025,0014,344,35 6,0030,000,000.00 7,0035,0019,285,85 3,0013,008,402,55 Table 1 Silica gel, 8 vol.% 0 in raw materials Silikel, JO otf.Z Oj in raw CH C | H CtHe 04 cot Ar t 46.00 230.00 100.00 100.0 35.73 98.96 68.93 33.12 71.97 197.92 27,00135, 1.00 5.00 0.00 10,0050,000.00 6,0030,00-0,00 7,0035,000.00 0.0046.50128.79 1,900,911,935.30 0.00 0.64 l, 7a 0.900 "431.012.79 0.00 2.84 7.87 14,597,0112,7735,12 0.00 10.58 29.30 0,000,000,250.70 0.00 2.52 10.19 4.90 8.41 23.14. 3.00 15.00 0.00 0.00 1.19 -3.28 3.50 1.66 3.65 10.04 Akhtivirovy coal, 10 vol. 2 O; in raw CH4 46.00 230.00 100.00 148.00 68.93 33.12 70.65 173.08 48.40171.80 . .-. CjIU 27.00 135.00 0.00 0.00 1.90 0.91 2.295.61 36.20 128.48 table 2 Tab CAC 0.0046.50128.79 1.90 0.00 0.64 l, 7a 0.90 0.00 2.84 7.87 14.59 0.00 10.58 29.30 0.00 0.00 2.52 10.19 T b and D tlH С | Н, With “HB Ot coj AT m " 46.00 230.00 100.00 130.00 70.64 35.70 71.86 212.40 39.42 111.70 26,00130,000,000,001,720,67Г, 90 1,00- 5,000,000,000,810,41 .0,95 1-2,0060,000,000, (0Г4,937,5513,87 5.5027,560,000,000,000,000.25 6.5032,500,009,008,684, 78 3.0015,000,000,003,231,633.39 5,6143,52123.53 2,800 41,014,03 | 1.45 .0,749,4326,76 23,011,805,10 10,031,183,; 34 Ip od lzh e ni etl four Product oe.Z nm) / h 43,52123.53 0, 4.03 | 1.45 9,4326,76 1,805,10 1.183; 34
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引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 NL266305A|1960-09-16|1900-01-01| NL136032C|1961-12-18|1900-01-01| NL297067A|1962-09-04|1900-01-01| CH417534A|1964-07-01|1966-07-31|Exxon Research Engineering Co|Adsorption process| US3430418A|1967-08-09|1969-03-04|Union Carbide Corp|Selective adsorption process| US3564816A|1968-12-30|1971-02-23|Union Carbide Corp|Selective adsorption process| US3636679A|1971-01-04|1972-01-25|Union Carbide Corp|Selective adsorption gas separation process| DE2461759B2|1974-01-02|1976-10-14|Union Carbide Corp., New York, N.Y. |METHOD OF PURIFYING CRUDE METHANE| US4025321A|1975-09-30|1977-05-24|Union Carbide Corporation|Purification of natural gas streams containing oxygen| DE2604305C2|1976-02-04|1988-01-21|Linde Ag, 6200 Wiesbaden, De| DE2840357A1|1978-09-16|1980-04-03|Linde Ag|ADIABATIC ADSORPTION METHOD FOR GAS PURIFICATION OR SEPARATION| DE2854060C2|1978-12-14|1991-07-11|Linde Ag, 6200 Wiesbaden, De| DE2916585A1|1979-04-24|1980-11-06|Linde Ag|PRESSURE CHANGE ADSORPTION METHOD| US4305734A|1979-09-19|1981-12-15|Mcgill Incorporated|Recovery of hydrocarbon components from a hydrocarbon-carrier gas mixture|DE3345379A1|1982-06-16|1985-06-27|Bergwerksverband Gmbh, 4300 Essen|Process for the isolation and recovery of gases relatively strongly adsorbable to adsorbents from gas mixtures otherwise containing essentially gases only weakly adsorbable| US4595490A|1985-04-01|1986-06-17|Union Carbide Corporation|Processing of high normal paraffin concentration naphtha feedstocks| US4769047A|1987-06-29|1988-09-06|Shell Oil Company|Process for the production of ethylene oxide| CA1320735C|1987-11-24|1993-07-27|Ramakrishnan Ramachandran|Process for the production of nitriles and anhydrides| US4849537A|1988-02-09|1989-07-18|The Boc Group, Inc.|Process for the production of nitriles| US5008412A|1988-07-06|1991-04-16|The Boc Group, Inc.|Process for the production of oxides| US4990632A|1988-03-23|1991-02-05|The Boc Group, Inc.|Process for the production of oxides| US4849538A|1988-03-23|1989-07-18|The Boc Group, Inc.|Process for the production of nitriles| US4868330A|1988-04-06|1989-09-19|The Boc Group, Inc.|Process for the production of nitriles| US4870201A|1988-12-08|1989-09-26|The Boc Group, Inc.|Process for the production of nitriles| US5008414A|1988-12-08|1991-04-16|The Boc Group, Inc.|Process for the production of oxides| US5177225A|1990-07-09|1993-01-05|The Boc Group, Inc.|Process for the production of alkylene oxide| US5232473A|1992-05-07|1993-08-03|The Boc Group, Inc.|Pressure swing adsorption with countercurrent feed pressurization| JPH0760048A|1993-08-26|1995-03-07|Mitsubishi Petrochem Eng Co Ltd|Recovery of ethylene from exhaust gas of ethylene oxide production plant| ES2166632T3|1998-03-18|2002-04-16|Boc Group Inc|PROCEDURE FOR THE SEPARATION OF ALKINS AND ALKANS.| KR100279881B1|1998-06-29|2001-03-02|손재익|Adsorbents and methods for the separation of ethylene and propylene AND/OR unsaturated hydrocarbons from mixed gases| AT500315T|2001-08-16|2011-03-15|Statoil Asa|METHOD FOR CUTTING| US6576043B2|2001-10-12|2003-06-10|Air Products And Chemicals, Inc.|Recovery of nitrogen and light hydrocarbons from polyalkene purge gas| US20030073788A1|2001-10-12|2003-04-17|Golden Timothy Christopher|Recovery of olefin monomers| US6699307B1|2002-10-11|2004-03-02|H2Gen Innovations, Inc.|High recovery PSA cycles and apparatus with reduced complexity| US8262771B2|2006-10-31|2012-09-11|Osaka Gas Co., Ltd.|Flammable gas concentration device and flammable gas concentration method| CN106232206A|2014-04-22|2016-12-14|国际壳牌研究有限公司|The method being reclaimed methane by the gas stream containing methane and ethylene| CN106660903A|2014-06-30|2017-05-10|国际壳牌研究有限公司|Process for recovering methane from a gas stream comprising methane and ethylene| RU2642560C2|2016-04-26|2018-01-25|Общество с ограниченной ответственностью "НПО Пылеочистка"|Method of distilling liquids in inert gas environment| WO2019113230A1|2017-12-05|2019-06-13|Bp Corporation North America Inc.|Method of recovering paraxylene in a pressure swing adsorption unit with varying hydrogen purge flow direction|
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申请号 | 申请日 | 专利标题 DE19813150137|DE3150137A1|1981-12-18|1981-12-18|ADSORPTION METHOD FOR SEPARATING HYDROCARBONS| 相关专利
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