EP1711581A1 - Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps - Google Patents
Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic stepsInfo
- Publication number
- EP1711581A1 EP1711581A1 EP04703646A EP04703646A EP1711581A1 EP 1711581 A1 EP1711581 A1 EP 1711581A1 EP 04703646 A EP04703646 A EP 04703646A EP 04703646 A EP04703646 A EP 04703646A EP 1711581 A1 EP1711581 A1 EP 1711581A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalytic distillation
- recited
- catalyst
- fixed bed
- distillation column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/002—Apparatus for fixed bed hydrotreatment processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
Definitions
- the present invention relates to a method for 'the production of olefins and particularly to processing the cracking heater effluent to more effectively recover the product and process the by-products.
- a method for 'the production of olefins and particularly to processing the cracking heater effluent to more effectively recover the product and process the by-products.
- the net effluent from the pyrolysis heaters typically referred to as charge gas, requires processing for the separation of the byproducts and removal of the diolefins and acetylenes from the primary olefin products .
- the patent relates to a system that is described as being capable of removing 70% and more of the hydrogen in the cracked gas prior to the required cryogenic separation by the hydrogenation of the C2 to C 4 acetylenes and dienes and the Ci and heavier olefins to paraffins. Removal of 70% or more of the hydrogen improves the economicS 'through a significant lowering of the energy requirements for separation of the C2 and heavier components. By reducing the hydrogen partial pressure, separation is achieved at lower pressures and with reduced refrigeration . However, it has been shown that such extensive hydrogenation in a single step system cannot occur without substantial loss of ethylene and propylene to paraffins by hydrogenation. The process as described in USP 5,679 ,241 has significant limitations.
- the C2 acetylene specifically must be removed via hydrogenation since its removal via distillation is extremely difficult requiring extensive equipment and energy costs. Since acetylene is a polymerization catalyst poison, it must be removed to low levels, often less than 1 -2 ppm. The ability to hydrogenate all of the C2 acetylene to that level in a single catalytic distillation column while observing no ethylene loss or preferably a gain was not possible at reasonable catalyst
- ABBLU /260 d A significant variation in catalyst activity will occur with variations in the carbon monoxide in the feed. Such variations if seen in a single step process, will result in loss of acetylene removal efficiency and subsequent products which do not meet specification. This impact on performance due to the loss of catalytic activity via CO poisoning is equivalent to the impact on performance due to catalyst aging. e. A significant variation in feedstock to the ethylene cracking heaters will result in substantial changes in both the acetylenes and dienes as well as the hydrogen flow. As the ratio of hydrogen to reactants changes, a single step process has limited ability to follow such changes.
- the present invention relates to an improved process for the processing of the charge gas effluent from the pyrolysis of a variety of feedstocks.
- the primary objective is still to remove a significant fraction of the hydrogen in the effluent by hydrogenating the C2 to Cs diolefins and acetylenes in the feed while achieving essentially total hydrogenation of the C2 acetylene without significant hydrogenation of the ethylene and propylene.
- This is achieved even with disturbances in the carbon monoxide concentration, varying diene and acetylenic feed concentrations and catalyst deactivation as well as other foreseeable processing upsets.
- the invention relates to catalytic distillation with improved liquid
- ABBLU /260 recycle in combination with fixed bed hydrogenation reactor systems is made possible by the fixed bed hydrogen ation system in
- Figure 1 is a flow diagram of the prior art involving catalytic I 5 distillation alone with the bottoms recirculation for temperature control .
- Figure 2 is a flow diagram -illustrating the present invention .
- Figure 3 is a graph illus trating the ethylene g ain or loss versus the diene output level for the present invention compared to the prior 0 art.
- Figure 4 is a flow diagram similar to Figure 2 but illustrating another embodiment of the present invention.
- Figure 5 is a flow diagram of an alternate embodiment of the present invention .
- Figure 6 is a flow diagram illustrating an alternate embodiment of the process of Figure 5.
- Figure 7 is a flow diagram similar to Figure 2 but illustrating an alternate embodiment of the present invention.
- Figure 1 of the drawings of the present invention is essentially a copy of a drawing from that prior patent simplified to identify only those features relevant to the present invention.
- the charge gas 1 50 is compressed and fed to the catalytic distillation column 1 56.
- This column as in the present invention, simultaneously carries out a catalytic reaction and distillation.
- the column has a stripping section 1 58 below the feed and a rectifying/reaction section 1 60 above the feed containing the catalyst beds 1 66, 1 68 and 1 70. Descending liquid is withdrawn as sidestreams through the intercondensers 1 80 and reinjected back into the column over the next lower catalyst bed . A portion of the heat of reaction is removed by these ' intercondensers.
- a liquid recycle stream 260 from the stripping section is recycled to the column overhead .
- This recycle 260 may be a portion 262 of the bottoms and/or a portion 264 from within the stripping section.
- the overhead from column 1 56 passes into condensers 1 86 and 1 88 and the partially condensed stream enters separation vessel 1 90.
- the product C2 to C5 vapor overhead 1 94, containing ethylene and propylene, then passes out to subsequent separation while the condensed hydrocarbons are utilized as reflux 1 96 for the column. Since the objective of the invention is to completely remove the acetylene impurities from ethylene with no loss of the ethylene entering the column, this must be accomplished in this single step operation (one catalytic distillation column) .
- the overhead vapor stream passes into additional fractionation (not shown) where the individual carbon number fractions are isolated .
- the hydrogenation in catalytic distillation column 1 56 occurs in the liquid phase.
- the column is operated such that liquid phase composition is primarily C5 components. This minimizes the liquid phase concentration of the ' ethylene and propylene and thus minimizes their reaction. However, the concentration of these two valuable olefins in the liquid will not be zero.
- the charge gas may or may not be preheated to match column temperatures.
- the charge gas would typically pass through one or more guard beds 1 5 to remove such poisons as lead (Pb), arsenic (As) and mercury (Hg) .
- Pb lead
- As arsenic
- Hg mercury
- the guard beds would be employed in a known manner to protect the catalytic distillation catalyst. Entering the catalytic distillation column, the 8 % to 20% by Weight diene and acetylenic feed is hydrogenated in catalyst beds 1 6 and 1 8 located in the rectification section 20 of the column.
- the catalytic beds could be of the same or
- the catalysts are known hydrogenation catalysts consisting primarily of one or more Group VIIIA metals (Ni, Pd, Pt) on a support Additives such as Ag or Au ⁇ nd/or alkali metals are typically used to control selectivity and activity Specific examples of selective hydrogenation catalysts particularly suited for this service are disclosed in U S Patents 6,41 7, 1 36, 5, 587,348, 5, 698,752 and 6, 1 27, 588
- the catalytic systems used within a catalytic distillation column can consist of either a single catalyst, a catalyst with different metal loadings to adjust activity located in different portions of the column, or mixtures of catalysts of different metals located in different portions of the column
- the hydrogenation occurs in the liquid phase in catalytic distillation fashion Although only two reactive catalytic beds 1 6 and 1 8 are shown, this is only by way of example and could be any number of beds depending on the requirements of any particular plant or the desire to adjust catalyst activity through the use of more complex catalyst systems Fractionation internals 22 and 24,
- ABBLUM/260 recover heat. It then passes to heater 66 where the temperature of the vapor entering the first fixed bed reactor 68 is controlled. In reactor 68, some portion of the C2 acetylene as well as some portion of the C3 and heavier acetylenes and dienes that were not converted in the catalytic distillation column are hydrogenated .
- the conditions and the number of fixed bed reactors employed are such that the C 2 acetylene is completely removed from effluent stream 74 with no loss of ethylene and propylene over the entire system (catalytic distillation plus fixed bed reactors) .
- the addition of the fixed bed reactor system to the catalytic distillation column dramatically increases both the performance of the entire system and the ability of that system to respond to process variations and catalyst deactivation.
- the operating criteria for the rectification section of the catalytic distillation column is that conditions be created wherein the unsaturated hydrocarbons are hydrogenated to the extent possible without any hydrogenation of . ethylene and propylene. This is accomplished by: 1 . Operating the column such that ethylene and propylene in the liquid phase is minimized, and 2. Operating the catalytic distillation column such that there are still unconverted C2 to C ⁇ acetylenes and diolefins remaining in column overhead 50. In the catalytic distillation operation of the present invention, the distillation function is designed and operated to distill essentially all of the Cs and lighter components as overhead and essentially all of the Ce and heavier components as bottoms.
- the split could be at the Ci carbon number where essentially all of the C4 and lighter components go overhead and the C5 and heavier components leave as bottoms.
- the C2 acetylenes, the C3 acetylenes and dienes, and the Ci and heavier acetylenes, dienes and olefins while leaving the ethylene and
- the rectification section 20 is operated such that there is a substantial concentration gradient of C and C ⁇ materials relative to C2 and C3 materials in the liquid phase where the majority of the hydrogenation reaction occurs. This can be controlled by variation of reboiler duty and reflux rate to achieve the desired overhead and bottoms composition.
- the choice of operation of the catalytic distillation column as either a depentanizer or a debutanizer will be a function of both the composition of the feed and the desired hydrogenation requirements for the products.
- the preferred operating conditions for a depentanizer will be a pressure of between 75 and 350 psig and a catalyst bed temperature between 50 and 1 50 C.
- the preferred operating conditions for a debutanizer column will be a pressure between 1 00 and 400 psig and a catalyst bed temperature between 30 and 1 30 C.
- the temperature and composition profiles over the reactive sections can be controlled by adjusting the rates of heat removal over the column and by recirculation of liquid within and/or around the catalyst beds. As shown in Figure 2, trays 30 and 31 collect the descending liquid which is withdrawn as side streams 32 and 34. These streams may or may not pass through the intercoolers 36 and 38 and then be reinjected back into the column through the distribution headers 40. This permits a portion of the heat of reaction to be removed in the intercoolers.
- the cooling medium can be water while the cooling in the overhead condensers may need to be at least partly provided by mechanical refrigeration.
- the use of the intercoolers can significantly reduce the portion of the heat of reaction which needs to be " removed by mechanical refrigeration.
- ABBLUM/260 the various components and the concentration of these components in the liquid phase at any particular point in the column.
- the C2 and C3 acetylenes and dienes are far more reactive than ethylene and propylene so that they react first and rapidly.
- the relative reactivities of ethylene, propylene and the C 4 and heavier olefins, dienes and acetylenes are very close.
- the concentration of the ethylene and propylene in the liquid phase must be minimized and the concentration and temperature profiles from top to bottom must be controlled.
- this control can be accomplished by adjusting the overhead reflux produced by the overhead condenser 44 and the side stream reflux from the intercoolers 36 and 38.
- the liquid compositions of ethylene and propylene can be kept low in the reactive zones through increases in the flow of reflux 48 and/or increased interbed cooling at 36 ' and 38.
- the recycle and pumparound circuits have been modified from the prior art as illustrated in Figure 1 . That prior art shows simple intercoolers 1 80 and an overall pumparound line 260.
- the system is modified to provide the flexibility to have both uncooled and cooled pumparounds in the catalyst zones 1 6 and 1 8 within the rectification section 20.
- This improvement permits the desired temperature and composition control with minimal disturbance to the overall distillation. This is accomplished by drawing off pumparound liquid immediately below the catalyst beds as stream 52 and/or 54 from withdrawal points 53 and 31 respectively and returning it through the pump 56 and heat exchanger 58 to the top of the same bed as streams 60 and/or 62. Alternatively, the liquid can be drawn from the bottom most catalyst bed and returned to the highest bed via stream 62. Cooling at 58 can be used, if necessary, to provide
- Another advantage of the new pumparound scheme is that it allows for relatively large liquid flow without affecting '' '.the overall column separa tion performance due to heavies in the overhead as in the prior art .
- the pumparound can provide the necessary liquid loading over the catalyst without the need for additional reflux .
- This permits operation of the catalytic distillation column at lower reflux ratios than previously possible without the penalty in distill ation efficiency observed with the prior art.
- Reflux ratios in the range of 0.5 to 1 .8 by weight are satisfactory for producing the necessary catalyst liquid wetting where values as high as 5 were required with the prior art.
- a variable feed location allowing for a main feed point below the stripping section 22 will provide some separation of any heavy components present in the feed before reaching both the catalyst bed 1 6 and the side stream 52 for the first pumparound . In this way, circulating the heavy, potentially fouling components over the catalyst bed is eliminated .
- feed points above the first catalyst bed can be incorporated to allow for turndown operation and thus avoid the problems of excess catalyst and resultant selectivity loss under these lower flow conditions.
- the bottoms 63 from the column 1 4 are sent for further processing as desired.
- the present invention includes the addition of a fixed bed trim reactor system providing further hydrogenation of stream 50.
- This system is typically two reactors with an intercooler but could be a series of reactors with intercoolers between successive reactors.
- the fixed bed reactor system provides four advantages: 1 .
- the catalytic distillation column no longer needs to operate for high levels of hydrogenation but can be operated for the maximum productivity from the catalyst ' , ⁇ a net ethylene gain with high acetylene, methyl acetylene, and propadiene conversion while maintaining acetylene C2 specification.
- FIG. 3 is a plot of the dienes at the outlet in ppm versus the ethylene gain or loss in weight percent for a catalytic distillation
- CDU 5 unit
- a CDU plus a fixed bed hydrogenation system As can be seen from ' Figure 3, allowing a certain quantity of highly reactive acetylenes and dienes to remain unreacted in the overhead from the catalytic distillation column, ethylene and propylene losses can be eliminated while still obtaining 1 00%) i o conversion of acetylene overall.
- C2 acetylene breakthrough With 1 0,000 to 55,000 and typically 20,000 ppm combined C3 and heavier dienes and acetylenes can be tolerated from the catalytic distillation column.
- a fixed bed reactor system For a fixed catalyst volume in the catalytic distillation column, increases in carbon monoxide or inlet diene and acetylenic concentrations result in lower conversion and thus higher releases of these undesired products into stream 50. Compensation for such anticipated disturbances would be difficult with the prior art alone as shown in Figure 1 . It would require increases in operating pressure or temperature impacting the performance of the entire fractionation system. In the improved process including a fixed bed reactor system, the temperature of the vapor 50 entering the fixed bed reactor system can be adjusted to either increase or decrease reactivity of the reactor system and thus follow changes in catalytic distillation reaction activity and maintain complete C2 acetylene removal and high hydrogen removal efficiency. Finally, a fixed bed hydrogenation reactor system is designed to include not only operating reactors but also spares.
- Catalyst deactivation will occur in both the fixed bed system and the catalytic distillation system. It is not possible to regenerate the catalytic distillation catalyst without shutting down the process or installing a parallel column. Both options are costly. However, a spare fixed bed vapor phase reactor is a relatively inexpensive option. By utilizing a fixed bed reactor system with a spare instead of the single column
- the net overhead 50 from the catalytic distillation passes through the cross flow heat exchanger 64 and inlet heater 66 into the first fixed bed reactor 68.
- the effluent from the first reactor 68 goes through the intercooler 70 to the second fixed bed hydrogenation in reactor 72.
- a series of fixed beds followed by intercoolers can be used in the same fashion in order to achieve the necessary heat transfer when required .
- the effluent from the last reactor 72 then goes back through the cross flow heat exchanger 64 where heat is extracted and the feed 50 to the fixed bed reactors is heated .
- the inlet temperature to the fixed bed reactors can be quickly changed to either increase or decrease the extent of hydrogenation in the fixed bed reactors. Such control is necessary to successfully handle changes in carbon monoxide or diene and acetylene feed concentration. Up to a maximum adiabatic temperature rise of 80 ° F total for both beds, a stable fixed bed operation with no ethylene loss is possible. A typical adiabatic rise of 35 ° F is expected for normal operation.
- FIG. 5 illustrates an alternate embodiment of the present invention incorporating a pre-reactor. This arrangement is advantageous for bulk selective hydrogenation of feeds high in dienes and acetylenes.
- the vapor phase feedstock is admixed with recirculation liquid 76 from the bump 56 of column 1 4 and the two phase mixture passed co-currently through a fixed bed reactor 78. Hydrogenation occurs and the presence of liquid serves to control the temperature rise through vaporization. Hydrogenation reactor 78 can be designed as an operating reactor plus a spare to allow for extending the onstream operation of the system.
- the liquid/vapor mixture can be either sent to the column directly as a mixed feed or separated in a separation drum and the liquid and vapor fed separately to the column.
- the latter is preferred since any oligomers formed in the initial hydrogenation will be in the liquid phase and can be fed to the column below the catalyst beds thus reducing fouling.
- Performing the fixed bed hydrogenations before the catalytic distillation column 1 4 will allow for possibly higher catalyst utilization without experiencing ethylene loss for that portion of the hydrogenation due to the large amount of preferentially absorbed dienes and acetylenes of higher reactivity available for hydrogenation. At higher catalyst utilization, lower catalyst volumes would be necessary making the process more economical .
- a catalytic distillation unit is still required following a pre-reactor to reach hydrogenation specifications. It is anticipated that a maximum o f 50% and typically 20 % of the hydrogenation duty can be accomplished in the pre-reactor.
- the catalyst could either be nickel or palladium. Nickel catalyst for example would be able to catalyze the reaction of the sulfur compound thiophene with butadiene to form a heavy mercaptan. This mercaptan would then be removed in the stripping section 22 of column 1 4 and thus never contact the palladium catalyst.
- a still further advantage is that the external pre- reactor system could have a spare and thus allow for regeneration without the requirement for shutting the entire plant down for catalyst replacement.
- the liquid 76 from pump 56 can flow downwards through the ' fixed bed 78 and the vapor stream from the compressor 1 2 can flow upwards. Liquid from the bottom of the fixed bed reactor 78 then flows -to a lower portion of column 1 4
- ABBLUM/260 ABBLUM/260 and vapor flows to a higher entry point.
- the advantage of this counter-current process sequence is that oligomers resulting from polymerization reactions of the unsaturated hydrocarbons are removed from the catalyst bed as formed and do not pass over the remaining portion of the catalyst bed. Also this liquid is sent to column 26 at a lower entry point, minimizing any potential contamination of the catalyst in column 1 4. Oligomers which can foul the catalytic distillation catalyst are easily separated and do not rise in the column to contaminate the catalyst. Further, as in the co-current flow option, the pre-reactor catalyst bed can have a spare, allowing for regeneration while the rest of the system is operating .
- FIG. 7 illustrates a further embodiment of the present invention which incorporates fixed bed reactors within the liquid pumparound or intercooler streams that are withdrawn from the column 1 4.
- the fixed bed hydrogenation reactors 82 and 84 are placed in the side stream from collecting tray 30 and the side stream from collecting tray 31 , respectively. These fixed beds 82 and 84 are in addition to the reactive hydrog-enation sections 1 6 and 1 8 in the hydrogenation sections 1 6 and 1 8 in the catalytic distillation column 1 4.
- a mass transfer zone 85 in the form of structured packing or trays is also added above the withdrawal point and below the catalyst bed. This zone allows for hydrogen to be saturated into
- Example 1 This example represents prior art outlined in the previous U . S . Patent 5, 679, 241 ( Figure 1 ) based on a one step catalytic distillation column operating with a reflux ratio of 4.4. With a typical front end acetylene hydrogenation catalyst containing palladium levels below 2000 ppm and operating at pressure of 1 95 psig and average catalyst temperature of 230 °F C2 acetylene conversion reached 84%o with 0% > ethylene loss/gain. At the reactor outlet there were 370 ppm of C2 acetylene and a , total of 1 9070 ppm dienes and acetylenics. Total acetylene/diene conversion is 79.5 %) . This example represents the case where the single column is operated for
- Example 2 5 This example also represents prior art and is based on the single catalytic distillation column of Example 1 with higher catalyst temperature and slightly lower reflux ratio of 4.1 .
- the hydrogenation severity of a single column can be increased to reach low C2 acetylene levels. This can be accomplished by raising temperature or
- Example 3 This example represents prior art and is based on the single catalytic distillation column of Example 1 w-ith higher carbon monoxide levels in the feed . Carbon monoxide acts as a catalyst
- Example 4 This example represents the improved combined operation of the catalytic distillation column and a fixed bed reactor described in Figure 2. This combined operation is necessary in order to realize ethylene gains with 1 00% C2 acetylene conversion and 50%o to 95 %) conversion of all other diene and acetylene compounds. Operation of the catalytic distillation column at 1 95 psig and average catalyst temperature of 230 ° F and 1 95 psig pressure resulted in 1 2,000 ppm by weight dienes and acetylenes in the catalytic distillation overhead which was then fed to the fixed bed hydrogenation reactor system.
- Example 5 This example represents the improved combined operation of the catalytic distillation column and a fixed bed reactor at high carbon monoxide levels in the feed. At carbon monoxide levels of 0. 1 mol % in the feed with constant operating conditions for the catalytic
- the proposed improvement of the present invention will perform 1 00% C2 acetylene hydrogenation with stable 90%) + hydrogenation of the C3 to C5 and heavier acetylenes, 90%o + hydrogenation of C and C ⁇ dienes, and 50%) + conversion of C3 diene in a feed stream without hydrogenating the C2 and C3 olefins.
- the resulting hydrogen removal with the present invention will remain steady at 30 to 40 and typically 30% depending on the feed composition.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2004/001379 WO2005080530A1 (en) | 2004-01-20 | 2004-01-20 | Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
Publications (1)
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EP1711581A1 true EP1711581A1 (en) | 2006-10-18 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP04703646A Withdrawn EP1711581A1 (en) | 2004-01-20 | 2004-01-20 | Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps |
Country Status (6)
Country | Link |
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EP (1) | EP1711581A1 (en) |
JP (1) | JP4376908B2 (en) |
CN (1) | CN1961059B (en) |
BR (1) | BRPI0418414A (en) |
CA (1) | CA2553962C (en) |
WO (1) | WO2005080530A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101433841B (en) * | 2007-12-13 | 2010-04-14 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
CN104974792B (en) * | 2014-04-01 | 2017-10-17 | 中国石化工程建设有限公司 | A kind of fluidized-bed hydrogenation system and method for hydrotreating |
CN107646028B (en) * | 2015-01-29 | 2021-07-16 | 鲁姆斯科技公司 | Preparation of C5 olefins from steam cracker C5 feed |
US20230024175A1 (en) * | 2021-07-16 | 2023-01-26 | Uop Llc | Process for saturating aromatics in a pyrolysis stream |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US4404124A (en) * | 1981-05-06 | 1983-09-13 | Phillips Petroleum Company | Selective hydrogenation catalyst |
ZA945342B (en) * | 1993-12-08 | 1995-03-01 | Chemical Res & Licensin | Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams |
US5679241A (en) * | 1995-05-17 | 1997-10-21 | Abb Lummus Global Inc. | Olefin plant recovery system employing catalytic distillation |
US6576588B2 (en) * | 2000-04-07 | 2003-06-10 | Catalytic Distillation Technologies | Process for selective hydrogenation of alkynes and catalyst therefor |
CN1163457C (en) * | 2000-10-18 | 2004-08-25 | 中国石化集团齐鲁石油化工公司 | Combined technological and comprehensive utilizing method in C5 prodn. splitting process |
US6420619B1 (en) * | 2001-01-25 | 2002-07-16 | Robert J. Gartside | Cracked gas processing and conversion for propylene production |
-
2004
- 2004-01-20 JP JP2006551012A patent/JP4376908B2/en not_active Expired - Lifetime
- 2004-01-20 CN CN200480042493XA patent/CN1961059B/en not_active Expired - Fee Related
- 2004-01-20 BR BRPI0418414-9A patent/BRPI0418414A/en not_active Application Discontinuation
- 2004-01-20 WO PCT/US2004/001379 patent/WO2005080530A1/en active Application Filing
- 2004-01-20 CA CA2553962A patent/CA2553962C/en not_active Expired - Fee Related
- 2004-01-20 EP EP04703646A patent/EP1711581A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2005080530A1 * |
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Publication number | Publication date |
---|---|
CA2553962A1 (en) | 2005-09-01 |
CA2553962C (en) | 2011-08-30 |
BRPI0418414A (en) | 2007-05-15 |
JP2007518864A (en) | 2007-07-12 |
WO2005080530A1 (en) | 2005-09-01 |
CN1961059A (en) | 2007-05-09 |
CN1961059B (en) | 2010-04-28 |
JP4376908B2 (en) | 2009-12-02 |
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