WO1997033953A1 - Hydrogenation et distillation catalytique de composes insatures lourds dans une installation de fabrication d'olefines - Google Patents

Hydrogenation et distillation catalytique de composes insatures lourds dans une installation de fabrication d'olefines Download PDF

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Publication number
WO1997033953A1
WO1997033953A1 PCT/US1997/002354 US9702354W WO9733953A1 WO 1997033953 A1 WO1997033953 A1 WO 1997033953A1 US 9702354 W US9702354 W US 9702354W WO 9733953 A1 WO9733953 A1 WO 9733953A1
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WIPO (PCT)
Prior art keywords
components
stream
bottoms
recited
overhead
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PCT/US1997/002354
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English (en)
Inventor
Stephen J. Stanley
Charles Sumner
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Abb Lummus Global Inc.
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Publication date
Application filed by Abb Lummus Global Inc. filed Critical Abb Lummus Global Inc.
Priority to AU22735/97A priority Critical patent/AU2273597A/en
Publication of WO1997033953A1 publication Critical patent/WO1997033953A1/fr

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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • 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
    • C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
    • C10G70/02—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by hydrogenation

Definitions

  • the present invention relates to a process system for the production of olefins and particularly to processing the charge gas feed to more effectively recover the product and process the by-products.
  • Ethylene, propylene and other valuable petrochemicals are produced by the thermal cracking of a variety of hydrocarbon feedstocks ranging from ethane to heavy vacuum gas oils.
  • hydrocarbon feedstocks ranging from ethane to heavy vacuum gas oils.
  • a wide variety of products are produced ranging from hydrogen to pyrolysis fuel oil.
  • the effluent from the cracking step commonly called charge gas or cracked gas, is made up of this full range of materials which must then be separated (fractionated) into various product and by-product streams followed by reaction (hydrogenation) of at least some of the unsaturated by-products.
  • the typical charge gas stream in addition to the desired products of ethylene and propylene, contains C 2 acetylenes, C 3 acetylenes and dienes and C 4 and heavier acetylenes, dienes and olefins as well as a significant quantity of hydrogen.
  • the C 2 acetylenes and C 3 acetylenes and dienes and the C 5 and heavier dienes, acetylenes and olefins are catalytically hydrogenated in fixed bed reactors using a series of commercially available catalysts.
  • the C 4 acetylenes, dienes, and olefins are also catalytically hydrogenated in fixed bed reactors.
  • the second tower in this sequence the depropanizer, produces an overhead stream containing the C 3 acetylenes, dienes, olefins and paraffins.
  • This stream is sent to a fixed bed, vapor or liquid phase reactor where the C 3 acetylenes and dienes are selectively hydrogenated using the hydrogen cryogenically separated earlier from the charge gas stream.
  • the third tower the debutanizer, produces an overhead stream containing the C 4 acetylenes, dienes, olefins, and paraffins. This stream is then sent either to battery limits as a final product or to a fixed bed, liquid phase reactor where the dienes, acetylenes, and in some instances the olefins are hydrogenated using the hydrogen cryogenically recovered previously from the charge gas.
  • the bottoms of the third tower contains the C 6 and heavier dienes, acetylenes, olefins and paraffins.
  • This stream is sent to a series of two fixed bed, liquid phase reactors. In the first, the acetylenes and dienes are catalytically hydrogenated.
  • the olefins are catalytically hydrogenated in the second reactor. Both reactors utilize the hydrogen cryogenically recovered previously from the charge gas.
  • the third tower produces an overhead stream containing both the C 4 and C 5 acetylenes, dienes, olefins, and paraffins. These are hydrogenated as discussed previously for the C 4 's alone, in a single fixed bed, liquid phase reactor.
  • the C ⁇ and heavier dienes, acetylenes, olefins and paraffins exit in the bottoms of the third tower and are hydrogenated as discussed previously in two fixed bed, liquid phase reactors.
  • the cracked gas is compressed to between 2.07 and 3.45 MPa (300 and 500 psia) and sent to a fractionation tower.
  • the overhead of the tower is the C 3 and lighter portion of the charge gas. It is sent to a series of fixed bed, vapor phase reactors where the C 2 acetylene and a portion of the C 3 acetylenes and dienes are hydrogenated using a small portion of the hydrogen contained in the C 3 and lighter stream.
  • the unhydrogenated portion of the C 3 acetylenes and dienes as well as the C 4 and heavier acetylenes, dienes, and olefins are hydrogenated in a fashion similar to that described above.
  • butadienes are hydrogenated to olefins or butadienes and butenes are totally hydrogenated to butanes.
  • the saturated C 4 's, and in some instances the saturated C 6 's also, are recycled to the cracking heaters.
  • the present invention involves the recovery of ethylene and propylene in an olefins plant and the hydrogenation and separation of the heavier unsaturates.
  • An object of the present invention is to provide a method for the hydrogenation of the C 2 acetylenes, the C 3 acetylenes and dienes and the C 4 and heavier acetylenes, dienes and olefins and the selective separation of the resulting products in a process scheme which minimizes the required number of reactors and fractionators thereby minimizing capital and operational costs. More specifically, the invention involves the use of combined reaction-fractionation steps known as catalytic distillation to simultaneously carry out the hydrogenation reactions and the desired separations.
  • Figure 1 is a flow sheet for a conventional prior art olefin plant.
  • Figure 2 is a flow sheet for a modified prior art olefin plant.
  • Figure 3 is a flow sheet for an olefin plant according to the present invention.
  • Figures 4 to 8 are flow sheets similar to the flow sheet of Figure 3 but illustrating alternate embodiments of the present invention.
  • FIG. 1 which illustrates a conventional prior art olefin plant
  • the typical pyrolysis and associated heat recovery units generally designated 4
  • the charge gas 6 is first compressed at 12 up to a pressure of 2.76 to 4.14 MPa (400 to 600 psia).
  • the majority of the compressed gas then undergoes cryogenic treatment at 14 to separate hydrogen 15 followed by separation of methane at 16.
  • a small portion of the C 3 and heavier material condenses in the compressor train and often bypasses the cryogenic demethanization and deethanization steps going directly to the depropanizer 30 as stream 31.
  • the gas stream 18 is then deethanized at 20 with the C 2 acetylenes in the C 2 gas stream being hydrogenated at 22 with hydrogen 15 and fractionated at 24 to produce essentially ethylene 26 and ethane 28.
  • the bottoms 29 from the deethanizer 20 are depropanized at 30 with the separated C 3 acetylenes and dienes in the C 3 stream 32 being hydrogenated at 34 also with hydrogen 15 and fractionated at 36 to produce essentially propylene 38 and propane 40.
  • the bottoms from the depropanizer 30 are debutanized at 42 producing the C 4 stream 44 which is hydrogenated at 46.
  • the C 5 + stream 48 is fed to the gasoline hydrotreater 50 along with the heavies 8 from the front end of the system and hydrogen 15.
  • the C 6 + stream including the heavies from the front end are usually hydrogenated in two stages. In the first stage, the diolefins and acetylenes are hydrogenated. In the second stage, olefins are hydrogenated and sulfur compounds are converted to hydrogen sulfide.
  • the partially hydrogenated product 52 from the first gasoline hydrotreater 50 is then fractionated at 54 which removes the C 6 's to C ⁇ 's as overhead 56 leaving the C ⁇ + as a bottoms product 58.
  • the overheads 56 are then further hydrogenated at 60 followed by fractionation at 62 producing the overhead 64 of saturated C 6 's and a bottoms gasoline product 66 of saturated C ⁇ 's to C ⁇ 's.
  • the C 5 stream 64 is combined with the saturated C 4 stream from the hydrogenation step 46 and the combined stream 65 of the C 4 's and C s 's is usually recycled to the pyrolysis heaters.
  • the ethane and propane streams 28 and 40 may also be recycled to the pyrolysis heaters.
  • Figure 2 illustrates a prior art variation of the process shown in Figure 1 wherein the C 4 and C G unsaturates are processed together rather than processing the C 4 's separate from the C 6 's as in Figure 1 where the C 5 's are processed with the gasoline.
  • the C 4 + bottoms from the depropanizer 30 together with the heavies 8 from the front end of the system are fed to the fractionator 42 which is now operated as a depentanizer to separate the C 4 's and C ⁇ 's in the overhead 44.
  • the overhead 44 is hydrogenated at 46 to produce essentially the same C 4 and C 5 stream 65 as in Figure 1.
  • the bottoms stream 48 from the depentanizer 42 which now contains the C ⁇ + components including those from the heavies stream 8, is again fed to the gasoline hydrotreater 50 for partial hydrogenation, to the fractionator 54 for separation of the C 9 + fraction and to the hydrotreater 60 for final hydrogenation leaving the C ⁇ to C ⁇ gasoline stream 66 just as in Figure 1.
  • this Figure 2 embodiment employs one less fractionator than the Figure 1 embodiment but both of these schemes use five separate hydrogenators or hydrotreaters.
  • the object in these processes is to separate the desired fractions and to selectively hydrogenate the C 2 and C 3 acetylenes and dienes as well as the C 4 and acetylenes, dienes and olefins without hydrogenating the desired olefins, i.e., the ethylene and propylene.
  • the selective hydrogenation of a propylene cut is not only essential for the production of high purity propylene but the hydrogenation of the methyl acetylene and propadiene in this cut (collectively referred to as MAPD) produces additional propylene resulting in a high yield.
  • these separations and hydrogenation are carried out at least in part by catalytic distillation hydrogenation.
  • Catalytic distillation is a process which combines conventional distillation with catalytic reactions.
  • the catalytic reaction is hydrogenation.
  • Catalytic distillation employs the catalytic material within the distillation column as both a catalyst for the reaction and as a column packing for the distillation.
  • the catalyst has both a distillation function and a catalytic function.
  • the deethanizer bottoms 29 are fed to the catalytic distillation hydrogenation/depropylenizer 68 usually together with the heavies 8 from the front end and compressor condensates 36.
  • the catalytic distillation hydrogenation/depropylenizer 68 usually together with the heavies 8 from the front end and compressor condensates 36.
  • one preferred catalyst is 0.3 wt. % palladium oxide on a spherical aluminum oxide support with a particle size of about 1/8 inch (3.2 mm).
  • the depropylenizer 68 has a catalyst bed 70 above and another catalyst bed 72 below the generally centrally located feed zone 74.
  • the MAPD is hydrogenated mostly in the upper section 70 of the tower while the C 4 +components are at least partially hydrogenated in the lower section 72.
  • the depropylenizer is operated under conditions of pressure and temperature such that the overheads 76 are essentially all propylene and the bottoms 78 contain most of the propane and C 4 +components. Hydrogen 15 from the cryogenic separation unit 14 may be fed to the feed zone 74 and/or into the bottom of the tower.
  • the depropylenizer bottoms since they are now significantly hydrogenated, are much less subject to fouling and can be fractionated at relatively higher temperatures than in a normal process thereby decreasing refrigeration requirements.
  • the bottoms 78 from the depropylenizer 68 are fed to the depentanizer 80 which is a distillation unit functioning to remove the propane and the C 4 's and C 5 's as overhead 82 and the C ⁇ + components as bottoms 84.
  • the overhead 82 which is for the most part now the saturated C 3 , C 4 and C 5 's, is preferably recycled to the pyrolysis heater.
  • the bottoms 84 from the depentanizer 80 which are already at least partially hydrogenated, are fractionated at 86 to remover the C 9 + components as bottoms 88 and then hydrotreated at 90 to complete the hydrogenation.
  • the product 92 is a saturated C ⁇ - C 8 gasoline.
  • this embodiment of the present invention substitutes the one catalytic distillation hydrogenation unit 68 for the depropanizer 30, the hydrogenation 34, the f ractionation 36, the hydrogenation 46 and the hydrotreater 50 of the prior art Figure 2 arrangement.
  • Figure 4 depicts another embodiment of the present invention which includes a depropylenizer 68 similar to the Figure 3 embodiment. The bottoms 78 from the depropylenizer 68 are fed to a depentanizer 94 which in this Figure 4 embodiment is another catalytic distillation hydrogenation tower containing the catalyst beds 96 and 98.
  • This unit 100 contains a catalyst bed 102 in the upper portion above the feed and a second catalyst bed 104 in the lower portion below the feed. MAPD, C 4 's and C 5 's are mostly hydrogenated in the upper portion while the C 6 + are mostly hydrogenated in the lower portion.
  • the overhead 106 from the depentanizer 100 containing the C 3 - C 6 components is fed to the depropylen izer 108 where the propylene product 110 is separated from the basically saturated C 3 - C 6 components 112 which are recycled to the pyrolysis heater.
  • the C ⁇ + bottoms 114 from the depentanizer 100 is fractionated at 86 to remove C fl + components and hydrotreated at 90 to produce C ⁇ - C 8 gasoline 92.
  • Figure 6 is a variation of the invention shown in Figure 4 and involves the use of catalytic distillation hydrogenation in conjunction with the deethanizer.
  • a hydrogenation catalyst bed 116 is placed in the bottom of the deethanizer column 118.
  • the overhead from the deethanizer, which still contains the C 2 acetylenes, the ethylene and the ethane, is handled the same as in Figure 4.
  • the C 3 + acetylenes and dienes can be totally or at least mostly hydrogenated. This minimizes the chances of fouling caused by unsaturates in the bottom of the deethanizer.
  • any excess or unreacted hydrogen from deethanizer 118 flows to the hydrogen ator 22 along with the hydrogen 15 for hydrogenation of acetylene. Since hydrogenation is now taking place in the deethanizer, the depropylenizer 120 need not have catalytic distillation and hydrogenation as in the Figure 4 arrangement. The depropylenizer 120 now merely involves fractionation to separate the propylene from the bottoms 78 which are processed the same as in Figure 4. In this scheme, the balance of the hydrogenation which is not completed in the deethanizer 118 is essentially completed in the depentanizer 94. Although not shown in Figure 6, the deethanizer 118 would require a side condenser to remove the heat of the hydrogenation reaction. As a variation, the overhead from the deethanizer 118 could also contain the C 3 components.
  • FIG. 7 depicts still another variation of the invention in which the bottoms from the deethanizer 20 together with the streams 8 and 31 are fed to the catalytic distillation hydrogenation unit 122 which is operated as a depropanizer.
  • the MAPD is hydrogenated in the upper catalyst bed 124 and the C 3 + acetylenes and dienes are hydrogenated in the lower catalyst bed 126.
  • the overhead 128 comprising the C 3 's is fed to the depropylenizer 130 where the propylene 132 is separated from the propane 134.
  • the bottoms 136 from the catalytic distillation hydrogenation unit 122 are fed to the catalytic distillation hydrogenation unit 138 which is operated as a depentanizer and in which all the olefins are converted to saturates.
  • the overhead C 6 - stream 140 is combined with the propane stream 134 to form the stream 142 for recycle to the pyrolysis heater.
  • the bottoms stream 144 of C 6 + is then processed the same as in Figures 3 to
  • Figure 8 is a variation on the Figure 7 embodiment. This involves the same catalytic distillation hydrogenation unit 122 and depropylenizer 130 but the bottoms 136 from the unit 122 are fed to a catalytic distillation unit 146 which is now operated as a debutanizer. Again, the MAPD and the C 4 acetylene and dienes are hydrogenated in the depropanizer 122 while the remaining hydrogenation to saturates occurs in the debutanizer 146.
  • the overhead 148 from the debutanizer 146 now contains the saturated C 4 's and it is joined with the propane stream 134 to form stream 150 for recycle.
  • the bottoms stream 152 containing the C 6 + is fractionated at 154 to produce a C s product 156.
  • the C 6 + bottoms 158 from the fractionator 154 is then handled in the same manner as the C ⁇ + streams in the other schemes.
  • the catalytic distillation tower 68 can be operated at conditions which produce totally or mostly saturated products. In this mode of operation, stream 82 is totally or mostly saturated hydrocarbons and typically would be recycled to the cracking heaters to produce additional desired dehydrogenated products. It is possible to also operate catalytic distillation tower 68 to remove acetylenes and dienes only, preferably with minimum co-current conversion of olefins. In this case, stream 82 has a high olefin content and can then be further processed to produce butane products, methy tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), or utilized in gasoline alkylation, or for other suitable processing as well known in the prior art. This same variation can also be applied to the other flow schemes of the present invention.
  • MTBE methy tertiary butyl ether
  • TAME tertiary amyl methyl ether

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une installation de production et de récupération de l'éthylène et du propylène. Dans cette installation, l'hydrogénation de l'acétylène en C2, celle des acétylènes et des diènes en C3 et celle des acétylènes, des diènes et des oléfines en C4 et plus lourds, ainsi que la séparation sélective des produits résultants se fait en utilisant différents systèmes comprenant une ou plusieurs colonnes de réaction/distillation. Ces colonnes contiennent un catalyseur d'hydrogénation et elles assurent, en même temps, une réaction d'hydrogénation et une distillation.
PCT/US1997/002354 1996-03-12 1997-02-13 Hydrogenation et distillation catalytique de composes insatures lourds dans une installation de fabrication d'olefines WO1997033953A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU22735/97A AU2273597A (en) 1996-03-12 1997-02-13 Catalytic distillation and hydrogenation of heavy unsaturates in an olefins plant

Applications Claiming Priority (2)

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US61359496A 1996-03-12 1996-03-12
US08/613,594 1996-03-12

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WO1997033953A1 true WO1997033953A1 (fr) 1997-09-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999009118A1 (fr) * 1997-08-19 1999-02-25 Abb Lummus Global Inc. Distillation et hydrogenation catalytiques de substances insaturees dans une usine d'olefines
WO2003044125A3 (fr) * 2001-11-16 2004-12-29 Chevron Phillips Chemical Co Procede de production d'un courant d'ethylene dilue et d'un courant de propylene dilue
US6846959B2 (en) 2002-10-07 2005-01-25 Air Products And Chemicals, Inc. Process for producing alkanolamines

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995015934A1 (fr) * 1993-12-08 1995-06-15 Chemical Research & Licensing Company Hydrogenation selective de composes hautement insatures dans un courant d'hydrocarbures
WO1996006900A1 (fr) * 1994-08-26 1996-03-07 Exxon Chemical Patents Inc. Procede d'hydrogenation selective d'hydrocarbures de craquage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995015934A1 (fr) * 1993-12-08 1995-06-15 Chemical Research & Licensing Company Hydrogenation selective de composes hautement insatures dans un courant d'hydrocarbures
WO1996006900A1 (fr) * 1994-08-26 1996-03-07 Exxon Chemical Patents Inc. Procede d'hydrogenation selective d'hydrocarbures de craquage

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999009118A1 (fr) * 1997-08-19 1999-02-25 Abb Lummus Global Inc. Distillation et hydrogenation catalytiques de substances insaturees dans une usine d'olefines
AU735400B2 (en) * 1997-08-19 2001-07-05 Abb Lummus Global Inc. Catalytic distillation and hydrogenation of heavy unsaturates in an olefins plant
WO2003044125A3 (fr) * 2001-11-16 2004-12-29 Chevron Phillips Chemical Co Procede de production d'un courant d'ethylene dilue et d'un courant de propylene dilue
US6846959B2 (en) 2002-10-07 2005-01-25 Air Products And Chemicals, Inc. Process for producing alkanolamines

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Publication number Publication date
ID18844A (id) 1998-05-14
AU2273597A (en) 1997-10-01

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