WO2002081417A1 - Process for improved yields of higher molecular weight olefins from lower molecular weight olefins - Google Patents
Process for improved yields of higher molecular weight olefins from lower molecular weight olefins Download PDFInfo
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- WO2002081417A1 WO2002081417A1 PCT/US2002/010806 US0210806W WO02081417A1 WO 2002081417 A1 WO2002081417 A1 WO 2002081417A1 US 0210806 W US0210806 W US 0210806W WO 02081417 A1 WO02081417 A1 WO 02081417A1
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- WIPO (PCT)
- Prior art keywords
- distillation column
- reactive distillation
- olefin
- containing hydrocarbon
- feed stock
- Prior art date
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 282
- 238000000034 method Methods 0.000 title claims abstract description 111
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 175
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 147
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 145
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 127
- 238000000066 reactive distillation Methods 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000004821 distillation Methods 0.000 claims abstract description 47
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 31
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000012808 vapor phase Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- -1 olefin hydrocarbons Chemical class 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims 4
- 239000000047 product Substances 0.000 abstract description 41
- 239000007795 chemical reaction product Substances 0.000 abstract description 15
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 15
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 3
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 3
- 229910003449 rhenium oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical class O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/226—Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/32—Manganese, technetium or rhenium
- C07C2523/36—Rhenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- This invention relates to a controlled process for improving the yields of heavier olefins by using a substantially narrow range of lighter olefin-containing hydrocarbon feed stock which are fed into a reaction distillation column at a predetermined point and using varying arrangements of isomerizing and disproportionating catalysts in relation to the point of feeding the narrow range of lighter olefin-containing hydrocarbon feed stock.
- the controlled process provides for keeping the reaction mixture in a state of vapor / liquid phase equilibrium for separating the lighter products overhead and collecting the heavier reaction products in the bottoms by maintaining controlled pressure and temperature profiles in relation to the narrow range of lighter olefin-containing hydrocarbon feed stock being used and the desired range of heavier olefin-containing hydrocarbon products desired as product in the bottoms of the reaction distillation column. Further at least one or more zones for the purpose of vapor/liquid contacting are created in the reaction distillation column for improving the separation of lighter reaction olefin products from the heavier reaction olefin products and the olefin-containing hydrocarbon feed stock and for reducing the cost of the process.
- the prior art further just used metal catalysts for disproportionating and isomerizing either singularly or in admixtures, but made no distinction between where these were located relative to the input of these feed stocks or which catalyst should be the first for reaction with the feed stock.
- the objective in the prior art was thus to make the deepest possible internal olefin of both light and heavy species before or during the disproportionation including symmetrical internal olefins. This was highly desirable when the goal was to create a mid-range olefin-containing hydrocarbon, but not for the production of heavier olefin-containing hydrocarbons from lighter olefin- containing hydrocarbons, where specifically a formation of asymmetrical olefins is desired.
- the removal of the lighter olefin-containing hydrocarbons and other light hydrocarbons occurs.
- An object of the process of this invention is to create the improved yields of heavier olefins without using high temperatures and/or longer residence time in the systems of these processes, so as to limit the formation of unwanted by-products which are undesirable in the desired product and which may interfere with the formation of the desired heavier olefins or reduce the yields thereof.
- Yet a further object of the process of this invention is to shift the equilibrium of the reaction toward the formation of heavier olefin-containing hydrocarbon feed stock by reacting the lighter olefin-containing hydrocarbon feed stock with the metal catalysts and then controlling the pressure and temperature to allow the lightest unwanted olefins and other light products produced by the reaction with the metal catalysts to go into vapor phase for its removal from the reaction distillation vessel overhead.
- an object of this process invention is to allow even the lightest olefin- containing hydrocarbon feed stocks such as 1- and 2-butene and propylene to be reacted with metal catalysts in the controlled temperatures and pressures of this process for the creation of more valuable heavier olefin-containing hydrocarbon products such as C ⁇ to C10, which have significantly greater monetary value than the products of 2-pentene and 3-hexene.
- the object of the process of this invention further allows the creation of heavier olefins from a narrow range of lighter olefin-containing hydrocarbon feed stock and then running the narrow range of heavier olefins created in another step to create yet heavier olefins.
- a yet further object of this process invention is to utilize the isomerization process to adjust the location of the olefinic double bond to a predominantly asymmetrical location in the olefin molecules and then disproportionate the carbon molecules, which effectively cuts them at the double bond and recombines the asymmetrical fragments with other olefin molecules which have been disproportionated to create heavier olefin molecules and light olefin molecules and then isomerlzed those heavier olefin molecules and then disproportionate them again.
- the lighter undesirable olefin- containing hydrocarbons are removed in the vapor phase leaving the heavier olefins to be isomerized again before the process continues in the steps to the desired heavier olefin product.
- an object of this invention is the use of both isomerization and disproportionation catalysts with olefin-containing hydrocarbon feed stocks and reaction products in a vapor and liquid phase in relative low temperatures and pressures to achieve a desired range of heavier olefin end products.
- FIG. 1 is a diagrammatic drawing of a reactive distillation column used with the process of this invention utilizing a narrow range of lighter olefin-containing hydrocarbon feed stock of C ⁇ and higher carbon numbers being fed into the reactive distillation column at a predetermined point and with isomerizing catalyst near the predetermined feed point and disproportionating catalyst in place and in alternating arrangement with the isomerizing catalyst and with at least one vapor/liquid zone created at the top of the reactive distillation column for producing C ⁇ through C10 carbon number olefins.
- FIG. 2 is a diagrammatic drawing of a reactive distillation column used with the process of this invention utilizing a narrow range of lighter olefin-containing hydrocarbon feed stock of C ⁇ through Cio and higher carbon numbers being fed into the reactive distillation column at a predetermined point and with isomerizing catalyst near the predetermined feed point and disproportionating catalyst in place and in alternating arrangement with the isomerizing catalyst and with at least one vapor/liquid zone created at the top of the reactive distillation column for producing C10 and higher carbon number olefins.
- FIG. 3 is a diagrammatic drawing of a reactive distillation column used with the process utilizing a range of lighter olefin-containing hydrocarbon feed stock of C3 to C4 carbon numbers being fed into the reactive distillation column at a predetermined point and with disproportionating catalyst near the predetermined feed point and isomerizing catalyst in place and in alternating arrangement with disproportionating catalyst and with at least one vapor/liquid zone created at the top of the reactive distillation column for producing C5 to C10 carbon number olefins.
- FIG. 4 is a diagrammatic drawing of a series of reactive distillation columns connected together for utilizing an initial range of lighter olefin-containing hydrocarbon feed stock of C3 to C4 carbon numbers for producing Cio and higher carbon number olefins by feeding the bottom products in stages from the first to the second and to the third reactive distillation column.
- the present invention relates to a process for improving the yields of heavier olefins by using a substantially narrow range of lighter olefin-containing hydrocarbon feed stock, which is fed into a reaction distillation column, generally referred to at reference numeral 10.
- the process of this invention commences with the feeding of the substantially narrow range of lighter olefin-containing hydrocarbon feed stock from C6 and heavier carbon numbers into the reaction distillation column 10 at a predetermined point 11 in the reaction distillation column 10.
- an isomerization catalyst 14 for isomerizing the olefin-containing hydrocarbon feed stock as it is passed into the reactive distillation column 10.
- the isomerization catalyst 14 would be located both near the predetermined feed point 11 and directly above and below the predetermined feed point 11 for first isomerizing the olefin-containing hydrocarbon feed stock as completely as possible.
- the predetermined feed point 11 would be located on the reactive distillation column for first directly feeding the olefin-containing hydrocarbon feedstock into the reactive distillation column 10 between the isomerization catalysts 14.
- Isomerizing the olefin means that the double bonds between the carbon atoms, which characterize an olefin, are moved from one pair of carbon atoms to another pair of carbon atoms with the purpose of creating predominantly an olefin molecule, which is not symmetrical, provided the olefin molecule has 5 or more carbonatoms.
- a disproportionation catalyst 15 for disproportionating of the now isomerized olefin-containing hydrocarbon feed stock.
- a disproportionating catalyst 15 would be located above and below the isomerization catalysts 14.
- This arrangement of catalysts may be either in separate trays or as molecular mixtures of the catalysts which are created in admixture thereof.
- Disproportionating the olefin means that a splitting process occurs at the point of the olefinic bond on the olefin-containing hydrocarbon and a re-combining of the split parts with other split parts from other olefins which are being disproportionated at the same time to create both larger olefins and smaller olefins.
- the disproportionation catalyst 15 located above and below the isomerizing catalysts 14 the olefins are as soon as they are isomerized move to be disproportionated in the reaction distillation column, as shown in FIG 1.
- alternating process steps of disproportionating and isomerizing of the olefin- containing hydrocarbon feed stock after its initial feed into the predetermined feed point 11 of the reaction distillation column 10 and its first isomerization This alternating of the process steps of disproportionating and isomerizing said olefin- containing hydrocarbon feed stock will continue depending on the size of the reaction distillation column 10, but will generally have as it last process step a disproportionating step before reaching the bottoms 18 of the reaction distillation column 10.
- the disproportionation catalysts are selected from the groups of molybdenum, tungsten, cobalt, and rhenium metals and their oxides either individually or as combinations thereof and supported on porous substrates.
- the disproportionation catalyst selected from a group of heavy metals is used which contains tungsten or rhenium oxides on a porous alumina or silica-containing supports.
- porous alumina or silica-containing support used in this embodiment is catalytic grade gamma-alumina or silica-alumina, but any other substrate which would be effective to make the catalysts available for reaction with the olefins may be used and not depart from the teachings of this invention.
- Some of the conventional methods of preparing the disproportionation catalyst mixture includes dry mixing, impregnation or co-precipitation.
- a solution containing aqueous salts of rhenium or rhenium oxide and/or tungsten or tungsten oxide is prepared. Once prepared it is added to an alumina support which can be in the form of conventional dumped distillation packing, such as, saddles, rings, spheres to enhance mass transfer and reactive surface during disproportionating and fractionation or separation to the extent the operating parameters are appropriate .
- the catalyst After impregnations, the catalyst would be calcined at 300 degrees Centigrade to 700 degrees Centigrade in the flow of air and/or nitrogen to activate the catalyst.
- the disproportionation catalyst contained 5 to 20% by weight rhenium or 5 to 35% tungsten.
- isomerization catalysts are selected from the groups of alkali metals such as sodium, potassium, rubidium or cesium either individually or as combinations thereof and then supported on alumina support.
- alkali metals such as sodium, potassium, rubidium or cesium either individually or as combinations thereof
- carbonates, chelates, hydroxides, alkoxylates and other compounds can be used as the catalysts as long as they can be decomposed to leave some form of metal oxides on the surface for reaction with the olefins.
- the metals of potassium carbonate and/or potassium carboxylates may be used, but after they are impregnated on a surface, they would be activated by being calcined at 400 degrees Centigrade to 800 degrees Centigrade in the presence of air flow.
- the isomerization catalyst of an alkali metal on the alumnia substrate should be from 5 to 20% by weight.
- a vapor/liquid contacting zone 16 is located in the upper part of the reactive distillation column 10 for providing a vapor/liquid contacting zone for separation of the lighter reaction products from the heavier olefin-containing hydrocarbon feed stock.
- This vapor/liquid contacting zone 16 may consist as shown in this embodiment of several stages of structured packing or trays located in the upper most stages of the upper part 17 of the reaction distillation column 10. At this point the olefin-containing hydrocarbon feed stock has been both isomerized and disproportionated and olefin reaction products have been produced which are both heavier, lighter and approximately the same size as the feed stock.
- the advantage of providing at least one vapor/liquid zone 16 is that it improves the separation or fractionation of the lighter olefin reaction products from the heavier olefin reaction products produced from the olefin- containing hydrocarbon feedstock in the reaction distillation column 10. This is especially true at the top of the column, where reaction is inhibited by low temperatures and the light species are flashed off thus preventing their recombination with the other reactants. This removal of the light species thus shifts the equilibrium conversion of the feedstock toward heavier olefin-containing hydrocarbons. These light olefin reaction products are then removed by the overhead line 19 located in the top 13 of the reaction distillation column 10.
- the process variables of temperature and pressure used in the reaction distillation column 10 to practice this invention will vary and depend on the olefin- containing hydrocarbon feedstock used, and the desired extent of reaction required to achieve the desired conversion and selectivity.
- the temperature range will be between -50° degrees Fahrenheit to 200° degrees Fahrenheit at the top 13 where the lighter olefin reactant products are taken off by the overhead stream19.
- the temperature range will be between 200° degrees Fahrenheit to 600° degrees Fahrenheit .
- the pressures in general will range from -14.5 PSIG to 250 PSIG but will also be varied by the required process temperature to achieve the desired conversion and selectivity of the desired olefin product.
- These process variables will require those skilled in the art who practice this invention to do some experimentation within these variables and within the ranges set out herein to maximize their results because these variables are dependant on the olefin-containing hydrocarbon feedstock and the desired product ranges. How these process variables may be adjusted will become more clear to those skilled in the art from the following examples herein set out and disclosed.
- the resultant product collected at the bottoms 18 for removal as desired heavier olefins would be a composition in the wt% as follows: Cs 4.7 Ce 38.5 C? 38.2 Ca 18.6 thus producing a slightly different heavier olefins of substantially from C ⁇ through Cio.
- the resultant product collected at the bottoms 18 for removal as desired heavier olefins would be a composition in the wt% as follows: Cs 3.77 C9 20.16 Cio 34.97 C11 25.1 C12 10.37 C13 3.87 Ci4 2.16 Ci ⁇ 0.59 thus producing a slightly different heavier olefins of substantially from Cio through C20.
- Cis 0.4 thus producing a slightly different heavier olefins of substantially from Cio through
- the yield in this process to heavy products (C ⁇ and heavier) is thought to be in the range of 20% to 80% by weight, more preferably 50 % to 75% by weight. Most preferably, the yield to heavy products will be about 70% by weight.
- the product distribution can be controlled or modified by varying temperatures and pressure variables in the reaction distillation column.
- the process of this invention commences with the feeding of a substantially narrow range of lighter olefin-containing hydrocarbon feed stock from C3 to C4, with C being composed at least partially of 1- and 2-butene, into the reaction distillation column 10 at a predetermined point 11 between the bottom 12 and the top 13 of the reaction distillation column 10.
- the resultant products are ethylene, propylene and some 2-butene which will be taken out by the overhead line or stream 19 off the top 13 of the reaction distillation column 10 and C ⁇ through C10 which will be taken from the bottoms 18 of the bottom 12 of the reaction distillation column 10 by a line 20.
- a disproportionation catalyst 15 for disproportionating the olefin-containing hydrocarbon feed stock as it is passed into the reactive distillation column 10, is provided and located near the predetermined point of feed 11. As shown in FIG 3 the disproportionating catalyst 15 would be located both near the predetermined feed point 11 and directly above and below the feed point 11 for first disproportionating the olefin-containing hydrocarbon feed stock as completely as possible. Thus in this preferred embodiment the predetermined feed point 11 would be located on the reactive distillation column 10 for first directly feeding the olefin-containing hydrocarbon feedstock into the reactive distillation column 10 between the disproportionation catalyst 15.
- an isomerization catalyst 14 for isomerization of the now disproportionated olefin- containing hydrocarbon feed stock.
- an isomerization catalyst 14 would be located above and below the disproportionation catalyst 15 for isomerizing the reaction product from the disproportionation catalyst 15.
- the disproportionating catalyst 15 is located for first reacting the olefin-containing feedstock in this embodiment for at least the reason that the feedstock of C3 and C4, with C4 being composed of 1- and 2- butenes, which can only be isomerizied to predominantly 2-butene and that yields only 2-butene when it is disproportionated by the disproportionation catalyst 15.
- FIG 4 a serial process using multiple columns is shown with the first stage being generally shown at reference number 21, which is generally the process of Fig 3, the second stage is generally shown at reference number 22, which is generally the process of FIG 1 , and the third stage is generally shown at reference number 23, which is generally the process of FIG 2.
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002443638A CA2443638C (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins |
MX2007000398A MX2007000398A (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins. |
MXPA03009256A MXPA03009256A (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins. |
BR0208752-9A BR0208752A (en) | 2001-04-09 | 2002-04-08 | Process for better yields of higher molecular weight olefins from lower molecular weight olefins |
EP02719451A EP1385807A1 (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins |
KR1020037013223A KR100777379B1 (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins |
JP2002579405A JP4537002B2 (en) | 2001-04-09 | 2002-04-08 | Production method for obtaining high molecular weight olefin in high yield from low molecular weight olefin |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/828,771 | 2001-04-09 | ||
US09/828,771 US6515193B2 (en) | 2001-04-09 | 2001-04-09 | Process for production of higher linear internal olefins from butene |
US10/059,744 | 2002-01-29 | ||
US10/059,744 US6518469B2 (en) | 2001-04-09 | 2002-01-29 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002081417A1 true WO2002081417A1 (en) | 2002-10-17 |
Family
ID=26739125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/010806 WO2002081417A1 (en) | 2001-04-09 | 2002-04-08 | Process for improved yields of higher molecular weight olefins from lower molecular weight olefins |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1385807A1 (en) |
JP (1) | JP4537002B2 (en) |
CN (1) | CN100425582C (en) |
BR (1) | BR0208752A (en) |
CA (1) | CA2443638C (en) |
MX (1) | MXPA03009256A (en) |
RU (1) | RU2272016C2 (en) |
WO (1) | WO2002081417A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005073177A1 (en) * | 2004-01-29 | 2005-08-11 | Basf Aktiengesellschaft | Isomerisation of cis-2-pentenenitrile to form 3-pentenenitrile in a reactive distillation |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9567267B2 (en) * | 2012-11-12 | 2017-02-14 | Uop Llc | Process for oligomerizing light olefins including pentenes |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3600456A (en) * | 1968-01-08 | 1971-08-17 | British Petroleum Co | Production of c7-c20 olefins |
US4709115A (en) * | 1986-05-15 | 1987-11-24 | The Dow Chemical Company | Disproportionation of alkenes |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4684760A (en) * | 1986-02-24 | 1987-08-04 | Phillips Petroleum Company | Catalyst compositions useful for olefin isomerization and disproportionation |
-
2002
- 2002-04-08 MX MXPA03009256A patent/MXPA03009256A/en active IP Right Grant
- 2002-04-08 BR BR0208752-9A patent/BR0208752A/en not_active Application Discontinuation
- 2002-04-08 CN CNB028113152A patent/CN100425582C/en not_active Expired - Fee Related
- 2002-04-08 RU RU2003132583/04A patent/RU2272016C2/en not_active IP Right Cessation
- 2002-04-08 JP JP2002579405A patent/JP4537002B2/en not_active Expired - Fee Related
- 2002-04-08 CA CA002443638A patent/CA2443638C/en not_active Expired - Fee Related
- 2002-04-08 WO PCT/US2002/010806 patent/WO2002081417A1/en active Application Filing
- 2002-04-08 EP EP02719451A patent/EP1385807A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3600456A (en) * | 1968-01-08 | 1971-08-17 | British Petroleum Co | Production of c7-c20 olefins |
US4709115A (en) * | 1986-05-15 | 1987-11-24 | The Dow Chemical Company | Disproportionation of alkenes |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005073177A1 (en) * | 2004-01-29 | 2005-08-11 | Basf Aktiengesellschaft | Isomerisation of cis-2-pentenenitrile to form 3-pentenenitrile in a reactive distillation |
US7612224B2 (en) | 2004-01-29 | 2009-11-03 | Basf Aktiengesellschaft | Isomerisation of cis-2-pentenenitrile to form 3-pentenenitrile in a reactive distillation |
KR101143744B1 (en) | 2004-01-29 | 2012-05-11 | 바스프 에스이 | Isomerization of cis-2-pentenenitrile to form 3-pentenenitrile in a reactive distillation |
Also Published As
Publication number | Publication date |
---|---|
JP2004532842A (en) | 2004-10-28 |
EP1385807A1 (en) | 2004-02-04 |
MXPA03009256A (en) | 2004-01-29 |
RU2272016C2 (en) | 2006-03-20 |
CN100425582C (en) | 2008-10-15 |
BR0208752A (en) | 2004-06-22 |
RU2003132583A (en) | 2005-03-20 |
CN1512973A (en) | 2004-07-14 |
CA2443638C (en) | 2009-11-24 |
CA2443638A1 (en) | 2002-10-17 |
JP4537002B2 (en) | 2010-09-01 |
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