US2456435A - Alkylation process - Google Patents
Alkylation process Download PDFInfo
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- US2456435A US2456435A US609214A US60921445A US2456435A US 2456435 A US2456435 A US 2456435A US 609214 A US609214 A US 609214A US 60921445 A US60921445 A US 60921445A US 2456435 A US2456435 A US 2456435A
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- United States
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- hydrofluoric acid
- phase
- liquid
- olefin
- alkylation
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- 238000005804 alkylation reaction Methods 0.000 title description 54
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 201
- 239000012071 phase Substances 0.000 description 95
- 239000007788 liquid Substances 0.000 description 85
- 238000000605 extraction Methods 0.000 description 81
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 79
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 59
- 150000001336 alkenes Chemical class 0.000 description 57
- 230000029936 alkylation Effects 0.000 description 49
- 239000004215 Carbon black (E152) Substances 0.000 description 48
- 229930195733 hydrocarbon Natural products 0.000 description 48
- 150000002430 hydrocarbons Chemical class 0.000 description 48
- -1 aliphatic olefin Chemical class 0.000 description 40
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 39
- 238000000034 method Methods 0.000 description 37
- 239000002253 acid Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000004821 distillation Methods 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 125000000217 alkyl group Chemical group 0.000 description 23
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 22
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 238000009835 boiling Methods 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- 150000001349 alkyl fluorides Chemical class 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 11
- 239000001282 iso-butane Substances 0.000 description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 230000002152 alkylating effect Effects 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- SZURZHQMGVKJLV-UHFFFAOYSA-N 1,2-ditert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1C(C)(C)C SZURZHQMGVKJLV-UHFFFAOYSA-N 0.000 description 1
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical group CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 1
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- HDJLSECJEQSPKW-UHFFFAOYSA-N Methyl 2-Furancarboxylate Chemical compound COC(=O)C1=CC=CO1 HDJLSECJEQSPKW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- CRLNTRZMHKNJSR-UHFFFAOYSA-N furan-2-yl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CO1 CRLNTRZMHKNJSR-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
- C07C2/70—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1206—Hydrogen fluoride
Definitions
- This invention relates to an alkylation process and more particularly to an improved process for reacting a low-boiling aliphatic olefin with an alkylatable cyclic organic compound to produce alkyl derivatives thereof wherein hydrogen atoms on the ring are replaced by alkyl groups corresponding to the olefin. Still more particularly it relates to a process for the alkylation of benzene, toluene or other aromatic compound, furan, derivatives of furan, cycloparaffins, and any other cyclic organic compounds which are capable of being alkylated vby replacement of hydrogen on the ring with alkyl groups.
- inert diluents in the feed reduce the maximum production capacity of alkylating equipment and, if present in high proportion, cause reductions in yield and quality of the product.
- diluents are sometimes removed from feeds by preliminary fractional distillation, such distillation in many instances.is not economically feasible, particularly in the utilization of olefinic streams that contain only a few per cent of olefin.
- the present process advantageously efiects removal of inerts without such preliminary distillation.
- the principal object of the present invention is to provide an improved process for the alkylation of an alkylatable cyclic organic compound with a low-boiling aliphatic olefin. Another object is to provide such a process for the alkylation of aromatic hydrocarbons. Another object is to provide such a process for the alkylation of a so-called superaromatic such as furan. Another object is to provide such a process wherein the olefin employed is in admixture with large proportions of inert materials especially the corresponding paraflin.
- Another object is to provide such a process wherein the olefin is an isoolefin such as isobutylene and is in admixture with large proportions of the corresponding isoparafiin such as isobutane, as for example, in the case where the olefin-containing feed is prepared by the catalytic dehydrogenation of isobutane followed by known treatment to segregate the C4 fraction.
- the olefin-containing feed is prepared by the catalytic dehydrogenation of isobutane followed by known treatment to segregate the C4 fraction.
- Another object is to minimize the alkylation of isoparafiin in a process of the type mentioned in the preceding sentence whereby consumption of olefin by alkylation of isoparaflln is kept at a minimum and a maximum of the olefin contained in the feed is converted to the desired principal product, namely, alkylate of the cyclic organic compound.
- Another object is to provide a process as just outlined wherein the isoparafiin present in the feed is eliminated ahead of the alkylation zone wherein alkylation of the cyclic organic compound takes place, said elimination removing both the isoparamn present as such and the small proportion thereof which is inevitably alkylated prior to the alkylation zone proper.
- Another object is to provide a process as in the foregoing wherein the by-product higher isoparaffln, usually isooctane, formed by unavoidable alkylation of isoparaflin prior to the main alkylation zone is separately recovered in a novel and advantageous manner.
- Another object is to provide a process which accomplishes the foregoing objects in a simple, economical manner requiring a minimum of control and which is readily controlled to effect the desired results to an optimum extent.
- the present invention involves a process for reacting a low-boiling aliphatic olefin, and especially the C: to C6 olefins, namely, propylene, any of the three butylenes, and any of the pentenes, with an alkylatable cyclic organic compound, especially aromatic hydrocarbons and furan, to eifect replacement of hydrogen atoms on the ring with alkyl groups corresponding to the olefin by intimately admixing the olefincontaining hydrocarbon material which almost invariably contains large proportions of the corresponding parafiln with liquid concentrated hydrofluoric acid in amount substantially equimolar to the olefin, maintaining the resulting mixture under conditions effecting substantially complete hydrofiuorination of the olefin content as substantially the sole reaction, 1.
- this invention is an improvedprocess for reacting a low-boiling olefin and benzene to produce an alkylate in the presence of hydrofluoric acid, which comprises intlmately admixing with a hydrocarbon material containing a low-boiling olefin hydrofluoric acid in a proportion substantially equimolecular to the olefin, maintaining the resulting mixture for not more than about 30 minutes, extracting said mixture with substantially anhydrous liquid hydrofluoric acid in an extraction step at an extraction temperature not greater than about 100 F., mixing with the resulting extract benzene in an alkylation zone under conditions such as to produce an alkylate, separating the eflluent from said alkylation zone into a relatively light phase and arelatlvely heavy hydrofluoric acid phase, recovering said alkylate from said light phase, passing a major portion of said acid phase to said extraction step as a part of the extraction solvent, passing the raif
- Any cyclic organic compound which is alkylatable with a low-boiling olefin in the presence of liquid substantially anhydrous hydrofluoric acid may be employed in carrying out the present invention.
- an aromatic hydrocarbon especially the normally monocycllc aromatics such as benzene, toluene, xylene, cumene, mesitylene, ethylbenzene, etc., or a socalled superaromatic" such as furan.
- furan its. alkylatable homologs and derivatives may be used such as Z-furoic acid, methyl 2- furoate, 2-furyl-phenyl-ketone and the like.
- Furan is more easily alkylated than benzene and other alkylatable aromatics although it has a smaller number of replaceable hydrogen atoms per molecule.
- Similar alkylatable compounds which in part may be characterized as having at least two conjugated double bonds in a ring, may be employed, examples being phenol, pyrrol, thiophene and homologs, but usually benzene and its homolog's or furan is to be preferred.
- Olefin-containing material I may use any aliphatic olefin-containing material whlchcontains any of the low-boiling olefins in admixture with a substantial proportion of diluent hydrocarbon so that separation by fracvention obviates such preliminary separation since the diluent which is generally low-boiling awn although hydrogen may also be present,
- the olefin is com- ⁇ monly a C: to C5 olefin or mixture of such olefins. Since alkylation of isoparaillns with ethyl fluoride with anhydrous hydrogen fluoride as the catalyst is somewhat more difficult than in the case of propyl fluoride and the higher alkyl 1 fluorides, the C3 or higher oleflns are often preferred.
- C6 streams are often more valuable for other purposes, a C3 and/or C4 stream is more frequently employed in carrying out the present invention.
- a feed containing isobutylene and isobutene is very advantageously employed in the process of the present invention, the isobutylene giving'valuable tertiary butyl derivatives and the isobutane being alkylated to only a limited extent in the hydrofluorination and alkylation steps of the invention and being rejected in the rafflnate in the extraction step.
- the olefin-containing stream may be derived from any suitable source.
- a suitable feed stock such as crude oil, gas oil, naphtha, the corresponding paraflln, etc. It may be a by-product or the principal product of the cracking operation.
- a suitable feed stock such as crude oil, gas oil, naphtha, the corresponding paraflln, etc. It may be a by-product or the principal product of the cracking operation.
- undesired heavier and lighter materials are removed prior to the process of the present invention.
- fixed gases such as hydrogen and methane are readily removed in the conventional manner and materials heavier than the desired olefin, such as tars, etc, are likewise easily removed.
- the olefin-containing feed is free from sulfur, oxygen and nitrogen compounds including mercaptan and hydrogen sulfide as well as elementary sulfur, since the presence of such compounds in the process ordinarily is undesirable.
- the olefin-containing feed usually contains large proportions of the corresponding paraflin or parafflns. Generally, the feed will contain over 50% of parafiln and often more than thereof ranging up to or even 99%, the balance being olefin. It is a major advantage of the present invention that such dilute streams can be employed even in the case where an isoparaflin is present, since such isoparaflln is but little alkylated so that a maximum of the olefin is converted to the desired product, namely, the alkylated cyclic organic compound.
- any isoparaflin that is alkylated is converted to highly branched higher isoparaifin Hudrofluorinatirm step
- the olefin-containing feed is intimately admixed with substantially anhydrous liquid HF in an amount substantially stoichiometrically equal to the olefin and the mixture is subjected to reaction conditions efiecting hydrofluorination of substantially all the olefin as substantially the sole reaction.
- the temperature may be in the range of 40 to 200 F. and preferably below F.
- the pressure should be such as to maintain the hydrocarbons predominantly in-liquld phaseand may range from 100 to 300 pounds gage.
- the mol proportion of HF to olefin should preferably be within the range of from 1 to 1.1 times the total olefin. At proportions much'above this range polymerization of Extraction step
- the volume of hydrofluoric acid used should be equivalent in mols to about -20 or more times the number of mols of the alkyl fluorides present. Lesser proportions are likely to result in incomplete extraction of alkyl fluorides whereas greater proportions place an unnecessarily large quantity of hydrofluoric acid in circulation in the system and cause an excessive consumption of alkyl fluorides by alkylation of isoparaflln where present.
- the conditions of the extraction step are such that liquid-liquid extraction is accomplished, the hydrocarbon phase and the hydrofluoric acid phase being intimately mixedor emulsified with one another followed by a separation of the rafflnate phase containing the inert components including any isoparaflin and the extract phase in a conventional manner.
- the time of contacting may range from seconds to 5 minutes. The shorter the contacting the better is the result as long as intimate contacting of acid and hydro- Alkulation step
- the extractfrom the extraction step is passed to an alkylation zone to which is also supplied carbon is attained. When the time is excessively objectionable side reactions.
- the extraction may be very satisfactorily conducted with the amount of separate liquid hydrofluoric acid phase ranging from approximately 0.2 to 0J3 times the volume of the hydrocarbon phase.
- the amount of separate liquid hydrofluoric acid phase in the extraction step alkylation of the isopara'flin derived from the olefin containing feed is kept at a desirable minimum;
- the rafiinate from the extraction step is ordinarily passed to a fractionation step wherein the hydrofluoric acid contained therein is recovered as an overhead for recycle to the extraction step from a bottoms product containing inert material.
- a fractionation step wherein the hydrofluoric acid contained therein is recovered as an overhead for recycle to the extraction step from a bottoms product containing inert material.
- isoparaflin is present in the feed and alkylation thereof to any substantial extent takes place in the hydrofluorination and/or extraction step, the resulting higher isoparamn may be recovered by fractional distillation of the rafllnate.
- the reaction conditions in the alkylation zone are well known to those skilled in the art of hydrofluoric acid alkylation and may comprise a temperature in the range of -20 to 200 F., sufllcient pressure to maintain liquid phase, an average reaction time in the range of from 1 to minutes. good agitation, a mol ratio of cyclic organic compound to alkyl fluoride of from 1.5 to 10 or more, a ratio of from 5 to 10 being preferred, and a hydrocarbon-to-catalyst volume ratio in the range of from 0.2 to 4.
- the conditions of the alkylation are so adjusted that the mono-alkyl derivatives of the cyclic organic compound is the predominant or nearly the entire (say at least 00%) alkylated product of the alkylation reaction, since generally the polyalkyl derivatives are not as desirable as the monoalkyl compounds.
- Any of the usual contacting devices commonly employed in alkylation may be employed.
- the alkylation eliluent is allowed to separate by gravity or other means into two liquid phases, namely, a lighter organic phase containing the desired alkylated organic compound and a heavier acid phase.
- the organic phase is treated in any suitable manner usually by fractionation to recover the alkylated organic compound as the product of the process. Any hydrofluoric acid dissolved therein may also be recovered or recycled to the extraction step.
- the acid phase is preferably in part recycled to the extraction step and in part passed to the same fractionation column wherein the railinate described above is distilled.
- the hydrogen fluoride is recovered as an overhead for recycle to the extraction step from a bottoms product containing in addition to the inert compounds derived from the rafflnate the acid-soluble oils contained in the acid phase.
- the olefin containing feed and substantially pure hydrofluoric acid are fed via lines I and 2, respectively, to mixer 3.
- the mixture is held in time tank 4 for the necessary period of time to accomplish hydrofluorination of olefin.
- the resulting mixture is then passed into extractor 5 where it is liquid-liquid extracted with liquid by drofluoric acid introduced by line 6.
- the rainnate passes via lines 1 and 8 to column 9 or, where isoparaflin alkylation takes place to limited extent, via line I0 into the column II which separates it into an overhead of hydrofluoric acid and isobutane which may be recycled via lines l2 and I3 and a bottoms product containing the isoparaffin alkylate withdrawn via line l4.
- the extract separated in extractor 5 is passed via line IS, with added HF introduced via line It if desired, to alkylator 'I'l where the alkylation takes place.
- Benzene or other cyclic organic compound to be alkylated is introduced to alkylator ll via line I 8 which may enter unit I! at any suitable point therein.
- the alkylation eilluent is fed into separator l9 where phase separation takes place.
- the organic phase is passed via line 20 to fractionation unit 2
- wherein is separated, for example, a benzene recycle which is returned via line 22 to the alkylation zone, a fraction of unreacted HF which is recycled to the extraction step via lines 23 and I3 and a fraction of alkylated benzene or other cyclic organic-compound withdrawn as bottoms product via line 24.
- the acid phase separated in unit I9 is withdrawn via line 25 and conventionally separated into two streams, one stream being recycled to extraction unit 5 via line 26 and the second, which should be sufllciently large to keep the hydrofluoric acid in the system at the desired level of purity, is passed via line 21 into column 8 wherein it is distilled together with the raflinate feed thereto via line a.
- the hydrogen fluoride contained in this portion of the acid phase is recovered in purified form from the acidsoluble oils which are recovered in admixture with the inert components of the raillnate via line 28.
- Example I To a refinery fraction comprising about 10 mol to a reaction vessel maintained at a temperature below about 80 to 90 F. by cold water coils. The residence time in this vessel is about 10 to minutes.
- the vessel is provided with a stirrer to prevent the separation of a hydrofluoric acid layer in the bottom. From this vessel the mix ture passes to another centrifugal-type mixer into which is introduced an additional quantity of concentrated hydrofluoric acid approximately equal in volume to the total original propylenecontaining stream. The resulting mixture passes to a centrifugal separator, from which the heavier or hydrofluoric acid phase is withdrawn and passes immediately to an alkylating zone.
- benzene in a moi proportion about 5 to 10 times that of the original propylene.
- the alkylation temperature is about 80 to 120 F.; the pressure, about 50 to 150 p. s. i.; and the reaction time, about 5 to minutes.
- the eiliuent mixture from the alkylating zone is separated into an1acid layer which is recycled to the two mixers mentioned hereinbefore, and a hydrocarbon phase which is further separated by fractional distillation into hydrofluoric acid and unreacted-benzene recycle fractions and into an alkylate product fraction.
- the exact nature of the product depends somewhat on the alkylation conditions, as is indicated by the following illustrative data:
- Example If able dehydrogenation conditions, in a manner well-known to the art.
- the resulting eilluent is cooled and is substantially freed from light gases.
- hydrofluoric acid in a proportion approximately molecularly equivalent to the butylene content.
- the resulting mixture is rapidly countercurrently extracted with approximately 0.2 to 0.3 times its own volume of additional liquid hydrofluoric acid, or, generally, with the minimal volume sufficient to remove substantially all of the tertiary butyl fluoride from the mixture, whereby concomitant alkylation of isobutane is minimized.
- the extract ls passed immediately to an alkylation zone at approximately the alkylation conditions cited in Example I, wherein it is intimately agitated with a several-fold molecular excess of benzene; additional hydrofluoric acid is added, to increase the acid-to-hydrocarbon ratio to approximately 1:1 by volume.
- the resulting mixture is then separated into two liquid layers, and the lower layer is recycled and/or purified.
- the upper layer is freed from acid and is then fractionally distilled to isolate the alkylate product boiling above benzene.
- Illustrative data for this product are:
- An improved process for reacting a lowboiling olefin and an alkylatable cyclic organic compound to produce alkyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid' catalyst which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F.
- An improved process for reacting a low-boiling olefin and an alkylatable aromatic hydrocarbon to produce alkyl derivatives of said aromatic hydrocarbon by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F.
- An improved process for reacting a low-boiling olefin and benzene to produce alkyl derivatives of benzene by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst which comprises intimately admixing ahydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperasubstantially equimolar to said olefin, maintaining said admixture for not more than about minutes, intimately admixing with the resulting material asubstantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F.
- An improved process for reacting a low-boiling olefin and iuran to produce alkyl derivatives of furan by replacement of hydrogen atoms on -the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount ture not greater than about F.
- An improved process for reacting propylene with benzene to produce propyl derivatives of said benzene by replacement of hydrogen atoms on the ring with propyl groups which comprises intimately admixing a normally gaseous hydrocarbon material containing propylene and propane with liquid hydrofluoric acid in an amount substantially equimolar to said propylene, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F.
- An improved process for reacting propylene with iuran to produce propyl derivatives of said furan by replacement of hydrogen atoms on the ring with propyl groups which comprises intimately admixing a normally gaseous hydrocarbon material containing propylene and propane with liquid hydrofluoric acid in an amount substantially equimolar to said propylene, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F.
- An improved process for reacting isobutylene and an alkylatable cyclic organic compound to produce tertiary butyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about-30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a hydrocarbon phase and a first hydrofluoric acid phase, intimately admixing an alkylatable cyclic organic compound with said liquid hydrofluoric acid phase under reaction conditions such as to eflect alkylation of said cyclic organic compound to produce
- An improved process for reacting isobutylene and benzene to produce tertiary butyl derivatives of benzene by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a first hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing benzene with said first liquid hydrofluoric acid phase under reaction conditions such as to effect alkylation of benzene to produce tertiary butyl derivatives thereof, separating e
- An improved process for reacting isobutylene and furan to produce tertiary butyl derivatives of furan by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about 30 minutes, intimately admixing with the re-.
- sulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a hydrocarbon phase and a first hydrofluoric acid phase, intimately admixing furan with said liquid hydrofluoric acid phase under reaction conditions such as to efiect alkylation of furan to produce tertiary butyl derivatives thereof, separating eiiiuents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, and recovering said tertiary butyl derivatives of furan from said organic phase.
- a process for reacting a low-boiling aliphatic olefin and an alkylatable cyclic organic compound to produce alkyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin which comprises intimately admixing a hydrocarbon material containing said olefin and the corresponding paraflln with liquid hydrofluoric acid in amount substantially equimolar tosaid olefin, maintaining the resulting mixture under conditions efiecting substan- 13.
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Description
Patented Dec. 14, 1948 ALKYLATION PROCESS Maryan P. Matuszak, Bartlesville, Okla... assignor to Phillips Petroleum Company, a corporation of Delaware Application August 6,1945, Serial No. 609,214
20 Claims. (Cl. 260-845) This invention relates to an alkylation process and more particularly to an improved process for reacting a low-boiling aliphatic olefin with an alkylatable cyclic organic compound to produce alkyl derivatives thereof wherein hydrogen atoms on the ring are replaced by alkyl groups corresponding to the olefin. Still more particularly it relates to a process for the alkylation of benzene, toluene or other aromatic compound, furan, derivatives of furan, cycloparaffins, and any other cyclic organic compounds which are capable of being alkylated vby replacement of hydrogen on the ring with alkyl groups.
This application is a continuation-in-part of my prior and copending application, Ser. No. 467,874, filed December 4, 1942, now Patent No. 2,387,162.
In present-day acid-catalyzed alkylation processes, it is necessary, for obtaining optimum results, to limit the proportions of inert diluents in the feed to the alkylating zone. Diluents in the feed reduce the maximum production capacity of alkylating equipment and, if present in high proportion, cause reductions in yield and quality of the product. Although diluents are sometimes removed from feeds by preliminary fractional distillation, such distillation in many instances.is not economically feasible, particularly in the utilization of olefinic streams that contain only a few per cent of olefin. The present process advantageously efiects removal of inerts without such preliminary distillation.
The principal object of the present invention is to provide an improved process for the alkylation of an alkylatable cyclic organic compound with a low-boiling aliphatic olefin. Another object is to provide such a process for the alkylation of aromatic hydrocarbons. Another object is to provide such a process for the alkylation of a so-called superaromatic such as furan. Another object is to provide such a process wherein the olefin employed is in admixture with large proportions of inert materials especially the corresponding paraflin. Another object is to provide such a process wherein the olefin is an isoolefin such as isobutylene and is in admixture with large proportions of the corresponding isoparafiin such as isobutane, as for example, in the case where the olefin-containing feed is prepared by the catalytic dehydrogenation of isobutane followed by known treatment to segregate the C4 fraction. Another object is to minimize the alkylation of isoparafiin in a process of the type mentioned in the preceding sentence whereby consumption of olefin by alkylation of isoparaflln is kept at a minimum and a maximum of the olefin contained in the feed is converted to the desired principal product, namely, alkylate of the cyclic organic compound. Another object is to provide a process as just outlined wherein the isoparafiin present in the feed is eliminated ahead of the alkylation zone wherein alkylation of the cyclic organic compound takes place, said elimination removing both the isoparamn present as such and the small proportion thereof which is inevitably alkylated prior to the alkylation zone proper. Another object is to provide a process as in the foregoing wherein the by-product higher isoparaffln, usually isooctane, formed by unavoidable alkylation of isoparaflin prior to the main alkylation zone is separately recovered in a novel and advantageous manner. Another object is to provide a process which accomplishes the foregoing objects in a simple, economical manner requiring a minimum of control and which is readily controlled to effect the desired results to an optimum extent.
Many other aims, objects and advantages of the present invention will be apparent to those skilled in the art from this description taken in conjunction with the accompanying drawing which portrays diagrammatically one arrangement of equipment which has been found very suitable for carrying out the present invention in an embodiment thereof wherein benzene is alkylated.
General In one aspect, the present invention involves a process for reacting a low-boiling aliphatic olefin, and especially the C: to C6 olefins, namely, propylene, any of the three butylenes, and any of the pentenes, with an alkylatable cyclic organic compound, especially aromatic hydrocarbons and furan, to eifect replacement of hydrogen atoms on the ring with alkyl groups corresponding to the olefin by intimately admixing the olefincontaining hydrocarbon material which almost invariably contains large proportions of the corresponding parafiln with liquid concentrated hydrofluoric acid in amount substantially equimolar to the olefin, maintaining the resulting mixture under conditions effecting substantially complete hydrofiuorination of the olefin content as substantially the sole reaction, 1. e., to the substantial exclusion of alkylation of any isoparafiln present in the feed, extracting the resulting mixture with sufficient added liquid concentrated hydrofluoric acid to form a separate liquid acid phase under conditions such that substantially complete extraction of the alkyl fluorides in said liquidhy'drofluoricacid j sult, separating the resulting extract from the v raflinatewhich contains the, paraflln and anyv f- "small amount of alkylate formed by alkylati-an of a small. amount of any isoparaflin .present concomltantly,wlth'the extraction, directly admixing r the extract with a molar excess of the alkylatable cyclic organic compound and subjecting the re- I suiting mixture to conditions efl'ecting alkylation of the cyclic organic compound with substanti'allyall of the alkyl fluorides, and recovering the allgvl derivatives so produced as the product-of the process.
phase the principal re- In one specific embodiment, this invention is an improvedprocess for reacting a low-boiling olefin and benzene to produce an alkylate in the presence of hydrofluoric acid, which comprises intlmately admixing with a hydrocarbon material containing a low-boiling olefin hydrofluoric acid in a proportion substantially equimolecular to the olefin, maintaining the resulting mixture for not more than about 30 minutes, extracting said mixture with substantially anhydrous liquid hydrofluoric acid in an extraction step at an extraction temperature not greater than about 100 F., mixing with the resulting extract benzene in an alkylation zone under conditions such as to produce an alkylate, separating the eflluent from said alkylation zone into a relatively light phase and arelatlvely heavy hydrofluoric acid phase, recovering said alkylate from said light phase, passing a major portion of said acid phase to said extraction step as a part of the extraction solvent, passing the raifinate from said extraction step to a-distillation step for recovery of dissolved hydrofiuoric acid therefrom, passing a minor portion of -sald acid phase to said distillation step for removal of organic impurities, and passing purified and recovered hydrofluoric acid from said distillation step to said extraction step.
Compounds alkylated Any cyclic organic compound which is alkylatable with a low-boiling olefin in the presence of liquid substantially anhydrous hydrofluoric acid may be employed in carrying out the present invention. Ordinarily I alkylate either an aromatic hydrocarbon especially the normally monocycllc aromatics such as benzene, toluene, xylene, cumene, mesitylene, ethylbenzene, etc., or a socalled superaromatic" such as furan. Instead of furan, its. alkylatable homologs and derivatives may be used such as Z-furoic acid, methyl 2- furoate, 2-furyl-phenyl-ketone and the like. Furan is more easily alkylated than benzene and other alkylatable aromatics although it has a smaller number of replaceable hydrogen atoms per molecule. Similar alkylatable compounds, which in part may be characterized as having at least two conjugated double bonds in a ring, may be employed, examples being phenol, pyrrol, thiophene and homologs, but usually benzene and its homolog's or furan is to be preferred.
Olefin-containing material I may use any aliphatic olefin-containing material whlchcontains any of the low-boiling olefins in admixture with a substantial proportion of diluent hydrocarbon so that separation by fracvention obviates such preliminary separation since the diluent which is generally low-boiling awn although hydrogen may also be present,
is rejected as the raflinate'in the extraction step which follows the hydrofiuorination. Very often the diluent is the paraflin corresponding to the olefin. Hydrogen and methane have usually been removed by'the usual means. The olefin is com- {monly a C: to C5 olefin or mixture of such olefins. Since alkylation of isoparaillns with ethyl fluoride with anhydrous hydrogen fluoride as the catalyst is somewhat more difficult than in the case of propyl fluoride and the higher alkyl 1 fluorides, the C3 or higher oleflns are often preferred. Since C6 streams are often more valuable for other purposes, a C3 and/or C4 stream is more frequently employed in carrying out the present invention. A feed containing isobutylene and isobutene is very advantageously employed in the process of the present invention, the isobutylene giving'valuable tertiary butyl derivatives and the isobutane being alkylated to only a limited extent in the hydrofluorination and alkylation steps of the invention and being rejected in the rafflnate in the extraction step. The olefin-containing stream may be derived from any suitable source. Generally, it is prepared either by cracking or by dehydrogenation of a suitable feed stock such as crude oil, gas oil, naphtha, the corresponding paraflln, etc. It may be a by-product or the principal product of the cracking operation. Generally, undesired heavier and lighter materials are removed prior to the process of the present invention. For example, fixed gases such as hydrogen and methane are readily removed in the conventional manner and materials heavier than the desired olefin, such as tars, etc, are likewise easily removed. Preferably the olefin-containing feed is free from sulfur, oxygen and nitrogen compounds including mercaptan and hydrogen sulfide as well as elementary sulfur, since the presence of such compounds in the process ordinarily is undesirable.
The olefin-containing feed usually contains large proportions of the corresponding paraflin or parafflns. Generally, the feed will contain over 50% of parafiln and often more than thereof ranging up to or even 99%, the balance being olefin. It is a major advantage of the present invention that such dilute streams can be employed even in the case where an isoparaflin is present, since such isoparaflln is but little alkylated so that a maximum of the olefin is converted to the desired product, namely, the alkylated cyclic organic compound. Any isoparaflin that is alkylated is converted to highly branched higher isoparaifin Hudrofluorinatirm step In this step the olefin-containing feed is intimately admixed with substantially anhydrous liquid HF in an amount substantially stoichiometrically equal to the olefin and the mixture is subjected to reaction conditions efiecting hydrofluorination of substantially all the olefin as substantially the sole reaction. The temperature may be in the range of 40 to 200 F. and preferably below F. The pressure should be such as to maintain the hydrocarbons predominantly in-liquld phaseand may range from 100 to 300 pounds gage. The mol proportion of HF to olefin should preferably be within the range of from 1 to 1.1 times the total olefin. At proportions much'above this range polymerization of Extraction step The reaction mixture leaving the hydrofluorination zone and consisting essentially of alkyl fluoride and the inerts. usually essentially paraffln-ic, is extracted with substantially anhydrous liquid hydrofluoric acid in amount sufficient to form a separate liquid phase sufliciently large to dissolve substantially all of the alkyl fluoride.
The volume of hydrofluoric acid used should be equivalent in mols to about -20 or more times the number of mols of the alkyl fluorides present. Lesser proportions are likely to result in incomplete extraction of alkyl fluorides whereas greater proportions place an unnecessarily large quantity of hydrofluoric acid in circulation in the system and cause an excessive consumption of alkyl fluorides by alkylation of isoparaflln where present. The conditions of the extraction step are such that liquid-liquid extraction is accomplished, the hydrocarbon phase and the hydrofluoric acid phase being intimately mixedor emulsified with one another followed by a separation of the rafflnate phase containing the inert components including any isoparaflin and the extract phase in a conventional manner. The time of contacting may range from seconds to 5 minutes. The shorter the contacting the better is the result as long as intimate contacting of acid and hydro- Alkulation step The extractfrom the extraction step is passed to an alkylation zone to which is also supplied carbon is attained. When the time is excessively objectionable side reactions.
I have found that the extraction may be very satisfactorily conducted with the amount of separate liquid hydrofluoric acid phase ranging from approximately 0.2 to 0J3 times the volume of the hydrocarbon phase. By limiting the amount of separate liquid hydrofluoric acid phase in the extraction step, alkylation of the isopara'flin derived from the olefin containing feed is kept at a desirable minimum;
The rafiinate from the extraction step is ordinarily passed to a fractionation step wherein the hydrofluoric acid contained therein is recovered as an overhead for recycle to the extraction step from a bottoms product containing inert material. Where isoparaflin is present in the feed and alkylation thereof to any substantial extent takes place in the hydrofluorination and/or extraction step, the resulting higher isoparamn may be recovered by fractional distillation of the rafllnate.
the cyclic organic compound which is to be alkylated in accordance with the present invention. The reaction conditions in the alkylation zone are well known to those skilled in the art of hydrofluoric acid alkylation and may comprise a temperature in the range of -20 to 200 F., sufllcient pressure to maintain liquid phase, an average reaction time in the range of from 1 to minutes. good agitation, a mol ratio of cyclic organic compound to alkyl fluoride of from 1.5 to 10 or more, a ratio of from 5 to 10 being preferred, and a hydrocarbon-to-catalyst volume ratio in the range of from 0.2 to 4. Ordinarily the conditions of the alkylation are so adjusted that the mono-alkyl derivatives of the cyclic organic compound is the predominant or nearly the entire (say at least 00%) alkylated product of the alkylation reaction, since generally the polyalkyl derivatives are not as desirable as the monoalkyl compounds. Any of the usual contacting devices commonly employed in alkylation may be employed. The alkylation eliluent is allowed to separate by gravity or other means into two liquid phases, namely, a lighter organic phase containing the desired alkylated organic compound and a heavier acid phase. The organic phase is treated in any suitable manner usually by fractionation to recover the alkylated organic compound as the product of the process. Any hydrofluoric acid dissolved therein may also be recovered or recycled to the extraction step. The acid phase is preferably in part recycled to the extraction step and in part passed to the same fractionation column wherein the railinate described above is distilled. In this way the hydrogen fluoride is recovered as an overhead for recycle to the extraction step from a bottoms product containing in addition to the inert compounds derived from the rafflnate the acid-soluble oils contained in the acid phase.
Drawing Referring to the accompanying drawing the olefin containing feed and substantially pure hydrofluoric acid are fed via lines I and 2, respectively, to mixer 3. The mixture is held in time tank 4 for the necessary period of time to accomplish hydrofluorination of olefin. The resulting mixture is then passed into extractor 5 where it is liquid-liquid extracted with liquid by drofluoric acid introduced by line 6. The rainnate passes via lines 1 and 8 to column 9 or, where isoparaflin alkylation takes place to limited extent, via line I0 into the column II which separates it into an overhead of hydrofluoric acid and isobutane which may be recycled via lines l2 and I3 and a bottoms product containing the isoparaffin alkylate withdrawn via line l4.
The extract separated in extractor 5 is passed via line IS, with added HF introduced via line It if desired, to alkylator 'I'l where the alkylation takes place. Benzene or other cyclic organic compound to be alkylated is introduced to alkylator ll via line I 8 which may enter unit I! at any suitable point therein. The alkylation eilluent is fed into separator l9 where phase separation takes place. The organic phase is passed via line 20 to fractionation unit 2| wherein is separated, for example, a benzene recycle which is returned via line 22 to the alkylation zone, a fraction of unreacted HF which is recycled to the extraction step via lines 23 and I3 and a fraction of alkylated benzene or other cyclic organic-compound withdrawn as bottoms product via line 24.
The acid phase separated in unit I9 is withdrawn via line 25 and conventionally separated into two streams, one stream being recycled to extraction unit 5 via line 26 and the second, which should be sufllciently large to keep the hydrofluoric acid in the system at the desired level of purity, is passed via line 21 into column 8 wherein it is distilled together with the raflinate feed thereto via line a. In this way the hydrogen fluoride contained in this portion of the acid phase is recovered in purified form from the acidsoluble oils which are recovered in admixture with the inert components of the raillnate via line 28.
Example I To a refinery fraction comprising about 10 mol to a reaction vessel maintained at a temperature below about 80 to 90 F. by cold water coils. The residence time in this vessel is about 10 to minutes. The vessel is provided with a stirrer to prevent the separation of a hydrofluoric acid layer in the bottom. From this vessel the mix ture passes to another centrifugal-type mixer into which is introduced an additional quantity of concentrated hydrofluoric acid approximately equal in volume to the total original propylenecontaining stream. The resulting mixture passes to a centrifugal separator, from which the heavier or hydrofluoric acid phase is withdrawn and passes immediately to an alkylating zone. Into the alkylating zone is introduced benzene in a moi proportion about 5 to 10 times that of the original propylene. The alkylation temperature is about 80 to 120 F.; the pressure, about 50 to 150 p. s. i.; and the reaction time, about 5 to minutes. The eiliuent mixture from the alkylating zone is separated into an1acid layer which is recycled to the two mixers mentioned hereinbefore, and a hydrocarbon phase which is further separated by fractional distillation into hydrofluoric acid and unreacted-benzene recycle fractions and into an alkylate product fraction. The exact nature of the product depends somewhat on the alkylation conditions, as is indicated by the following illustrative data:
Run A B Temperature, E 118 118 Pressure. n. s. i 61 61 Contact time, min. 2o. 3 30. 9 Benzene/propylene, mol 8. 3 5. 4 Hydrocarbon/HF v0 l. 3 l. 4 Benzene-free alkyiate:
Yield, Wt. per cent of oleiln 249 220 Olefin c ntent, Wt. per cent 0. 0 0. 0 Organic fluorine, Wt. per cent 0. 0005 0. 0004 Composition, vol. per cent lsopropylbenzene 93. 5 9i. 0 Diisflnropylbenzen 5. 5 8. 0 Heavier l. 0 l. 0
Example If able dehydrogenation conditions, in a manner well-known to the art. The resulting eilluent is cooled and is substantially freed from light gases. To it in liquefied condition is added hydrofluoric acid in a proportion approximately molecularly equivalent to the butylene content. After a reaction period of about 10 to 15 minutes, the resulting mixture is rapidly countercurrently extracted with approximately 0.2 to 0.3 times its own volume of additional liquid hydrofluoric acid, or, generally, with the minimal volume sufficient to remove substantially all of the tertiary butyl fluoride from the mixture, whereby concomitant alkylation of isobutane is minimized. The extract ls passed immediately to an alkylation zone at approximately the alkylation conditions cited in Example I, wherein it is intimately agitated with a several-fold molecular excess of benzene; additional hydrofluoric acid is added, to increase the acid-to-hydrocarbon ratio to approximately 1:1 by volume. The resulting mixture is then separated into two liquid layers, and the lower layer is recycled and/or purified. The upper layer is freed from acid and is then fractionally distilled to isolate the alkylate product boiling above benzene. Illustrative data for this product are:
Yield, Wt. per cent of olefin 200 Olefin content, Wt. per cent 0.0 Organic fluorine, Wt. per cent 0.0003 Composition, vol. per cent:
Tert-butylbenzene 92.0 Di-tert-butylbenzene 7.5 Heavier 0.5
The foregoing description is to be taken as illustrative only and not as limiting the invention which is to be interpreted as limited solely by the language of the appended claims.
I claim:
An improved process for reacting a lowboiling olefin and an alkylatable cyclic organic compound to produce alkyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid' catalyst, which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a hydrocarbon phase and a first liquid hydrofluoric acid phase. intimately admixing an alkylatable cyclic organic compound with said liquid hydrofluoric acid extract phase under reaction conditions such as to efl'ect alkylation of said cyclic organic compound to produce said alkyl derivatives thereof, separating eifluents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, recovering said alkyl derivatives of said cyclic organic compound from said organic phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
2. An improved process for reacting a low-boiling olefin and an alkylatable aromatic hydrocarbon to produce alkyl derivatives of said aromatic hydrocarbon by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a first hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing aromatic hydrocarbon with said liquid hydrofluoric acid phase under reaction. conditions such as to effect alkylation of said aromatic hydrocarbon to produce said alkyl derivatives thereof, separating eiiiuents of said reaction into a second hydrocarbon phase and a second liquid hydrofluoric acid phase, recovering said alkyl derivatives of said aromatic hydrocarbon from said second hydrocarbon phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said first hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
3. An improved process for reacting a low-boiling olefin and benzene to produce alkyl derivatives of benzene by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing ahydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount substantially equimolar to said olefin, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperasubstantially equimolar to said olefin, maintaining said admixture for not more than about minutes, intimately admixing with the resulting material asubstantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a first hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing benzene with said liquid hydrofluoric acid phase under reaction conditions such as to effect alkylation of said benzene to produce said alkyl derivatives thereof, separating effluents of said reaction into a second hydrocarbon phase and a second liquid hydrofluoric acid phase, recovering said alkyl derivatives of said benzene from said second hydrocarbon phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said first hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
4. An improved process for reacting a low-boiling olefin and iuran to produce alkyl derivatives of furan by replacement of hydrogen atoms on -the ring with alkyl groups corresponding to said olefin in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing a hydrocarbon material containing a low-boiling olefin with liquid hydrofluoric acid in an amount ture not greater than about F. and subsequently separating a hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing furan with said liquid hydrofluoric acid phase under reaction conditions such as to effect alkylation of said furan to produce said alkyl derivatives thereof, separating effluents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, recovering said alkyl derivatives of said furan from said organic phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
5. An improved process for reacting propylene 'with an alkylatable cyclic organic compound to produce propyl derivatives of said cyclic organic carbon material containing propylene and propane with liquid hydrofluoric acid in an amount substantially equimolar to said propylene, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing an alkylatable cyclic organic compound with said liquid hydrofluoric acid phase under reaction conditions such as to efi'ect alkalation of said cyclic organic compound to produce said propyl derivatives thereof, separating eiiluents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, recovering said propyl derivatives of said cyclic organic compound from said organic phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said hydrocarbon phase to a distillationstep for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
6. An improved process for reacting propylene with benzene to produce propyl derivatives of said benzene by replacement of hydrogen atoms on the ring with propyl groups which comprises intimately admixing a normally gaseous hydrocarbon material containing propylene and propane with liquid hydrofluoric acid in an amount substantially equimolar to said propylene, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a first hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing benzene with said liquid hydrofluoric acid phase under reaction conditions such as to eflect alkylation of said benzene to produce said propyl derivatives thereof, separating efliuents of said reaction into a second hydrocarbon phase and a second liquid hydrofluoric acid hase, recovering said propyl derivatives of said benzene from said second hydrocarbon phase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said first hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
7. An improved process for reacting propylene with iuran to produce propyl derivatives of said furan by replacement of hydrogen atoms on the ring with propyl groups which comprises intimately admixing a normally gaseous hydrocarbon material containing propylene and propane with liquid hydrofluoric acid in an amount substantially equimolar to said propylene, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F. and subsequently separating a hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing furan with said liquid hydrofluoric acid phase under reaction conditions such as to effect alkylation of said furan to produce said propyl derivatives thereof, separating eflluents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, recovering said propyl derivatives of said furan from said organicphase, passing a major portion of said second acid phase to said extraction step as a part of said extraction liquid, passing said hydrocarbon phase to a distillation step for recovery of dissolved hydrogen fluoride therefrom, passing a minor portion of said second acid phase to said distillation step for removal of organic impurities, and recovering from said distillation step purified hydrogen fluoride and passing same to said extraction step.
8. An improved process for reacting isobutylene and an alkylatable cyclic organic compound to produce tertiary butyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about-30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a hydrocarbon phase and a first hydrofluoric acid phase, intimately admixing an alkylatable cyclic organic compound with said liquid hydrofluoric acid phase under reaction conditions such as to eflect alkylation of said cyclic organic compound to produce tertiary butyl derivatives thereot, separating emuents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, and recovering said tertiary butyl derivatives of said cyclic organic compound from said organic phase.
9. An improved process for reacting isobutylene and benzene to produce tertiary butyl derivatives of benzene by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about 30 minutes, intimately admixing with the resulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a first hydrocarbon phase and a first liquid hydrofluoric acid phase, intimately admixing benzene with said first liquid hydrofluoric acid phase under reaction conditions such as to effect alkylation of benzene to produce tertiary butyl derivatives thereof, separating efliuents of said reaction into a second hydrocarbon phase and a second liquid hydrofluoric acid phase, and recovering said tertiary butyl derivatives of benzene from said second hydrocarbon phase.
10. An improved process for reacting isobutylene and furan to produce tertiary butyl derivatives of furan by replacement of hydrogen atoms on the ring with tertiary butyl groups in the presence of a hydrofluoric acid catalyst, which comprises intimately admixing a normally gaseous hydrocarbon containing isobutylene and isobutane in liquid phase with liquid hydrofluoric acid in an amount substantially equal to the butylene content of said hydrocarbon, maintaining said admixture for not more than about 30 minutes, intimately admixing with the re-.
sulting material a substantial excess of liquid concentrated hydrofluoric acid as an extraction liquid in an extraction step at an extraction temperature not greater than about 100 F., subsequently separating a hydrocarbon phase and a first hydrofluoric acid phase, intimately admixing furan with said liquid hydrofluoric acid phase under reaction conditions such as to efiect alkylation of furan to produce tertiary butyl derivatives thereof, separating eiiiuents of said reaction into an organic phase and a second liquid hydrofluoric acid phase, and recovering said tertiary butyl derivatives of furan from said organic phase.
11. The process of claim 8 wherein higher isoparamn formed in said extraction step by alkylation 01' isobutane and appearing in said hydrocarbon phase is separately recovered by passing said hydrocarbon phase to a distillation zone and there separating said higher isoparaflin from the isobutane and hydrogen fluoride, and wherein said isobutane and hydrogen fluoride so recovered are recycled to said extraction step.
12. A process for reacting a low-boiling aliphatic olefin and an alkylatable cyclic organic compound to produce alkyl derivatives of said cyclic organic compound by replacement of hydrogen atoms on the ring with alkyl groups corresponding to said olefin which comprises intimately admixing a hydrocarbon material containing said olefin and the corresponding paraflln with liquid hydrofluoric acid in amount substantially equimolar tosaid olefin, maintaining the resulting mixture under conditions efiecting substan- 13. tially complete hydrofluorination of said oleflns as substantially the sole reaction, extracting the resulting mixture with sufilcient liquid hydrofluoric acid to form a separate liquid phase under conditions such that substantially complete extraction of the alkyl fluorides in said liquid of said cyclic organic compound from the alkylation eflluent. v
13. The process of claim 12 wherein said cyclic organic compound is introduced to said alkylation step in 8. mol proportion of from .to times that of the alkyl fluoride present.
14. The process of claim 12 wherein said corresponding paraflin is an isoparaflin, wherein substantial alkylation thereofin said hydrofluorination step is avoided, and wherein alkylation thereof in said extraction step is minimized.
15. The process of claim 8 wherein said extraction step is conducted as a liquid-liquid extraction at a temperature not greater than about 100 F. and with the amount of separate liquid hydrofluoric acid phase ranging from approximately 0.2 to 0.3 times the volume of the hydrocarbon phase. a
14 16. The process of claim 12 wherein said extraction step is conducted as a liquid-liquid extraction at a temperature not greaterthan about F. and with the amount of separate liquid hydrofluoric acid phase ranging from approximately 0.2 to 0.3 times the volumeof the hydrocarbon phase.
1'7. The process which comprises alkylating furan with a lower alkyl fluoride in the presence of liquid substantially anhydrous hydrofluoric acid as the catalyst.
18. The process which comprises alkylating an alkylatable organic compound having a fivemembered heterocyclic ring with an alkyl fluoride in the presence of liquid hydrofluoric acid as a catalyst.
19. A process which comprises alkylating an presence of hydrofluoric acid as a catalyst.
MARYAN P. MATUSZAK.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,387,162 Matuszak pct. 16, 1945
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| US609214A US2456435A (en) | 1945-08-06 | 1945-08-06 | Alkylation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US609214A US2456435A (en) | 1945-08-06 | 1945-08-06 | Alkylation process |
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| US2456435A true US2456435A (en) | 1948-12-14 |
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| US609214A Expired - Lifetime US2456435A (en) | 1945-08-06 | 1945-08-06 | Alkylation process |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2569400A (en) * | 1948-05-27 | 1951-09-25 | Monsanto Chemicals | Alkylation of polystyrene using a hydrogen fluoride catalyst |
| US2617839A (en) * | 1950-08-14 | 1952-11-11 | Texas Co | Recovery and utilization of olefins from gases |
| US2653980A (en) * | 1946-08-30 | 1953-09-29 | Phillips Petroleum Co | Alkylation of aromatic hydrocarbons with isoparaffins |
| US2681362A (en) * | 1949-10-07 | 1954-06-15 | Sun Oil Co | Alkyl substituted benzene sulfonate |
| US2681373A (en) * | 1949-06-02 | 1954-06-15 | Sun Oil Co | Catalytic alkylation of aromatic hydrocarbons |
| US2872493A (en) * | 1956-03-06 | 1959-02-03 | Phillips Petroleum Co | Utilization of alkylation by-products |
| US2943094A (en) * | 1957-04-05 | 1960-06-28 | British Petroleum Co | Catalytic conversion process |
| US4026961A (en) * | 1975-09-15 | 1977-05-31 | Phillips Petroleum Company | Isoparaffin HF alkylation with low-boiling alkyl fluoride-containing fraction |
| US4049728A (en) * | 1976-03-23 | 1977-09-20 | Phillips Petroleum Company | Hydrofluorination process |
| US4052469A (en) * | 1975-05-16 | 1977-10-04 | Phillips Petroleum Company | Ethylfluoride production |
| EP0479593A3 (en) * | 1990-10-05 | 1992-06-10 | Hoechst Celanese Corporation | Process for acylation or alkylation of aromatic compounds in hydrogen fluoride |
| US6783659B2 (en) | 2001-11-16 | 2004-08-31 | Chevron Phillips Chemical Company, L.P. | Process to produce a dilute ethylene stream and a dilute propylene stream |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2387162A (en) * | 1942-12-04 | 1945-10-16 | Phillips Petroleum Co | Conversion of hydrocarbons |
-
1945
- 1945-08-06 US US609214A patent/US2456435A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2387162A (en) * | 1942-12-04 | 1945-10-16 | Phillips Petroleum Co | Conversion of hydrocarbons |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2653980A (en) * | 1946-08-30 | 1953-09-29 | Phillips Petroleum Co | Alkylation of aromatic hydrocarbons with isoparaffins |
| US2569400A (en) * | 1948-05-27 | 1951-09-25 | Monsanto Chemicals | Alkylation of polystyrene using a hydrogen fluoride catalyst |
| US2681373A (en) * | 1949-06-02 | 1954-06-15 | Sun Oil Co | Catalytic alkylation of aromatic hydrocarbons |
| US2681362A (en) * | 1949-10-07 | 1954-06-15 | Sun Oil Co | Alkyl substituted benzene sulfonate |
| US2617839A (en) * | 1950-08-14 | 1952-11-11 | Texas Co | Recovery and utilization of olefins from gases |
| US2872493A (en) * | 1956-03-06 | 1959-02-03 | Phillips Petroleum Co | Utilization of alkylation by-products |
| US2943094A (en) * | 1957-04-05 | 1960-06-28 | British Petroleum Co | Catalytic conversion process |
| US4052469A (en) * | 1975-05-16 | 1977-10-04 | Phillips Petroleum Company | Ethylfluoride production |
| US4026961A (en) * | 1975-09-15 | 1977-05-31 | Phillips Petroleum Company | Isoparaffin HF alkylation with low-boiling alkyl fluoride-containing fraction |
| US4049728A (en) * | 1976-03-23 | 1977-09-20 | Phillips Petroleum Company | Hydrofluorination process |
| EP0479593A3 (en) * | 1990-10-05 | 1992-06-10 | Hoechst Celanese Corporation | Process for acylation or alkylation of aromatic compounds in hydrogen fluoride |
| US6783659B2 (en) | 2001-11-16 | 2004-08-31 | Chevron Phillips Chemical Company, L.P. | Process to produce a dilute ethylene stream and a dilute propylene stream |
| US6790342B1 (en) | 2001-11-16 | 2004-09-14 | Chevron Phillips Chemical Company Lp | Process to produce a dilute ethylene stream and a dilute propylene stream |
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