US3884986A - Catalytic conversion of polycyclic aromatic hydrocarbons in the presence of hydrogen - Google Patents
Catalytic conversion of polycyclic aromatic hydrocarbons in the presence of hydrogen Download PDFInfo
- Publication number
- US3884986A US3884986A US420988A US42098873A US3884986A US 3884986 A US3884986 A US 3884986A US 420988 A US420988 A US 420988A US 42098873 A US42098873 A US 42098873A US 3884986 A US3884986 A US 3884986A
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- United States
- Prior art keywords
- catalyst
- isomer
- polycyclic aromatic
- process according
- aromatic hydrocarbon
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- Expired - Lifetime
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010457 zeolite Substances 0.000 claims abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 23
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- -1 polycyclic hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000006317 isomerization reaction Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052776 Thorium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 12
- ZVGHRKGPUUKBPP-UHFFFAOYSA-N 1,2,3,5,6,7-hexahydro-s-indacene Chemical compound C1=C2CCCC2=CC2=C1CCC2 ZVGHRKGPUUKBPP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012530 fluid Substances 0.000 description 5
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 4
- 239000012080 ambient air Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LFAYMJXHGYUQNV-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydroanthracene Chemical compound C1CCCC2=C1C=C1CCCCC1=C2 LFAYMJXHGYUQNV-UHFFFAOYSA-N 0.000 description 1
- YSZLFGZFQTTZIQ-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydrophenanthrene Chemical compound C1CCCC2=C1C=CC1=C2CCCC1 YSZLFGZFQTTZIQ-UHFFFAOYSA-N 0.000 description 1
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- FUUGBGSHEIEQMS-UHFFFAOYSA-N 4a,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalene Chemical class C1CCCC2(C)CCCCC21C FUUGBGSHEIEQMS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000001260 acyclic compounds Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
Definitions
- Acidic alumino-silicate zeolites which can be utilized in the subject process have been described in copending application Ser. No. 590,225, filed Oct. 28, 1966, now US. Pat. No. 3,396,203 and in copending application Ser. No. 750,432, filed Aug. 2, 1968, of Ronald D. Bushick entitled Process for Producing Sym- Octahydroanthracene from Sym- Octahydrophenanthrene, and in copending application Ser. No. 581,129, filed Aug. 25, 1966, now abandoned of Francis William Kirsch, David S. Barmby and John D. Potts entitled: Process for ParaffinOlefin Alkylation" and in copending application Ser. No. 716,190, filed Mar.
- naphthenes such as perhydro-polycyclic hydrocarbons as traction fluids (or as components of a blended traction-fluid base stock) is taught in Ser. No. 33,023, filed Apr. 29, 1970 of Irl N. Duling and Frederick P. Glazier, entitled Combination of Tractive Drive and Traction Fluid Comprising Cyclic or Acyclic Compounds.
- Another utility of such naphthenes is found in an application filed on or about Feb. 19, 1971, entitled Lubrication of Controlled-Slip Differential, of David S. Gates, Paul E. Hagstrom and Marcus W. Haseltine, Jr.
- the conversion of s-hydrindacene to ashydrindacene, or the reverse conversion, is taught in Ser. No. 869,868, filed Oct. 27, 1969 Ronald D. Bushick.
- the disclosure of all of the above-cited applications is hereby incorporated in the present application.
- processes are disclosed for the catalytic conversion of polycyclic aromatic hydrocarbons (e.g., s-OHP to s-OHA) comprising contacting a hydrocarbonaceous feed, in a conversion zone at an elevated temperature, with an acidic aluminosilicate catalyst for sufficient time to permit the conversion to occur.
- the present invention as that of parent application Ser. No. 749,932, is an improvement on said processes, comprising (in one aspect) conducting such processes in the presence of from 55000 p.s.i. of hydrogen (preferably, 15-1500 p.s.i. of hydrogen).
- a hydrocarbon conversion process comprises contacting a polycyclic aromatic hydrocarbon (e.g., dicyclohexyl) in a conversion zone at an elevated conversion temperature with an acidic alumino-silicate catalyst in the presence of from 5-5000 p.s.i.
- a polycyclic aromatic hydrocarbon e.g., dicyclohexyl
- an acidic alumino-silicate catalyst in the presence of from 5-5000 p.s.i.
- an upgraded hydrocarbon conversion product e.g., dimethyl decalins
- Gd monovalent, divalent or trivalent metal
- metal hydride e.g., GdH
- metal hydroxide e.g., Gd-OH
- mixed metal hydride hydroxide e.g., Gd for every twelve atoms of aluminum in said a
- the metals (and catalysts) can be those disclosed in the aforementioned United States paten applications; however, in the preferred cations, the metal of the cations consists essentially of one or more metals from the group consisting of Al, Mg, Ca, Sr, Ba, Cr, Mn, Zn, Ag, Cd, In, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yh, Lu, Th, and U.
- Halide adjuvants e.g., Serial Nos.
- a hydrogenation catalyst e.g., see US. Pat. No. 3,396,203 and US. Pat. No. 3,534,114
- the catalyst (and reaction zone) not contain such metals (or cations of such metals) as Co, Ni, Cu, Nb, Mo, Ru, Th, Pd, W, Re, Os, Ir, or Pt.
- the present invention is especially useful for converting s-I-IIN to its isomer, as-HIN, or as-HIN to its isomer, s-HIN, by process comprising contacting a feed rich in one of the said isomers with an acidic alumino-silicate catalyst in the presence of 5l500 p.s.i. of hydrogen at a temperature above 40C. but below cracking temperature, whereby isomerization of the contacted isomer to the other isomer occurs. From 1 to 20 (preferably, from 2-12) percent of water, based on the weight of the catalyst, can also be present in the contact zone (some as in the form of hydroxyl groups). Means of recovering said other isomer from the isomerization mixture are disclosed for example, in the aforementioned application Ser. No. 869,868, filed October 27, 1969. The resulting depleted isomerization mixture can be recycled and further contacted with the catalyst.
- the preferred acidic alumino-silicate catalyst comprises a crystalline zeolite (and, more preferably, is at least 50% crystalline). Also preferred is an acidic alumino-silicate catalyst, wherein the atomic ratio Al/Si is from 0.65 to 0.2 and wherein (on analysis prior to said contacting) there is at least one trivalent or divalent metal, metal oxide or metal hydroxide cation for ever twelve atoms of aluminum in said alumino-silicate. Also preferred as such metals of the cation are the rare earths, especially Y, La and Gd.
- one preferred catalyst is the Gd aluminosilicate described in the aforementioned United States patent applications, Ser. No. 715,994, Ser. No. 715,998 and Ser. No. 718,980.
- the preferred conditions are a temperature above 5C. (more preferably in the range of 80120C.) at a weight hourly space velocity of 0. l20 (more preferably 025-), and in the presence of 5-500 (more preferably -250) p.s.i. of hydrogen.
- the hydrogen partial pressure in the conversion zone is preferably from 15 to 100 percent of the total gas pressure.
- the process can be conducted when the hydrocarbonaceous feed is contacted in liquid, vapor or mixed phase (e.g., at reflux or in trickle phase).
- the hydrogen can be recycled (as at rates up to 10,000 scf/bbl of feed). If the catalyst activity appreciably decreases in time, the catalyst can be separated from the hydrocarbon reactants and regenerated, as by burning in air. After such burning, water can be added by the means disclosed in the previously cited copending applications.
- GdHY acidic Gd alumino-silicate catalyst
- illutrate illustrate used of the GdHY catalyst in the subject process to isomerize s-OHA to s-OHP, to isomerize s-OHP to s-OHA, and to isomerize s-HIN to as-HIN or the reverse.
- EXAMPLE I An NH,,Y zeolite was prepared by contacting 625 g. NaY zeolite (sorptometer surface area of 758 m /g.) for 12 exchange cycles with fresh portions of a boiling 105C.) solution of535 g. NH Cl in 1425 mls. distilled water at 100C. (i.e., a 5.5 normal solution). The fresh solution had a pH at 100C. of 4.2-4.5 (which, when necessary, was obtained by adjusting with either NH OH or HCl). Prior to contact the solution was filtered to insure that it is free of undissolved salt particles.
- the equilibrated NaY zeolite (in ambient air for 24 hours) had a 25.7 percent weight loss on ignition and analyzed 10.16% Na, 45.99% SiO and 16.60% A]- O
- the NaY contained 0.442 moles Na per 100 g. zeolite.
- Each ammonium exchange cycle was for a /2 hour contact period followed by adjusting the pH to 5.5 with NH OH and then filtering the hot (80-90C.) slurry (filtrate pH ranged from 4.5 to 5.2). After the 12 NH C1 exchange cycles, the zeolite was washed for 8 cycles of 15 minutes contact, and then filtered, with 1.4 liters each of distilled H O. After this washing a test with silver nitrate showed that the filtrate contained no C1-.
- the washed zeolite cake was broken up and dried over night at 140C. On the next day, the dry zeolite was pulverized and screened through a 100 mesh screen.
- the resulting NH Y zeolite (after equilibration in ambient air for 24 hours) had a weight loss on ignition at 1,000C. (for two hours) of 29.9%, and analyzed 4.70 wt. N (0.426 moles NHf/IOO g. of waterfree NH Y zeolite). It contained less than 0.1 wt. Na (or less than 0.006 moles Na/ g. of water-free zeolite).
- the resulting GdNH Y zeolite was washed for 8 cycles each, of 15 minutes contact, with /2 liter distilled H O (a diphenyl amine test showed that no nitrate ion was present in the filtrate from the 8th wash cycle).
- the GdNH Y was dried over night at C. and then put through a 100 mesh screen.
- the resulting 100 mesh GdNH Y zeolite (after equilibration in ambient air) had a 24.1% weight loss on ignition (for 2 hours at 1000C.).
- the GdNH Y zeolite contained 0.46 wt. N (0.043 moles NHf/lOO g. water-free GdNH Y), 14.05 wt. Gd (0.116 moles Gd/100 g.) and less than 0.1% Na (less than 0.006 moles Na/l00 g.).
- the 100 mesh GdNH Y was activated by heating slowly in flowing dry air in a split tube furnace to 500C., held at 500C. for 4 hours and bottled hot.
- the activated GdHY zeolite had a sorptometer surface area of 757 m /g.
- EXAMPLE II 10 ml. portions of feed hydrocarbon (s-OHA or s- OHP) and 4.5 g. protions of the activated GdHY catalyst of Example I, were placed in a magnetically stirred Parr bomb into which hydrogen was introduced until the pressure was 1 10 p.s.i.g. The bomb was then heated to 100C. and that temperature was maintained for a desired period of time, after which the bomb was cooled to room temperature, the pressure was reduced and a sample of the catalyst-free reaction product was taken for chromatographic analysis.
- feed hydrocarbon s-OHA or s- OHP
- protions of the activated GdHY catalyst of Example I were placed in a magnetically stirred Parr bomb into which hydrogen was introduced until the pressure was 1 10 p.s.i.g. The bomb was then heated to 100C. and that temperature was maintained for a desired period of time, after which the bomb was cooled to room temperature, the pressure was reduced and a sample of the catalyst-free reaction product was taken for chromatographic analysis.
- s-OHA can be separated (as by crystallization) from the reaction mixture and dehydrogenated to produce anthracene.
- the subject process can also be used to convert prehnitene to durene or to convert durene to prehnitene.
- pseudocumene can be converted to mesitylene.
- Alkyltetralins can be converted to isomeric alkyltetralins.
- Example 11 is repeated except that the feed hydrocarbon is s-hydrindacene and the average temperature in the bomb is maintained at about C.
- the major reaction product is as-hydrindacene.
- the reverse reaction can also be effected at 150C. when the feed hydrocarbon consists essentially of as-hydrindacene.
- These reaction products per se, as useful as heat exchange fluids, as in a nuclear reactor, or they can be hydrogenated (to at least 95 percent saturation) to produce a naphthene mixture which is useful as a traction fluid component (e.g., 10 volume percent of the hydrogenated mixture can be blended with 90 volume percent of hydrogenated polybutylene oil having a viscosity of 10 c.s. at 210F. and a bromine number of less than 5).
- Process for converting a polycyclic aromatic hydrocarbon containing at least one saturated ring to an isomer, or the conversion of said isomer to said polycyclic aromatic hydrocarbon comprising contacting a feed rich in said polycyclic aromatic hydrocarbon, or rich in the said isomer with an acidic alumino-silicate catalyst in the presence of from 5-1500 p.s.i. of hydrogen at a temperature above 40C. but below cracking temperature, whereby isomerization of the contacted isomer to the other isomer occurs.
- said acidic alumino-silicate catalyst comprises a crystalline zeolite.
- said catalyst has an Al/Si atomic ratio of from 0.65 to 0.2 and contains at least 1 trivalent or divalent metal, metal oxide or metal hydroxide cation for ever 12 atoms of aluminum in said alumino-silicate.
- said acidic aluminosilicate catalyst comprises a crystalline zeolite.
- said catalyst contains metal cations consisting essentially of one or more met- 2115 from the group consisting of aluminum, magnesium, calcium, strontium, barium, chromium, manganese, zinc, silver, cadmium, indium, tin, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium and uranium.
- metal cations consisting essentially of one or more met- 2115 from the group consisting of aluminum, magnesium, calcium, strontium, barium, chromium, manganese, zinc, silver, cadmium, indium, tin, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium
Abstract
Polycyclic aromatic hydrocarbons (preferably containing at least three condensed rings) can be converted to other polycyclic hydrocarbons by a catalytic conversion process comprising contacting the hydrocarbon with an acidic alumino-silicate zeolite in the presence of from 5-5000 p.s.i. of hydrogen at an elevated temperature (e.g., at least 40*C., preferably 100200*C.) for a period of time sufficient to allow the catalytic conversion to occur. For example, s-hydrindacene (s-HIN) can be converted to as-hydrindacene (as-HIN) by so contacting the s-HIN with a GdHY zeolite at 100-200*C. (e.g., 150*C.) in the presence of 15-250 p.s.i.g. of hydrogen at a weight hourly space velocity in the range of 0.1-20 (preferably 0.25-10).
Description
United States Patent Bushick et al.
CATALYTIC CONVERSION OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE PRESENCE OF HYDROGEN Inventors: Ronald D. Bushick, Glen Mills;
Alfred E. Hirschler, Springfield, both of Pa.
Sun Ventures, Inc., Marcus Hook, Pa.
The portion of the term of this patent subsequent to Feb. 23, 1988, has been disclaimed.
Filed: Dec. 3, 1973 Appl. No.: 420,988
Related U.S. Application Data Continuation of Ser. No. 118,177, Feb. 23, 1971, Pat. No. 3,776,968, Continuation-impart of Ser. No. 749,932, Aug. 5, 1968, Pat. No. 3,565,964.
Assignee:
Notice U.S. Cl. 260/668 F; 260/668 A Int. Cl. C07c 15/28 Field of Search 260/668 F References Cited UNITED STATES PATENTS 6/1968 Michalowicz 260/668 F 8/1968 Bushick 260/668 F ]*May 20, 1975 3,534,114 10/1970 Bushick 260/668 F 3,534,115 10/1970 Bushick 3,541,001 1 H1970 Hirschler 3,715,406 2/1973 Bushick 260/668 F FOREIGN PATENTS OR APPLICATIONS 1,039,246 8/1966 United Kingdom 260/668 F Primary Examiner-Veronica OKeefe Attorney, Agent, or Firm-George L. Church; .1. Edward Hess; Barry A. Bisson [57] ABSTRACT the presence of 15-250 p.s.i.g. of hydrogen at a weight v hourly space velocity in the range of 0.1-20 (preferably 025-10).
16 Claims, No Drawings CATALYTIC CONVERSION OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE PRESENCE OF HYDROGEN CROSS REFERENCES TO RELATED APPLICATIONS This application is a continuation of Ser. No. 1 18,177 filed Feb. 23, 1971, which issued Dec. 4, 1973 73 as US. Pat. No. 3,776,986, and said Ser. No. 118,177 is a continuation-in-part of Ser. No. 749,932, filed Aug. 5, 1968, which issued Feb. 23, 1971 as US. Pat. No. 3,565,964.
Acidic alumino-silicate zeolites which can be utilized in the subject process have been described in copending application Ser. No. 590,225, filed Oct. 28, 1966, now US. Pat. No. 3,396,203 and in copending application Ser. No. 750,432, filed Aug. 2, 1968, of Ronald D. Bushick entitled Process for Producing Sym- Octahydroanthracene from Sym- Octahydrophenanthrene, and in copending application Ser. No. 581,129, filed Aug. 25, 1966, now abandoned of Francis William Kirsch, David S. Barmby and John D. Potts entitled: Process for ParaffinOlefin Alkylation" and in copending application Ser. No. 716,190, filed Mar. 26, 1968 of Francis William Kirsch, David S. Barmby and John D. Potts entitled Process for Paraffin-Olefin Alkylation and in copending application Ser. No. 715,998, filed Mar. 26, 1968 of Francis William Kirsch, David S. Barmby and John D. Potts entitled Gd Zeolite and Hydrocarbon Conversion Process with Gd Zeolite Catalyst and in copending application Ser. No. 715,994, filed Mar. 26, 1968, now US. Pat. No. 3,541,001 of Alfred E. Hirschler and in copending application Ser. No. 718,980, filed Mar. 26, 1968, now US. Pat. No. 3,534,114, of Ronald D. Bushick and in copending application Ser. No. 749,714, filed Aug. 2, 1968 of Francis William Kirsch, David S. Barmby and John D. Potts entitled Dy Zeolite and Hydrocarbon Conversion Process with Dy Zeolite Catalyst, and in copending application Ser. No. 749,739, filed Aug. 2, 1968, now US. Pat. No. 3,534,1 15, of Ronald D. Bushick entitled Combination of Dy Alumino- Silicate Catalyst and Hydrogenation Catalyst, all of these being assigned to Sun Oil Company. Other Useful aluminosilicate catalysts (including acid-leached mordenite) in the present process are found in Ser. No. 28,608, filed Apr. 15, 1970 and Ser. No. 90,463, filed Nov. 17, 1970, both of Alfred E. Hirschler. The utility of naphthenes such as perhydro-polycyclic hydrocarbons as traction fluids (or as components of a blended traction-fluid base stock) is taught in Ser. No. 33,023, filed Apr. 29, 1970 of Irl N. Duling and Frederick P. Glazier, entitled Combination of Tractive Drive and Traction Fluid Comprising Cyclic or Acyclic Compounds. Another utility of such naphthenes is found in an application filed on or about Feb. 19, 1971, entitled Lubrication of Controlled-Slip Differential, of David S. Gates, Paul E. Hagstrom and Marcus W. Haseltine, Jr. The conversion of s-hydrindacene to ashydrindacene, or the reverse conversion, is taught in Ser. No. 869,868, filed Oct. 27, 1969 Ronald D. Bushick. The disclosure of all of the above-cited applications is hereby incorporated in the present application.
BACKGROUND OF THE INVENTION In the aforementioned copending US. Pat. applications having the Ser. Nos. 590,225, 715,994, 715,998,
718,980, 749,714 and 749,739, processes are disclosed for the catalytic conversion of polycyclic aromatic hydrocarbons (e.g., s-OHP to s-OHA) comprising contacting a hydrocarbonaceous feed, in a conversion zone at an elevated temperature, with an acidic aluminosilicate catalyst for sufficient time to permit the conversion to occur. The present invention, as that of parent application Ser. No. 749,932, is an improvement on said processes, comprising (in one aspect) conducting such processes in the presence of from 55000 p.s.i. of hydrogen (preferably, 15-1500 p.s.i. of hydrogen).
SUMMARY OF THE INVENTION A hydrocarbon conversion process comprises contacting a polycyclic aromatic hydrocarbon (e.g., dicyclohexyl) in a conversion zone at an elevated conversion temperature with an acidic alumino-silicate catalyst in the presence of from 5-5000 p.s.i. of hydrogen gas and recovering an upgraded hydrocarbon conversion product (e.g., dimethyl decalins), said acidic alumino-silicate catalyst containing less than one alkali metal cation and at least one cationic monovalent, divalent or trivalent metal (e.g., Gd), metal oxide (e.g., Gd=O or Gd-O-Gd), metal hydride (e.g., GdH), metal hydroxide (e.g., Gd-OH) or mixed metal hydride hydroxide (e.g., Gd for every twelve atoms of aluminum in said alumino-silicate framework. For example, s-hydrindacene can be converted to ashydrindacene, or the reverse conversion can be made.
FURTHER DESCRIPTION OF THE INVENTION The metals (and catalysts) can be those disclosed in the aforementioned United States paten applications; however, in the preferred cations, the metal of the cations consists essentially of one or more metals from the group consisting of Al, Mg, Ca, Sr, Ba, Cr, Mn, Zn, Ag, Cd, In, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yh, Lu, Th, and U. Halide adjuvants (e.g., Serial Nos. 581,129 and 716,190 and of previously cited applications entitled Dy Zeolite and Hydrocarbon Conversion Process with Dy Zeolite Catalyst and Combination of Dy Alumino-Silicate Catalyst and Hydrogenation Catalyst) can also be present in the reaction zone.
Although a hydrogenation catalyst (e.g., see US. Pat. No. 3,396,203 and US. Pat. No. 3,534,114) can also be present in the conversion zone (as for converting s-OHP to s-OHA), we prefer that the catalyst (and reaction zone) not contain such metals (or cations of such metals) as Co, Ni, Cu, Nb, Mo, Ru, Th, Pd, W, Re, Os, Ir, or Pt.
The present invention is especially useful for converting s-I-IIN to its isomer, as-HIN, or as-HIN to its isomer, s-HIN, by process comprising contacting a feed rich in one of the said isomers with an acidic alumino-silicate catalyst in the presence of 5l500 p.s.i. of hydrogen at a temperature above 40C. but below cracking temperature, whereby isomerization of the contacted isomer to the other isomer occurs. From 1 to 20 (preferably, from 2-12) percent of water, based on the weight of the catalyst, can also be present in the contact zone (some as in the form of hydroxyl groups). Means of recovering said other isomer from the isomerization mixture are disclosed for example, in the aforementioned application Ser. No. 869,868, filed October 27, 1969. The resulting depleted isomerization mixture can be recycled and further contacted with the catalyst.
The preferred acidic alumino-silicate catalyst comprises a crystalline zeolite (and, more preferably, is at least 50% crystalline). Also preferred is an acidic alumino-silicate catalyst, wherein the atomic ratio Al/Si is from 0.65 to 0.2 and wherein (on analysis prior to said contacting) there is at least one trivalent or divalent metal, metal oxide or metal hydroxide cation for ever twelve atoms of aluminum in said alumino-silicate. Also preferred as such metals of the cation are the rare earths, especially Y, La and Gd.
In the coversion of s-OHP to s-OHA (or of s-OHA to s-OHP), one preferred catalyst is the Gd aluminosilicate described in the aforementioned United States patent applications, Ser. No. 715,994, Ser. No. 715,998 and Ser. No. 718,980. For this conversion, the preferred conditions are a temperature above 5C. (more preferably in the range of 80120C.) at a weight hourly space velocity of 0. l20 (more preferably 025-), and in the presence of 5-500 (more preferably -250) p.s.i. of hydrogen. The hydrogen partial pressure in the conversion zone is preferably from 15 to 100 percent of the total gas pressure. The process can be conducted when the hydrocarbonaceous feed is contacted in liquid, vapor or mixed phase (e.g., at reflux or in trickle phase). The hydrogen can be recycled (as at rates up to 10,000 scf/bbl of feed). If the catalyst activity appreciably decreases in time, the catalyst can be separated from the hydrocarbon reactants and regenerated, as by burning in air. After such burning, water can be added by the means disclosed in the previously cited copending applications.
ILLUSTRATIVE EXAMPLES The following examples illustrate the preparation of an acidic Gd alumino-silicate catalyst (GdHY) which can be used in the subject process and illutrate illustrate used of the GdHY catalyst in the subject process to isomerize s-OHA to s-OHP, to isomerize s-OHP to s-OHA, and to isomerize s-HIN to as-HIN or the reverse.
EXAMPLE I An NH,,Y zeolite was prepared by contacting 625 g. NaY zeolite (sorptometer surface area of 758 m /g.) for 12 exchange cycles with fresh portions of a boiling 105C.) solution of535 g. NH Cl in 1425 mls. distilled water at 100C. (i.e., a 5.5 normal solution). The fresh solution had a pH at 100C. of 4.2-4.5 (which, when necessary, was obtained by adjusting with either NH OH or HCl). Prior to contact the solution was filtered to insure that it is free of undissolved salt particles. The equilibrated NaY zeolite (in ambient air for 24 hours) had a 25.7 percent weight loss on ignition and analyzed 10.16% Na, 45.99% SiO and 16.60% A]- O On a water-free basis, the NaY contained 0.442 moles Na per 100 g. zeolite. Each ammonium exchange cycle was for a /2 hour contact period followed by adjusting the pH to 5.5 with NH OH and then filtering the hot (80-90C.) slurry (filtrate pH ranged from 4.5 to 5.2). After the 12 NH C1 exchange cycles, the zeolite was washed for 8 cycles of 15 minutes contact, and then filtered, with 1.4 liters each of distilled H O. After this washing a test with silver nitrate showed that the filtrate contained no C1-.
The washed zeolite cake was broken up and dried over night at 140C. On the next day, the dry zeolite was pulverized and screened through a 100 mesh screen. The resulting NH Y zeolite (after equilibration in ambient air for 24 hours) had a weight loss on ignition at 1,000C. (for two hours) of 29.9%, and analyzed 4.70 wt. N (0.426 moles NHf/IOO g. of waterfree NH Y zeolite). It contained less than 0.1 wt. Na (or less than 0.006 moles Na/ g. of water-free zeolite).
47.7 g. of this NH Y zeolite was then exchanged for 16 cycles each with 239 mls. of a pH 4.3 solution of 67 g. Gd(NO 5H (99.9 percent pure) in 382 liters distilled water. The 4.3 pH was obtained by adjusting the pH 2.4 Gd-nitrate solution with NH OH. At the beginning of each contact period the zeolite slurry was adjusted to pH 5.0. The filtrate pH ranged from 4.6 to 5.2. After the 16 Gd-nitrate exchange cycles, the resulting GdNH Y zeolite was washed for 8 cycles each, of 15 minutes contact, with /2 liter distilled H O (a diphenyl amine test showed that no nitrate ion was present in the filtrate from the 8th wash cycle). The GdNH Y was dried over night at C. and then put through a 100 mesh screen.
The resulting 100 mesh GdNH Y zeolite (after equilibration in ambient air) had a 24.1% weight loss on ignition (for 2 hours at 1000C.). The GdNH Y zeolite contained 0.46 wt. N (0.043 moles NHf/lOO g. water-free GdNH Y), 14.05 wt. Gd (0.116 moles Gd/100 g.) and less than 0.1% Na (less than 0.006 moles Na/l00 g.).
The 100 mesh GdNH Y was activated by heating slowly in flowing dry air in a split tube furnace to 500C., held at 500C. for 4 hours and bottled hot.
The activated GdHY zeolite had a sorptometer surface area of 757 m /g.
EXAMPLE II 10 ml. portions of feed hydrocarbon (s-OHA or s- OHP) and 4.5 g. protions of the activated GdHY catalyst of Example I, were placed in a magnetically stirred Parr bomb into which hydrogen was introduced until the pressure was 1 10 p.s.i.g. The bomb was then heated to 100C. and that temperature was maintained for a desired period of time, after which the bomb was cooled to room temperature, the pressure was reduced and a sample of the catalyst-free reaction product was taken for chromatographic analysis.
The results of a series of such runs (designed as Runs A, B, D and E, and of blank runs (Runs C and H) made with no hydrogen gas present in the bomb is summarized in the following Tables 1 and 2. In Table 1, the feed hydrocarbon was s-OHA. In Table 2, the feed hydrocarbon was s-OI-IP. Runs F and G in Table 2 are runs which are reported in the previously cited application Ser. No. 590,225, now US. Pat. No. 3,396,203, using a mixed rare earth hydrogen Y zeolite and no hydrogen pressure.
s-OHA can be separated (as by crystallization) from the reaction mixture and dehydrogenated to produce anthracene.
The subject process can also be used to convert prehnitene to durene or to convert durene to prehnitene. Similarly, pseudocumene can be converted to mesitylene. Alkyltetralins can be converted to isomeric alkyltetralins.
EXAMPLE III Example 11 is repeated except that the feed hydrocarbon is s-hydrindacene and the average temperature in the bomb is maintained at about C. The major reaction product is as-hydrindacene. The reverse reaction can also be effected at 150C. when the feed hydrocarbon consists essentially of as-hydrindacene. These reaction products, per se, as useful as heat exchange fluids, as in a nuclear reactor, or they can be hydrogenated (to at least 95 percent saturation) to produce a naphthene mixture which is useful as a traction fluid component (e.g., 10 volume percent of the hydrogenated mixture can be blended with 90 volume percent of hydrogenated polybutylene oil having a viscosity of 10 c.s. at 210F. and a bromine number of less than 5).
The conversion of the present example is illustrated by the following equilibrium:
s-"tetrahyclrobenzindane" 3 ,5,6 ,7 ,8-hexahydrolH-benz [f] ind n s -hydrindacene a s -hydrindacene 2,3,6? 8.hydro- 1H-benz [e] indene l 2 3 l-tetrahydronaphthacene 1,2,3}; ,5,6 ,7,8,-octahydronaphthacene 1,2,3, l-tetr'ahydro l ,2-ben2anthracene octahydro-l,2-
benzanthracene fail 5,6-dimethyl-l,2,3, l-tet;rahydr'oanthr'uccne a 3 V H3 6,'/-dimethyl- 2 l 3 CH3 H we NH, I
H3 H I -3 4 5 6-dimethyl-l 2 3 l-tetrahydrophenanthrene (1)6 8-dimethyl-l, 2 3 1-1;ecrahydr-ophenant,'nre1e (2)6 'I-dimethyl-l 2 3 lOtetrahydrophenanthrene (3 5 ,7 or 6 7-dimethyl-l 2 ,3 l-tetr'ahydroanzhracene TABLE 1 CONVERSION OF s-OHA TO s-OHP AT 100C.
Product Type Reaction Distribution (wt.%) Run Catalyst Time H psig Conversion OHA OHP Other A GdHY 1.5 hrs. 110 41.2 58.8 41.2 B GdHY 5 hrs. 110 41.0 59.0 41.0 C GdHY 1.5 hrs. None 44.4 55.6 44.4
TABLE 2 CONVERSION OF s-OHP to s-OHA at 100C.
Product Type Reaction Distribution (wt.%) Run Catalyst Time H psig Conversion OHA OHP Other D GdHY 1.5 hrs. 110 56.3 54.2 43.7 2.1 E GdHY 5 hrs. 110 57.2 54.5 42.8 2.7 F RdHY 1 hr. None 12.2 10.2 87.8 2.0 G RdHY 5 hrs. None 25.4 20.8 74.6 4.5 H GdHY 1.5 hrs. None 14.3 12.2 85.7 2.1
The invention claimed is:
1. Process for converting a polycyclic aromatic hydrocarbon containing at least one saturated ring to an isomer, or the conversion of said isomer to said polycyclic aromatic hydrocarbon, said process comprising contacting a feed rich in said polycyclic aromatic hydrocarbon, or rich in the said isomer with an acidic alumino-silicate catalyst in the presence of from 5-1500 p.s.i. of hydrogen at a temperature above 40C. but below cracking temperature, whereby isomerization of the contacted isomer to the other isomer occurs.
2. Process according to claim 1 wherein said polycyclic aromatic hydrocarbon or said other isomer contains at least three condensed rings.
3. Process according to claim 2 wherein said polycyclic aromatic hydrocarbon or said isomer is recovered from the reaction and mixture after recovery the resulting depleted isomerization mixture is recycled and further contacted with said catalyst.
4. Process according to claim 1 wherein said acidic alumino-silicate catalyst comprises a crystalline zeolite.
5. Process according to claim 4 wherein said contacting is effected in the presence of from 2 to 12 percent of water, based on the weight of said catalyst.
6. Process according to claim 1 wherein said catalyst has an Al/Si atomic ratio of from 0.65 to 0.2 and contains at least 1 trivalent or divalent metal, metal oxide or metal hydroxide cation for ever 12 atoms of aluminum in said alumino-silicate.
7. Process according to claim 1 wherein said contacting is in the presence of from 15-1500 p.s.i. of hydrogen.
8. Process according to claim 7 wherein said catalyst comprises a crystalline zeolite.
9. Process according to claim 8 wherein said catalyst also contains a hydrogenation catalyst.
10. Process of claim 1 wherein said polycyclic aromatic hydrocarbon has at least one condensed ring.
11. Process of claim 10 wherein said condensed ring contains at least one saturated ring member.
12. Process of claim 10 wherein said acidic aluminosilicate catalyst comprises a crystalline zeolite.
13. Process of claim 1 wherein said catalyst contains metal cations consisting essentially of one or more met- 2115 from the group consisting of aluminum, magnesium, calcium, strontium, barium, chromium, manganese, zinc, silver, cadmium, indium, tin, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium and uranium.
14. Process of claim 1 wherein a halide adjuvant is present in the reaction zone.
15. Process of claim 1 wherein a hydrogenation catalyst is also present in the conversion zone.
16. Process of claim 1 wherein no hydrogenation catalyst is present in the conversion zone.
Claims (16)
1. PROCESS FOR CONVERTING A POLYCYCLIC AROMATIC HYDROCARBON CONTAINING AT LEAST ONE SATURATED RING TO AN ISOMER, OR THE CONVERSION OF SAID ISOMER TO SAID POLYCYCLIC AROMATIC HYDROCARBON, SAID PROCESS COMPRISING CONTACTING A FEED RICH IN SAID POLYCYCLIC AROMATIC HYDROCARBON, OR RICH IN THE SAID ISOMER WITH AN ACIDIC ALUMINO-SILICATE CATALYST IN THE PRESENCE OF FROM 5-1500 P.S.I. OF HYDROGEN AT A TEMPERATURE ABOVE 40*C. BUT BELOW CRACKING TEMPERATURE, WHEREBY ISOMERIZATION OF THE CONTACTED ISOMER TO THE OTHER ISOMER OCCURS.
2. Process according to claim 1 wherein said polycyclic aromatic hydrocarbon or said other isomer contains at least three condensed rings.
3. Process according to claim 2 wherein said polycyclic aromatic hydrocarbon or said isomer is recovered from the reaction and mixture after recovery the resulting depleted isomerization mixture is recycled and further contacted with said catalyst.
4. Process according to claim 1 wherein said acidic alumino-silicate catalyst comprises a crystalline zeolite.
5. Process according to clAim 4 wherein said contacting is effected in the presence of from 2 to 12 percent of water, based on the weight of said catalyst.
6. Process according to claim 1 wherein said catalyst has an Al/Si atomic ratio of from 0.65 to 0.2 and contains at least 1 trivalent or divalent metal, metal oxide or metal hydroxide cation for ever 12 atoms of aluminum in said alumino-silicate.
7. Process according to claim 1 wherein said contacting is in the presence of from 15-1500 p.s.i. of hydrogen.
8. Process according to claim 7 wherein said catalyst comprises a crystalline zeolite.
9. Process according to claim 8 wherein said catalyst also contains a hydrogenation catalyst.
10. Process of claim 1 wherein said polycyclic aromatic hydrocarbon has at least one condensed ring.
11. Process of claim 10 wherein said condensed ring contains at least one saturated ring member.
12. Process of claim 10 wherein said acidic alumino-silicate catalyst comprises a crystalline zeolite.
13. Process of claim 1 wherein said catalyst contains metal cations consisting essentially of one or more metals from the group consisting of aluminum, magnesium, calcium, strontium, barium, chromium, manganese, zinc, silver, cadmium, indium, tin, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium and uranium.
14. Process of claim 1 wherein a halide adjuvant is present in the reaction zone.
15. Process of claim 1 wherein a hydrogenation catalyst is also present in the conversion zone.
16. Process of claim 1 wherein no hydrogenation catalyst is present in the conversion zone.
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US420988A US3884986A (en) | 1971-02-23 | 1973-12-03 | Catalytic conversion of polycyclic aromatic hydrocarbons in the presence of hydrogen |
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US11817771A | 1971-02-23 | 1971-02-23 | |
US420988A US3884986A (en) | 1971-02-23 | 1973-12-03 | Catalytic conversion of polycyclic aromatic hydrocarbons in the presence of hydrogen |
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US420988A Expired - Lifetime US3884986A (en) | 1971-02-23 | 1973-12-03 | Catalytic conversion of polycyclic aromatic hydrocarbons in the presence of hydrogen |
Country Status (1)
Country | Link |
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US (1) | US3884986A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4073818A (en) * | 1975-04-15 | 1978-02-14 | Idemitsu Kosan Co., Ltd. | Process of producing acenaphthenes |
US5523505A (en) * | 1994-08-15 | 1996-06-04 | The Penn State Research Foundation | Zeolite-catalyzed isomerization of sym-octahydrophenanthrene to sym-octahydroanthracene |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3389188A (en) * | 1966-04-21 | 1968-06-18 | Koppers Co Inc | Process for preparing anthracene from phenanthrene |
US3396203A (en) * | 1966-10-28 | 1968-08-06 | Sun Oil Co | Alumino-silicate catalyzed reactions of polycyclic aromatic hydrocarbons |
US3534115A (en) * | 1968-08-02 | 1970-10-13 | Sun Oil Co | Combination of dy alumino-silicate catalyst and hydrogenation catalyst |
US3534114A (en) * | 1968-03-26 | 1970-10-13 | Sun Oil Co | Combination of gd alumino-silicate catalyst and hydrogenation catalyst |
US3541001A (en) * | 1968-03-26 | 1970-11-17 | Sun Oil Co | Hydrocarbon conversion process with gd catalyst |
US3715406A (en) * | 1968-08-02 | 1973-02-06 | Sun Oil Co | Process for producing sym-octahydroanthracene from sym-octahydrophenanthren |
-
1973
- 1973-12-03 US US420988A patent/US3884986A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3389188A (en) * | 1966-04-21 | 1968-06-18 | Koppers Co Inc | Process for preparing anthracene from phenanthrene |
US3396203A (en) * | 1966-10-28 | 1968-08-06 | Sun Oil Co | Alumino-silicate catalyzed reactions of polycyclic aromatic hydrocarbons |
US3534114A (en) * | 1968-03-26 | 1970-10-13 | Sun Oil Co | Combination of gd alumino-silicate catalyst and hydrogenation catalyst |
US3541001A (en) * | 1968-03-26 | 1970-11-17 | Sun Oil Co | Hydrocarbon conversion process with gd catalyst |
US3534115A (en) * | 1968-08-02 | 1970-10-13 | Sun Oil Co | Combination of dy alumino-silicate catalyst and hydrogenation catalyst |
US3715406A (en) * | 1968-08-02 | 1973-02-06 | Sun Oil Co | Process for producing sym-octahydroanthracene from sym-octahydrophenanthren |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4073818A (en) * | 1975-04-15 | 1978-02-14 | Idemitsu Kosan Co., Ltd. | Process of producing acenaphthenes |
US5523505A (en) * | 1994-08-15 | 1996-06-04 | The Penn State Research Foundation | Zeolite-catalyzed isomerization of sym-octahydrophenanthrene to sym-octahydroanthracene |
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