US3336399A - Dehydrogenating hydroxy-and oxocycloaliphatic compounds - Google Patents
Dehydrogenating hydroxy-and oxocycloaliphatic compounds Download PDFInfo
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- US3336399A US3336399A US305763A US30576363A US3336399A US 3336399 A US3336399 A US 3336399A US 305763 A US305763 A US 305763A US 30576363 A US30576363 A US 30576363A US 3336399 A US3336399 A US 3336399A
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- United States
- Prior art keywords
- catalyst
- naphthalene
- tetrahydro
- naphthol
- hydroxy
- Prior art date
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- Expired - Lifetime
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- 150000001875 compounds Chemical class 0.000 title claims description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 30
- JAAJQSRLGAYGKZ-UHFFFAOYSA-N 1,2,3,4-tetrahydronaphthalen-1-ol Chemical compound C1=CC=C2C(O)CCCC2=C1 JAAJQSRLGAYGKZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 14
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- SCWNNOCLLOHZIG-UHFFFAOYSA-N 5,6,7,8-tetrahydro-1-naphthol Chemical compound C1CCCC2=C1C=CC=C2O SCWNNOCLLOHZIG-UHFFFAOYSA-N 0.000 description 1
- 101100328086 Caenorhabditis elegans cla-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KMTLFVCFTQTMDH-UHFFFAOYSA-N naphthalen-1-ol 1,2,3,4-tetrahydronaphthalen-1-ol Chemical compound C1(=CC=CC2=CC=CC=C12)O.C1(CCCC2=CC=CC=C12)O KMTLFVCFTQTMDH-UHFFFAOYSA-N 0.000 description 1
- DUTMLANVXAVXHM-UHFFFAOYSA-N naphthalen-1-ol;1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CCCCC2=C1.C1=CC=C2C(O)=CC=CC2=C1 DUTMLANVXAVXHM-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxo 1,2,3,4 tetrahydro naphthalene Chemical compound 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
Definitions
- This invention relates to a process for the manufacture of heavy phenols from corresponding oxygenated cycloaliphatic compounds and, more particularly, to the production of naphthols by the dehydrogenation of alcohols and ketones derived from more or less hydrogenated naphthalene and alpha naphthol, from 1 hydroxy- 1,2,3,4 tetrahydro-naphthalene or 1 oxo -l,2,3,4 tetra hydro-naphthalene.
- a principal object of this invention is the provision of a method for dehydrogen-ating hydroxyand oxo-cycloaliphatic compounds and, more particularly, from l-hydroxy 1,2,3,4 tetrahydro naphthalene or 1 oxol,2,3,4 tetrahydro naphthalene of the corresponding naphthols with a high rate of transformation, practically free from tetrahydronaphthol.
- the single figure is a schematic diagram of apparatus for performing the process of the invention.
- the invention consists in the discovery of special catalysts to be used in the dehydrogenation of oxygenated cycloaliphatic compounds for the purpose of obtaining the corresponding heavy phenols. It has been discovered that, in "order for the dehydrogenation of the aliphatic ring to take place selectively, the catalytic mass 3,336,399 Patented Aug. 15, 1967 The new process consists, in the first place, of subjecting oxygenated cycloaliphatic compounds in the liquid state to heating in the presence of a dehydrogenation catalyst made up of one or more finely divided catalytic metals deposited on an oxide support of a basic or entirely neutral character and not containing any composition of an acid character in the free state.
- Catalytic metals which can be used as part of the catalyst of the invention may be one or more of the metals selected from the group consisting of nickel, copper, iron, cobalt, chromium, platinum, or other metals of the platinum group, such as iridium, palladium, and rhodium.
- Carriers which can be used with the catalyst include the basic oxides, particularly those of metals of Groups I and II of the Periodic Table, especially calcium oxide, magnesium oxide, copper oxide, strontium oxide, barium oxide, and zirconium oxide. Some oxides, such as silica, may be used, but only in a perfectly neutral form, such as kieselguhr, which does not contain any acid foci.
- Catalysts may be prepared in accordance with the invention by using 20 to parts by Weight of the finely divided catalytic metal per 100 parts of carrier.
- the catalytic metal makes up 50 to 100 parts per each 100 parts by weight of carrier.
- a preparation of these catalysts can be carried out in the usual manner. For instance, a mixture of a desired metal oxide with a selected support powder may take place by co-precipitation, by tabletting, or by granulation and reduction in hydrogen, preferably at a temperature equal to or in the vicinty of that at which the catalyst is to be used.
- the dehydrogenation take place at temperatures which are in the vicinity of the boiling point of the reaction liquid. It is particularly advantageous to work under boiling conditions at atmospheric pressure -or at any pressure from 1 to 5 atmospheres.
- the oxygenated cycloaliphatic compound which is to be treated is l oxo 1,2,3,4 tetrahydro naphthalene
- the best temperature to use for ob taining alpha-naphthol is in the range from 200 C. to 350 C.
- the velocity of the reaction and the rate of conversion increases with the temperature and the results are particularly favorable at the boiling point of the reaction mixture, which lies between 256 C. and 290 C. at atmospheric pressure. If the process is carried out at a slightly higher pressure in the range from absolute pressures from 1 to 3 kilograms per centimeter square, the
- favorable temperature range would be in the range from 305 C. to 340 C.
- the temperature at which dehydrogenation should take place is about 240 C.
- the process of the invention being preferably carried out in a paI- ticular manner; that is to say, by carrying out the reaction in two stages; (1) heating the mixture to boiling under reduced pressure with a contact time in the catalytic space, which is short (just long enough to convert virtually all of the 1 hydroxy 1,-2,3,4 tetrahydro naphthalene to 1 oxo 1,2,3,4 tetrahydro naphthalene, and (2) treatment at a higher temperature as indicated above in relation to 1 oxo 1,2,3,4 tetrahydro naphthalene.
- the first stage can advantageously be carried out at a pressure of 400 to 760 millimeters Hg which corresponds to boiling temperatures of about 225 C. to 250 C.
- the efiiciency of the process is increased by a vigorous agitation of the liquid while in contact with the catalyst. In the case of a fixed bed catalyst this agitation is obtained by a very rapid passage of liquid to be treated through the bed.
- Another means is by the bubbling of an inert gas (for example, nitrogen) through the liquid in contact with the catalyst. This bubbling should take place at regulated rates within certain limits, particularly 150 to 200 times the volume of the catalytic space per hour.
- the process of the invention can be carried out in two different ways: With a fixed catalytic bed, or with catalyst particles in suspension in the reaction medium.
- a fixed catalytic bed or with catalyst particles in suspension in the reaction medium.
- the catalyst be in the form of granules or particles of a size from 0.5 to 10 millimeters and, preferably, in the range from 2 to millimeters.
- the linear rates of flow for the reaction liquid through the catalytic bed are preferably from 4 to 100 meters per hour, and, preferably, from to 40 meters per hour, calculated for the theoretically empty apparatus.
- the preferred dimensions of the catalytic granules are less than that used in a fixed bed. They can be in the range from 0.1 to 5 millimeters, but preferably are in the range from 0.1 to 1 millimeter.
- the suspension can contain 10 to 40 parts by weight of the latter per 100 parts of liquid. However, the preferred proportions are from to parts per 100.
- This process can be carried out continuously or discontinuously. In the former case, it is recommended that several reactors be employed in series in order to take into account the rapid decrease in the rate of conversion as a function of time, which is characteristic of the reaction in question.
- the novel process can be carried out by use of various types of apparatus which allow operation with a fixed bed catalyst or a suspended catalyst.
- the apparatus is provided with a flask 11 which serves for the intermediate storage of liquid obtained by a dehydrogenation which takes place in a reactor 14 of the starting material obtained from a reservoir 15.
- a supply pump 16 causes the liquid to pass from the reservoir 15 into the bed of catalyst in the reactor 14.
- the bed receives the treated liquid from the flask 11 by way of a circulation pump 12.
- the liquid passes through a preheater 13 and arrives at a catalytic bed at the desired temperature, for instance, 250 C.
- the reactor 14 is provided with a heater 28 which permits the catalyst bed in the reactor 14 to be preheated.
- the reactor is provided with an enlargement 25 provided with an overflow pipe 26 which leads back to the flask 11.
- the top of the enlargement 25 is provided with a column 17 through which the vapors evolved by the reaction pass and, eventually, reach a condenser 18.
- a separator 20 is provided at the bottom of the condenser 18 in which water recovered separates out and is removed through the pipe 21. The hydrogen escapes through a vent 19 at the top of the separator.
- the decanted liquid from the separator 20 returns to the flask 11 through a pipe 22.
- a vent 24 at the top of the flask 11 is provided with a cooler for avoiding the escape of naphtholic vapors into the atmosphere.
- Withdrawal of the finished product is made by way of a takeoff valve 23 and a valve 27 regulates the flow of liquid from the pump 16 to the reactor 14.
- the reaction can also be carried out with a single passage of the reaction mixture through a tubular apparatus of sufficient length but which is divided into several sections for eliminating the hydrogen produced in each section. However, in order to achieve high rates of flow of liquid, in accordance with the invention, it is generally more advantageous to recirculate the reaction mass in a closed circuit through the catalyst in order to obtain the desired rate of conversion.
- the apparatus shown in the drawing is particularly suitable for this type of operation.
- a predetermined volume of the primary material is withdrawn from the reservoir 15 and the pump 16 forces it into the reactor 14.
- the valve 27 is then closed and operation takes place using the circulation pump 12.
- the liquid circulates around the various circuits, while the hydrogen formed in the reactor 14 is released through the pipe 19.
- the flask 11 contains the desired naphthol (or other heavy phenol) content
- the material is withdrawn through the valve 23 and a new charge of starting material from the reservoir 15 is introduced into the apparatus.
- A represents a catalyst prepared in the following manner:
- cupric oxide CuO
- ZnO zinc oxide
- Two kinds of particles were prepared in this manner: (1) Tablets in the form of cylinders which are 3 millimeters long and 3 millimeters in diameter, and (2) Granules of selected sizes from 0.2 to 0.5 millimeter; 0.5 to 1 millimeter; 1 to 2 millimeters; and 2 to 5 millimeters; formed by grinding and screening the tablets.
- the catalyst is reduced in hydrogen between C. and 275 C. to effect complete transformation of the CuO into finely divided metallic copper.
- the catalyst designated B in certain of the following examples is made up of metal deposited on kieselguhr, in the well-known manner.
- the catalyst contains 50% by weight of nickel and includes no acid foci.
- Kieselguhr is a mineral of completely neutral SiO
- This catalyst was made in two forms similar to those in catalyst A, that is to say, (1) cylindrical pastilles of 5 x 5 millimeters, and (2) four series of granules of pre-determined size in the range from 0.2 to 0.5 millimeter; 0.5 to 1 millimeter; 1 to 2 millimeters; and 2 to 5 millimeters; after reduction of the nickel oxide to metallic nickel is was superficially re-oxidized in order to stabilize the catalyst.
- Example I In an apparatus of the kind shown in the accompanying drawing, the reactor 14 had an internal diameter of T8 square centimeters and was filled with 1,000 grams of catalyst A in rods 3 millimeters long and 3 millimeters in diameter and preheated by means of the heater 28 to 250 C. 1700 grams of tetralone were preheated to 250 C. in the flask 11 and then circulated at the rate of 7.5 litres per hour, namely, at a linear velocity of 10 meters per hour through the catalyst bed. The composition of the mixture obtained as a function of time is given in Table I.
- Example II The operation proceeded in the same manner as Example I, but at temperatures of 230 C. and 200 C., re-
- Example IV and withdrawal were carried on cont1nuously at the rate
- 1,000 grams of catalyst B was introduced, as described in Example II, in the form of rods of 5 millimeters diameter and 5 millimeters long.
- the operation proceeded with 2,000 grams of 'tetralone at 250 C. with circulation at the rate of 10 meters per hour.
- Table II The results are tabulated in Table II below.
- Example V The operation took place exactly as in Example IV but at boiling temperature, namely 258 to 280 C.
- Example VI The operation took place exactly as in Example V but the linear velocity of the liquid over the catalyst was increased to 24 meters per hour. The results are shown in Table II.
- Example IX The process took place in the same manner as in Example VI using 1,000 grams of catalyst B. The mixture was at its boiling point but the charge was made up of 2,000 grams of mixture of 76% l-oxo-l,2,3,4-tetrahydronaphthalene and 24% 1 hydroxy-1,2,3,4 tetrahydronaphthalene. After one-half hour the rate of conversion was 100% for l-hydroxy-1,2,3,4-tetrahydro-naphthalene and 45% for l-oxo-l,2,3,4-tetrahydro-naphthalene. The mixture obtained contained 44% of alpha-naphthol.
- Example X Two forms of apparatus analogous to those in the drawing were mounted in series. The first was charged with 1,000 grams of catalyst A and an absolute pressure of 600 mm. Hg was maintained. The second was charged with 1,000 grams of catalyst B at atmospheric pressure. The assembly was supplied continuously with a mixture containing 62% 1-oxo-1,2,3,4 tetrahydro-naphthalene, and 38% 1-hydroxy-1,2,3,4 tetrahydro-naphthalene at the rate of 2,000 grams per hour. The two units were maintained at the boiling point of the liquid mixture.
- the yield in utilizable products with respect to the l-oxo- 1,2,3,4-tetrahydro-naphthalene varied between 97% and 92.5% in accordance with the duration of the reaction.
- Example X genation catalyst constituted by at least one divided metal selected from the groups consisting of nickel, copper, 01161115011 Was analogous to Example XIII but at the iron, cobalt, chromium, platinum, iridium, palladium, and boiling Point, namely Q and with rhodium, deposited on an inert carrier, the improvement chanical agitation using 250 grams of catalyst A in g which consists in heating a feed material consisting of ules of 1 to 2 mm.
- Example XVIII 3 A process in accordance with claim 1, wherein the The Operation was carried out in the same manner as catalyst is nickel and the carrier completely neutral sili- Example XVI but replacing the 1-oXo-1,2,3,4-tetrahydro- 2 naphthalene with a mixture of 24% 1-hydroxy-1,2,3,4- d process .reclted 1n.cla1.m.1wherem saldcatilyst tetrahydro-naphthalene and 76% 1-oXo-1,2,3,4 tetrag on i d W.” 15 m the form of parades hydro-naphthalene.
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Abstract
Alpha-naphthol is obtained by dehydrogenating alpha-tetralol and/or -tetralene in presence of a catalyst comprising finely-divided Ni, Cu, Cr, Fe, Co, Pt, Ir, Pd or Rh deposited on an oxide which contains no acid foci, e.g. kieselguhr, CaO, MgO, CuO, SrO, BaO or ZnO.
Description
Aug. 15,1967 7 RIQG'AC E'II'AL 3,336,399
DEHYDROGENATING HYDROXY-AND OXC-CYQLOALIPHATIC COMPOUNDS Filed Aug. 30, 1963 ROBERT GAC LOUIS ZEPPIERI INVENTORS.
United States Patent 3,336,399 DEHYDROGENATING HYDROXY- AND 0X0- CYCLOALIPHATIC COMPOUNDS Robert Gac, Caluire, and Louis Zeppieri, Oullius, France, assignors to Progil, Paris, France, a corporation of France Filed Aug. 30, 1963, Ser. No. 305,763 Claims priority, application France, Aug. 30, 1962,
4 Claims. ((51. 260621) This invention relates to a process for the manufacture of heavy phenols from corresponding oxygenated cycloaliphatic compounds and, more particularly, to the production of naphthols by the dehydrogenation of alcohols and ketones derived from more or less hydrogenated naphthalene and alpha naphthol, from 1 hydroxy- 1,2,3,4 tetrahydro-naphthalene or 1 oxo -l,2,3,4 tetra hydro-naphthalene.
In the past, various methods have been proposed for the preparation of heavy phenols by the dehydrogenation of the corresponding cycloaliphatic compounds. None of these methods has given complete satisfaction because, for instance, these known methods result in a low rate of transformation and in poor yields. Furthermore, the known processes generally give rise to the formation of considerable quantities of secondary products. For instance, when a catalytic metal is employed in a very active form, such as fresh Raney nickel or platinum sponge, for the dehydrogenation of l-hydroxyor l-oxo- 1,2,3,4 tetrahydro naphthalene, there occurs a simultaneous formation of 5,6,7,8 tetrahydro naphthol 1, which is very diflicult to separate later on from the alphan-aphthol. If the conventional dehydrogenation catalysts (made up of metal oxides) are used, the speed of dehydrogenation is too low and this permits a side reaction to take place to an excessive degree. The same disadvantage is found when using catalysts formed by the deposit of finely divided metal on carriers generally employed for catalytic members, particularly active carbon, clays, and oxides of elements of Groups III to VIII of the Periodic Table, particularly A1 0 TiO SiO and Cr O all compositions containing such oxides. These and other ditficulties experienced with the prior art have been obviated in a novel manner by the present invention.
A principal object of this invention is the provision of a method for dehydrogen-ating hydroxyand oxo-cycloaliphatic compounds and, more particularly, from l-hydroxy 1,2,3,4 tetrahydro naphthalene or 1 oxol,2,3,4 tetrahydro naphthalene of the corresponding naphthols with a high rate of transformation, practically free from tetrahydronaphthol.
With the foregoing and other objects in View, which will appear as the description proceeds, the invention resides in the combination and arrangement of steps and in the details of procedure hereafter described and claimed, it being understood that changes in the precise embodiment of the invention herein disclosed may be made within the scope of what is claimed without departing from the spirit of the invention. The character of the invention, however, may be best understood by reference to one apparatus for carrying out the method, as illustrated by the accompanying drawing, in which:
The single figure is a schematic diagram of apparatus for performing the process of the invention.
In general, the invention consists in the discovery of special catalysts to be used in the dehydrogenation of oxygenated cycloaliphatic compounds for the purpose of obtaining the corresponding heavy phenols. It has been discovered that, in "order for the dehydrogenation of the aliphatic ring to take place selectively, the catalytic mass 3,336,399 Patented Aug. 15, 1967 The new process consists, in the first place, of subjecting oxygenated cycloaliphatic compounds in the liquid state to heating in the presence of a dehydrogenation catalyst made up of one or more finely divided catalytic metals deposited on an oxide support of a basic or entirely neutral character and not containing any composition of an acid character in the free state. Catalytic metals which can be used as part of the catalyst of the invention may be one or more of the metals selected from the group consisting of nickel, copper, iron, cobalt, chromium, platinum, or other metals of the platinum group, such as iridium, palladium, and rhodium. Carriers which can be used with the catalyst include the basic oxides, particularly those of metals of Groups I and II of the Periodic Table, especially calcium oxide, magnesium oxide, copper oxide, strontium oxide, barium oxide, and zirconium oxide. Some oxides, such as silica, may be used, but only in a perfectly neutral form, such as kieselguhr, which does not contain any acid foci.
Catalysts may be prepared in accordance with the invention by using 20 to parts by Weight of the finely divided catalytic metal per 100 parts of carrier. In the preferred embodiment, the catalytic metal makes up 50 to 100 parts per each 100 parts by weight of carrier. A preparation of these catalysts can be carried out in the usual manner. For instance, a mixture of a desired metal oxide with a selected support powder may take place by co-precipitation, by tabletting, or by granulation and reduction in hydrogen, preferably at a temperature equal to or in the vicinty of that at which the catalyst is to be used.
Another important feature of the invention is that the dehydrogenation take place at temperatures which are in the vicinity of the boiling point of the reaction liquid. It is particularly advantageous to work under boiling conditions at atmospheric pressure -or at any pressure from 1 to 5 atmospheres. When the oxygenated cycloaliphatic compound which is to be treated is l oxo 1,2,3,4 tetrahydro naphthalene, the best temperature to use for ob taining alpha-naphthol is in the range from 200 C. to 350 C. The velocity of the reaction and the rate of conversion increases with the temperature and the results are particularly favorable at the boiling point of the reaction mixture, which lies between 256 C. and 290 C. at atmospheric pressure. If the process is carried out at a slightly higher pressure in the range from absolute pressures from 1 to 3 kilograms per centimeter square, the
favorable temperature range would be in the range from 305 C. to 340 C.
In the particular case where the cycloaliphatic compound to be dehydrogenated is 1 hydroxy 1,2,3,4- tetrahydro naphthalene, the temperature at which dehydrogenation should take place is about 240 C., the process of the invention being preferably carried out in a paI- ticular manner; that is to say, by carrying out the reaction in two stages; (1) heating the mixture to boiling under reduced pressure with a contact time in the catalytic space, which is short (just long enough to convert virtually all of the 1 hydroxy 1,-2,3,4 tetrahydro naphthalene to 1 oxo 1,2,3,4 tetrahydro naphthalene, and (2) treatment at a higher temperature as indicated above in relation to 1 oxo 1,2,3,4 tetrahydro naphthalene. It will be understood that this particular embodiment of the invention is applicable not to 1 hydroxy 1,2,3,4 tetrahydro naphthalene only, but also to starting mixtures which contain greater or lesser amounts of this compound. The first stage can advantageously be carried out at a pressure of 400 to 760 millimeters Hg which corresponds to boiling temperatures of about 225 C. to 250 C. The efiiciency of the process is increased by a vigorous agitation of the liquid while in contact with the catalyst. In the case of a fixed bed catalyst this agitation is obtained by a very rapid passage of liquid to be treated through the bed. Another means is by the bubbling of an inert gas (for example, nitrogen) through the liquid in contact with the catalyst. This bubbling should take place at regulated rates within certain limits, particularly 150 to 200 times the volume of the catalytic space per hour.
The process of the invention can be carried out in two different ways: With a fixed catalytic bed, or with catalyst particles in suspension in the reaction medium. When liquids containing principally 1 oxo 1,2,3,4 tetrahydronaphthalene or 1 hydroxy 1,2,3,4 tetra-hydro naphthalene are dehydrogenated to naphthol by passage through a fixed catalytic bed, it is recommended that the catalyst be in the form of granules or particles of a size from 0.5 to 10 millimeters and, preferably, in the range from 2 to millimeters. Larger dimensions lead to a poor utilization of the catalyst, while smaller dimensions increase the loss of charge and risk the formation of gummy residues involving agglomeration of the granules. The linear rates of flow for the reaction liquid through the catalytic bed are preferably from 4 to 100 meters per hour, and, preferably, from to 40 meters per hour, calculated for the theoretically empty apparatus. When the process employs the catalyst in suspension in the reaction liquid, the preferred dimensions of the catalytic granules are less than that used in a fixed bed. They can be in the range from 0.1 to 5 millimeters, but preferably are in the range from 0.1 to 1 millimeter. In fact, below 0.1 millimeter in size separation of the catalyst from the treated liquid after the reaction can be difficult, while granules which are greater than 1 millimeter size are not readily maintained in suspension and lead to a slow rate of dehydrogenation. According to the nature of the liquid and of the catalyst, the suspension can contain 10 to 40 parts by weight of the latter per 100 parts of liquid. However, the preferred proportions are from to parts per 100.
This process can be carried out continuously or discontinuously. In the former case, it is recommended that several reactors be employed in series in order to take into account the rapid decrease in the rate of conversion as a function of time, which is characteristic of the reaction in question. The novel process can be carried out by use of various types of apparatus which allow operation with a fixed bed catalyst or a suspended catalyst.
Referring -now to the accompanying drawing, it can be seen that the apparatus is provided with a flask 11 which serves for the intermediate storage of liquid obtained by a dehydrogenation which takes place in a reactor 14 of the starting material obtained from a reservoir 15. A supply pump 16 causes the liquid to pass from the reservoir 15 into the bed of catalyst in the reactor 14. At the same time, the bed receives the treated liquid from the flask 11 by way of a circulation pump 12. The liquid passes through a preheater 13 and arrives at a catalytic bed at the desired temperature, for instance, 250 C. The reactor 14 is provided with a heater 28 which permits the catalyst bed in the reactor 14 to be preheated. At its upper part, the reactor is provided with an enlargement 25 provided with an overflow pipe 26 which leads back to the flask 11. The top of the enlargement 25 is provided with a column 17 through which the vapors evolved by the reaction pass and, eventually, reach a condenser 18. At the bottom of the condenser 18 a separator 20 is provided in which water recovered separates out and is removed through the pipe 21. The hydrogen escapes through a vent 19 at the top of the separator.
The decanted liquid from the separator 20 returns to the flask 11 through a pipe 22. A vent 24 at the top of the flask 11 is provided with a cooler for avoiding the escape of naphtholic vapors into the atmosphere. Withdrawal of the finished product is made by way of a takeoff valve 23 and a valve 27 regulates the flow of liquid from the pump 16 to the reactor 14. The reaction can also be carried out with a single passage of the reaction mixture through a tubular apparatus of sufficient length but which is divided into several sections for eliminating the hydrogen produced in each section. However, in order to achieve high rates of flow of liquid, in accordance with the invention, it is generally more advantageous to recirculate the reaction mass in a closed circuit through the catalyst in order to obtain the desired rate of conversion. The apparatus shown in the drawing is particularly suitable for this type of operation. A predetermined volume of the primary material is withdrawn from the reservoir 15 and the pump 16 forces it into the reactor 14. The valve 27 is then closed and operation takes place using the circulation pump 12. The liquid circulates around the various circuits, while the hydrogen formed in the reactor 14 is released through the pipe 19. When the flask 11 contains the desired naphthol (or other heavy phenol) content, the material is withdrawn through the valve 23 and a new charge of starting material from the reservoir 15 is introduced into the apparatus.
In the examples which follow, two types of catalysts are used, indicated by the letters A and B.
CATALYST A In the examples, A represents a catalyst prepared in the following manner:
1 part by weight of cupric oxide (CuO) was mixed with 2 parts by weight of zinc oxide (ZnO) and made into tablets in the usual manner. Two kinds of particles were prepared in this manner: (1) Tablets in the form of cylinders which are 3 millimeters long and 3 millimeters in diameter, and (2) Granules of selected sizes from 0.2 to 0.5 millimeter; 0.5 to 1 millimeter; 1 to 2 millimeters; and 2 to 5 millimeters; formed by grinding and screening the tablets. In both cases, the catalyst is reduced in hydrogen between C. and 275 C. to effect complete transformation of the CuO into finely divided metallic copper.
CATALYST B The catalyst designated B in certain of the following examples is made up of metal deposited on kieselguhr, in the well-known manner. The catalyst contains 50% by weight of nickel and includes no acid foci. Kieselguhr is a mineral of completely neutral SiO This catalyst was made in two forms similar to those in catalyst A, that is to say, (1) cylindrical pastilles of 5 x 5 millimeters, and (2) four series of granules of pre-determined size in the range from 0.2 to 0.5 millimeter; 0.5 to 1 millimeter; 1 to 2 millimeters; and 2 to 5 millimeters; after reduction of the nickel oxide to metallic nickel is was superficially re-oxidized in order to stabilize the catalyst.
Example I In an apparatus of the kind shown in the accompanying drawing, the reactor 14 had an internal diameter of T8 square centimeters and was filled with 1,000 grams of catalyst A in rods 3 millimeters long and 3 millimeters in diameter and preheated by means of the heater 28 to 250 C. 1700 grams of tetralone were preheated to 250 C. in the flask 11 and then circulated at the rate of 7.5 litres per hour, namely, at a linear velocity of 10 meters per hour through the catalyst bed. The composition of the mixture obtained as a function of time is given in Table I.
Examples II and III The operation proceeded in the same manner as Example I, but at temperatures of 230 C. and 200 C., re-
spectively. The results are also given in Table I.
6 Example VIII TABLE I Composition Product (percent by weight) 1 Temp. Time Example C.) (hours) By-products Alpha- Tetrahydronaphthol naphthol Light Heavy 2 34. 6 0. 1 6 3. 0 3 40. 0 0. l 8 3. 9 4 41. 2 0. 1 9 5. 2 6 41. 9 0. 1 13 7. 3 2 230 1 20. 4 0 9 9. 4 2 28. 4 0 15. 0 12. 7 3 30. 2 0. 1 15. 5 13. 4 4 36. 0 0. 1 15. 5 13. 6 6 38. 5 0. 1 16. 0 14. 7 3 200 1 ll. 6 0 2 13. 6 0 3 15. 1 0 6 19. 3 0 10 22. 1 0
Example IV and withdrawal were carried on cont1nuously at the rate In the same apparatus as that shown in the drawings, 1,000 grams of catalyst B was introduced, as described in Example II, in the form of rods of 5 millimeters diameter and 5 millimeters long. The operation proceeded with 2,000 grams of 'tetralone at 250 C. with circulation at the rate of 10 meters per hour. The results are tabulated in Table II below.
Example V The operation took place exactly as in Example IV but at boiling temperature, namely 258 to 280 C. The
results are shown in Table II.
Example VI The operation took place exactly as in Example V but the linear velocity of the liquid over the catalyst was increased to 24 meters per hour. The results are shown in Table II.
Exam ple VII of 1,700 gallons per hour. The composition of the mixture withdrawn was stabilized at 28.2% alpha-naphthol, 8% light ends and 5% heavy ends.
Example IX The process took place in the same manner as in Example VI using 1,000 grams of catalyst B. The mixture was at its boiling point but the charge was made up of 2,000 grams of mixture of 76% l-oxo-l,2,3,4-tetrahydronaphthalene and 24% 1 hydroxy-1,2,3,4 tetrahydronaphthalene. After one-half hour the rate of conversion was 100% for l-hydroxy-1,2,3,4-tetrahydro-naphthalene and 45% for l-oxo-l,2,3,4-tetrahydro-naphthalene. The mixture obtained contained 44% of alpha-naphthol.
Example X Two forms of apparatus analogous to those in the drawing were mounted in series. The first was charged with 1,000 grams of catalyst A and an absolute pressure of 600 mm. Hg was maintained. The second was charged with 1,000 grams of catalyst B at atmospheric pressure. The assembly was supplied continuously with a mixture containing 62% 1-oxo-1,2,3,4 tetrahydro-naphthalene, and 38% 1-hydroxy-1,2,3,4 tetrahydro-naphthalene at the rate of 2,000 grams per hour. The two units were maintained at the boiling point of the liquid mixture. At the outlet from the first unit a mixture containing 11.5% of alpha-naphthol, 6.2% light ends, 3.7% heavy ends, and only 0.3% of l-hydroxy-1,2,3,4 tetrahydro- TABLE II Composition of Product; (percent by weight) Temp. Time Example 0.) (hours) By-products Alpha- Tetrahydronaphthol alpha-naphthol Light Heavy naphthalene. At the outlet of the second reactor, the final mixture contained 57.2% alpha-naphthol, 11.5% recoverable light ends (l,2,3,4 tetrahydro-naphthalene), 6.7% of tar, and 1.4% of tetrahydro-naphthol.
the yield in utilizable products with respect to the l-oxo- 1,2,3,4-tetrahydro-naphthalene varied between 97% and 92.5% in accordance with the duration of the reaction.
While it will be apparent that the illustrated embodi E l XI ments of our invention herein disclosed are well calcummp e lated to adequately fulfill the objects and advantages pri- In a reactor provided with mechanical stirrer and a marily stated, it is to be understood that the invention is reflux condenser serving as a hydrogen outlet, 1,000 grams susceptible to variation, modification and change within of 1-oxo-1,2,3,4-tetrahydro-naphthalene were introduced the spirit and scope of the sub-joined claims. at 250 C. and 250 grams of catalyst A in granules of The invention having been thus described, what is 0.5 to 1 mm., were added. After five hours of reaction, claimed as new and desired to secure by Letters Patent the rate of conversion was 70.1% and the wield of alphai naphthol was 73% with respect to the 1 oXo-1,2, 1. In a process for the manufacture of alpha-naphthol tetrahydro-naphthalene consumed. Also, the major part by dehydrogenation of at least one of the compounds of the by-products were recoverable and constituted by l-hydroxy 1,2,3,4 tetrahydro-naphthalene and l-oxonaphthalene and tetraline. 1,2,3,4-tetrahydro-naphthalene, with a metallic dehydro- Example X genation catalyst constituted by at least one divided metal selected from the groups consisting of nickel, copper, 01161115011 Was analogous to Example XIII but at the iron, cobalt, chromium, platinum, iridium, palladium, and boiling Point, namely Q and with rhodium, deposited on an inert carrier, the improvement chanical agitation using 250 grams of catalyst A in g which consists in heating a feed material consisting of ules of 1 to 2 mm. After five hours the rate of conversion at l t one f id compounds in the liquid state, in the WaS 835% and the yield of alpha-naphthol Was presence of said catalyst, said inert carrier being a metal- Example XIII lic oxide selected from the group consisting of basic Th d t th metallic oxides and neutral metallic oxides, containing E e process was (fame m e m manner as no compound of acidic character in the free state said xample XII but with catalyst A used in granules of h b t t b t C d 350 0.2 to 0.5 mm. After five hours the conversion rate was ea mg i a a tempera ure 8 ween an 865% andtheyieldOfalpha naphthO1-/8 5% C.; removing the hydrogen formed as a result of said heating and separately recovering the alpha-naphthol pro- Examples XIV through XVII duced by Said heating The process wa arried out i the same manner as 2. A process as recited in claim 1, wherein said carrier Examples XII and XIII but with 250 grams of catalyst is selected from the class consisting of MgO, CaO, CuO, B. Table III shows the results obtained. ZnO, SrO, and BaO.
TABLE III Ex. Catalyst B Time 0.5 hour 1 hour 1.5 hours 2 hours Dimensions oi granules; 14-. 5mm Conversion.-. 54.3 73.8 Yield 77. 5 76. 1 15 1-2mm Conversion... 60 79.3 84.3 Yield 70.5 73.5 16- 0.2-0.5 mm 80.9 35. a
Example XVIII 3. A process in accordance with claim 1, wherein the The Operation was carried out in the same manner as catalyst is nickel and the carrier completely neutral sili- Example XVI but replacing the 1-oXo-1,2,3,4-tetrahydro- 2 naphthalene with a mixture of 24% 1-hydroxy-1,2,3,4- d process .reclted 1n.cla1.m.1wherem saldcatilyst tetrahydro-naphthalene and 76% 1-oXo-1,2,3,4 tetrag on i d W." 15 m the form of parades hydro-naphthalene. After two hours of reaction, the rate an 15 Suspende m the hquld compounds to be dehydro' of conversion reached 100% for 1-hydroxy-1,2,3,4-tetragenated' hydro-naphthalene and 69% for 1-oXo-1,2,3,4-tetrahydro- References cued naphthalene and the yield of alpha-naphthol was 67%. UNITED STATES TENTS The total yield of the usable product was 21.5%. 2,321 551 6/1943 Loder Table III 'gIVFS the rates of conversion in yields of 2,503,641 4 1950 Taylor et alpha-naphthol in percent by weight with respect to the 1-oxo-1,2,3,4 tetrahydro-naphthalene consumed. Also, the greater part of the by-products was recoverable and LEON ZITVER, Primary Examiner.
D. M. HELPER, H. ROBERTS, Assistant Examiners.
Claims (1)
1. IN A PROCESS FOR THE MANUFACTURE OF ALPHA-NAPHTHOL BY DEHYDROGENATION OF AT LEAST ONE OF THE COMPOUNDS 1-HYDROXY - 1,2,3,4 - TETRAHYDRO-NAPHTHALENE AND 1-OXO1,2,3,4-TETRAHYDRO-NAPHTHALENE, WITH A MATELLIC DEHYDROGENATIONCATALYST CONSTITUTED BY AT LEAST ONE DIVIDED METAL SELECTED FROM THE GROUPS CONSISTING OF NICKEL, COPPER, IRON, COBALT, CHROMIUM, PLATINUM, IRIDIUM, PALLADIUM, AND RHODIUM, DEPOSITED ON AN INERT CARRIER, THE IMPROVEMENT WHICH CONSISTS IN HEATING A FEED MATERIAL CONSISTING OF AT LEAST ONE OF SAID COMPOUNDS IN THE LIQUID STATE, IN THE PRESENCE OF SAID CATALYST, SAID INERT CARRIER BEING A METALLIC OXIDE SELECTED FROM THE GROUP CONSISTING OF BASIC METALLIC OXIDES AND NEUTRAL METALLIC OXIDES, CONTAINING NO COMPOUND OF ACIDIC CHARACTER IN THE FREE STATE SAID HEATING BEING AT A TEMPERATURE BETWEEN 200*C. AND 350* C.; REMOVING THE HYDROGEN FORMED AS A RESULT OF SAID HEATING AND SEPARATELY RECOVERING THE ALPHA-NAPHTHOL PRODUCED BY SAID HEATING.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FR908203A FR1344298A (en) | 1962-08-30 | 1962-08-30 | Manufacture of heavy phenols |
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US3336399A true US3336399A (en) | 1967-08-15 |
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US305763A Expired - Lifetime US3336399A (en) | 1962-08-30 | 1963-08-30 | Dehydrogenating hydroxy-and oxocycloaliphatic compounds |
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US (1) | US3336399A (en) |
DE (1) | DE1518091A1 (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3514492A (en) * | 1967-01-04 | 1970-05-26 | Inst Francais Du Petrole | Dehydrogenation catalyst and a process for dehydrogenating cyclic alcohols and ketones |
US3534110A (en) * | 1965-12-08 | 1970-10-13 | Inst Francais Du Petrole | Production of phenol by the catalytic dehydrogenation of cyclohexanol and/or cyclohexanone |
US20070281203A1 (en) * | 2006-05-30 | 2007-12-06 | Toda Kogyo Corporation | Catalyst for removing metal carbonyl, process for producing mixed reformed gas containing hydrogen, process for removing metal carbonyl, and fuel cells system |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE2501770A1 (en) * | 1975-01-17 | 1976-07-22 | Hoechst Ag | PROCESS FOR THE PREPARATION OF 2-HYDROXYNAPHTHALINES |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2321551A (en) * | 1941-07-17 | 1943-06-08 | Du Pont | Catalytic dehydrogenation and hydrogenation |
US2503641A (en) * | 1947-04-09 | 1950-04-11 | Ici Ltd | Dehydrogenation of organic compounds |
-
1962
- 1962-08-30 FR FR908203A patent/FR1344298A/en not_active Expired
-
1963
- 1963-08-22 GB GB33326/63A patent/GB1038147A/en not_active Expired
- 1963-08-29 DE DE19631518091 patent/DE1518091A1/en active Pending
- 1963-08-30 US US305763A patent/US3336399A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2321551A (en) * | 1941-07-17 | 1943-06-08 | Du Pont | Catalytic dehydrogenation and hydrogenation |
US2503641A (en) * | 1947-04-09 | 1950-04-11 | Ici Ltd | Dehydrogenation of organic compounds |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3534110A (en) * | 1965-12-08 | 1970-10-13 | Inst Francais Du Petrole | Production of phenol by the catalytic dehydrogenation of cyclohexanol and/or cyclohexanone |
US3514492A (en) * | 1967-01-04 | 1970-05-26 | Inst Francais Du Petrole | Dehydrogenation catalyst and a process for dehydrogenating cyclic alcohols and ketones |
US20070281203A1 (en) * | 2006-05-30 | 2007-12-06 | Toda Kogyo Corporation | Catalyst for removing metal carbonyl, process for producing mixed reformed gas containing hydrogen, process for removing metal carbonyl, and fuel cells system |
Also Published As
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DE1518091A1 (en) | 1969-12-18 |
FR1344298A (en) | 1963-11-29 |
GB1038147A (en) | 1966-08-10 |
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