GB1563044A - Production of cyclohexanone - Google Patents
Production of cyclohexanone Download PDFInfo
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- GB1563044A GB1563044A GB43143/77A GB4314377A GB1563044A GB 1563044 A GB1563044 A GB 1563044A GB 43143/77 A GB43143/77 A GB 43143/77A GB 4314377 A GB4314377 A GB 4314377A GB 1563044 A GB1563044 A GB 1563044A
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- United Kingdom
- Prior art keywords
- catalyst
- palladium
- phenol
- cyclohexanone
- sodium
- Prior art date
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 115
- 239000003054 catalyst Substances 0.000 claims description 86
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 50
- 229910052763 palladium Inorganic materials 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000011065 in-situ storage Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JLYNSPSTPQAEAX-UHFFFAOYSA-N 4-cyclohexylcyclohexan-1-one Chemical compound C1CC(=O)CCC1C1CCCCC1 JLYNSPSTPQAEAX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 CveloZIexanosle Chemical compound 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J23/44—Palladium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(54) PRODUCTION OF CYCLOHEXANONE
(71) We, ALLIED CHEMICAL CORPORATION, a corporation organized and existing under the laws of the State of New Jersey, United States of America, of Columbia
Road, and Park Avenue, Morris Township, Morris County, New Jersey 07960, United
States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
In summary, this invention is a method for promoting the selective hydrogenation of phenol to cyclohexanone in the presence of an improved palladium-on-carbon catalyst which comprises effecting the hydrogenation reaction in the presence of an in situ promoter preferably from the group consisting of sodium hydroxide. sodium carbonate. and sodium phenate. The characteristic properties of the palladium-on-carbon catalyst used in this process are significantly different from commercially available catalyst. and the present invention involves apparent interaction of the ill situ promoter with the present unique catalyst. Respecting safety of operation, it is important that the present process and catalyst permit hydrogenation of phenol in the liquid phase utilizing at least 2, preferably 3 to 8, reactors in series with each reactor maintained at or below the atmospheric boiling point of the reaction mixture in the reactor.
This invention relates to the hydrogenation of phenol and, more particularly, to the promotion of the hydrogenation of phenol to cyclohexanone in the presence of a promoted palladium catalyst.
In the hydrogenation of phenol employing a palladium catalyst. the activity of the catalyst, and hence the rate of hydrogenation. decreases with continued use of the catalyst due to impurities present in the hydrogenation reaction mixture which poison the catalyst.
While processes, such as those disclosed in U. S. Patents 3.692.845 and 3.187.050, have been developed to purify organic compounds such as phenol to be hvdrogenated, the poisoning of metallic catalysts has not been entirely eliminated in large scale commercial processes due to long-term accumulation of impurities. such as those impurities which are introduced with the phenol and the hydrogen gas. and those impurities which are produced during the processing.
To avoid the economicallv prohibitive alternatives of discarding poisoned catalyst or continuing to use the poisoned catalyst at a reduced rate of hydrogenation, it is desirable to promote the rate of hydrogenation. thereby overcoming the disadvantages of continued use of such poisoned palladium catalysts. The hydrogenation of phenol to cyclohexanone has been promoted by the use of "promoted palladium-on-carbon catalysts." i.e., catalysts which have been treated prior to their addition to the hydrogenation reaction mixture, to incorporate on the catalysts a material which enhances their activity. Thus. in U.S. Patent 3,076,810, cyclohexanone is produced by hydrogenating phenol using a sodium-promoted catalyst. i.e.. a palladium catalyst which has been modified prior to its introduction to the reaction mixture, to incorporate sodium thereon. Alkaline reacting agents in limited amounts are also disclosed as being added to assist in promotion when the sodium promoted catalysts of that reference are employed. However, such catalyst systems have not been entirely satisfactory, and research has continued to develop an improved process and/or catalyst.
Surprisingly, the present invention provides significantly improved catalyst selectivity and activity in the hydrogenation of phenol to cyclohexanone; moreover it is applicable to present commercial plants. Further, the present invention provides an improved process that will produce less by-products and can be operated at a lower temperature than present commercial plants without sacrificing production rate. Obviously, reaction at relatively low temperature is highly desirable as a factor increasing safety of the overall operation.
In accordance with the present invention, we provide a process for producing cyclohexanone comprising hydrogenating phenol by passing hydrogen in contact with phenol in the presence of a palladium catalyst, preferably promoted by sodium in an amount of at least 1000 ppm, based on the weight of the catalyst. at a temperature of 135"C to 185 C., preferably 145"C. to 185"C.. said catalyst being further characterized in that it is composed of palladium coated carbon particles. said carbon particles having diameters of 3 to 300 microns and a surface area of 100 to 2000 m2/gram, said phenol containing a small amount of an it situ promoter selected from alkali metal hydroxides, carbonates. phenates.
bicarbonates and nitrates, said amount being 10 to 300 ppm, preferably 11 to 150 ppm. in terms of alkali metal of said promoter.
Although in U. S. Patent 3,076,810, it was said that higher concentrations. i.e., more than 10 ppm, of an alkaline reacting compound in the phenol favored the formation of cyclohexanol, we have found that in the presence of our improved palladium-on-carbon catalyst, not only is the reaction rate enhanced but also the production of cvclohexanol is reduced by operating within the range of 10 to 300 ppm of alkali metal in the phenol. The reason for this surprising discovery is not known with certainty. but it is believed that the unexpected element of the present invention involves the apparent interaction of the in sint promoter with the present unique catalyst, together with careful control of the reaction temperature as specified hereinabove.
The palladium catalysts useful in the present invention contain palladium. in either its elemental or combined form. as a catalytically active metal. Preferably. 30 to 75 percent of the total palladium is present as elemental palladium. i.e.. as palladium zero. The palladium is desirable absorbed or coated on the surface of a support consisting of carbon particles, said carbon particles having diameters of 3 to 300 microns and a surface area of 100 to 2000 m2/gram. It is preferred that the catalyst have about 95 to 9 weight percent of the particles between 4 and 150 microns in diameter. While the amount of palladium incorporated on the selected support may vary widely. the catalyst preferably contains from about 0.1 to 50 weight percent palladium. and most preferably from about 0.2 to lo weight percent. A satisfactory and readily prepared catalyst contains 1 to 5 weight percent palladium on charcoal. In addition, the palladium catalysts useful in the present invention may contain catalytically active metals in addition to palladium. Such additional catalytically active metals which may be employed are those selected from elements of the platinum series. Exemplary of platinum series elements which may be employed are ruthenium. rhodium. osmium, iridium. platinum and mixtures thereof.
The preferred promoters of the present invention are members selected from sodium hydroxide. sodium carbonate, sodium phenate. and mixtures thereof. Particularly preferred as promoters in the present invention are sodium hydroxide and sodium phenate.
with sodium phenate being especiallv preferred. The selected promoter may be added to the hydrogenation reaction mixture as a phenol slurrv containing up to about 25 weight percent, and peferably from about 1 to 1() weight percent. of the selected promotor.
Alternatively, the promoter may be added to the hydrogenation reaction mixture as an aqueous solution.
The phenol which may be emploved in the present invention may be obtained from conventional sources. such as the oxidation of cumene to form cumene hvdroperoxide and the decomposition of the resulting hydroperoxide. However. the phenol treated in accordance with the process of the present invention will generally contain no more than about 100 ppm sulfur impurities. and preferably not greater than about 10 ppm sulfur impurities containing divalent sulfur. not greater than about 20 ppm sulfur impurities containing tetravalent sulfur and not greater than about HO ppm. and most preferably not greater than about 40 ppm. sulfur impurities containing hexavalent sulfur.
The phenol also preferably contains not greater than 2 ppm. and most preferably not greater than 1 ppm. iron values (calculated as elemental iron): and preferably not greater than 100 ppm. and most preferably not greatel than 5() ppm. acetol (i.e.. hydroxy-2propanone).
The phenol hydrogenated in accordance with the process of the present invention may also contain a wide variety of other impurities. these impurities incude. for example.
halogen compounds and deleterious nitrogen compounds, i.e., nltrogen-containing compounds which inhibit the hydrogenation of phenol to cyclohexanone employing palladium catalysts. Typical deleterious nitrogen compounds includes aromatic amines, ammonium salts, polyamines and tertiary and primary amines. Preferably, the phenol contains less than 10 ppm halogen and less than 50 ppm of nitrogen as deleterious nitrogen compounds. Continuous or batch techniques can be used in this improved process for hydrogenating phenol to cyclohexanone, the equipment used being that which is usual in such processes.
The selected promoter may be introduced to the hydrogenation reaction mixture either prior to hydrogenation or during hydrogenation. Thus, the conditions of temperature under which the promoter may be added to the hydrogenation mixture are not critical and may vary widely. For example, the temperature at which the promoter is added to the hydrogenation reaction mixture may vary from about 25"C. to about 185"C. and the pressure may vary from about atmospheric to 30() psig. While an improved rate of hydrogenation is generally observed immediately upon addition to the hydrogenation reaction mixture of a promoter of the present invention. even more improved results may be obtained where the hydrogenation reaction mixture is maintained at a temperature within the range of about 135"C. to 185"C. and a pressure of 80-200 psig. for a period of 15 to 30 minutes after addition thereto of the selected promoter.
The selected in situ promoter may be added to the hydrogenation reaction mixture and the reaction product may be withdrawn from the hydrogenation vessel either continuously or batchwise. Upon withdrawal of the hydrogenation product from the reaction vessel, the palladium catalyst may be recovered from the product stream and returned to the vessel for hydrogenation of additional phenol. The recovery of the catalyst from the product stream may be effected by any standard solids separation procedure e.g. centrifugation and vacuum filtering.
Vessels which may be employed during the hydrogenation are conventional. and include the typical hydrogenation apparatus such as. for example. the apparatus described in U. S.
Patent 3,076,810.
The present invention is further illustrated by reference to the following examples wherein parts and percentages are by weight unless otherwise indicated. The improved catalyst and the improved rates of hydrogenation achieved by the process of the present invention are especially significant in view of the large tonnages of palladium catalysts used annually by industry in the hydrogenation of phenol to cvclohexanone. Furthermore, the in situ promoters of the present invention have been unexpectedly found to promote the hydrogenation of phenol to cyclohexanone while appreciably decreasing the amount of cyclohexanol produced by the further hydrogenation of the desired cvclohexanone hydrogenation product. Thus. recovery of cyclohexanone from the hvdrogenation product stream, as by distillation. is not further complicated by the formation ol substantial amounts of undesired products. i.e.. cyclohexanol.
Example 1
Part A: About 1000 parts of phenol containing less than l ppm of soluble iron. less than 2 ppm of sulfur, less than 5 ppm of halogen. less than -CO ppm of nitrogen as deleterious nitrogen compounds and 0.23 parts of sodium carbonate is mixed with l() parts of sodium-promoted. palladium-on-carbon catalyst having a sodium content of 0.32 percent, said catalyst being further characterized in that it is composed of about (1.93 percent palladium coated on carbon particles having diameters of about 4 to 15() microns and a surface area of 500 to 1500 m-/gram. The mixture is heated in a reaction vessel under nitrogen to 1600C.. then agitated at that temperature while hydrogen is admitted through a diffuser located near the bottom of the vessel and at a rate sufficient to maintain a pressure of 80 psig. Periodically, the reaction mixture is sampled and analyzed. Results are tabulated in Table 1.
TABLE 1
Hydrogenation Cyclohexanol, Cyclohexanone, Phenol,
Time, Minutes Percent Percent Percent
62 0 38.5 61.5
90 0 53.8 46.2 120 0.5 65.6 33.8 150 0.6 74.9 24.4 180 0.8 82.3 16.9 210 1.1 87.5 11.4
Less than 0.1 percent of cyclohexyl-cyclohexanone is found in the reaction mixture. At the end of the experiment, the catalyst is recovered and is found to contain 0.93 percent palladium (60% to 75% of total as elemental palladium) and 0.76 percent sodium.
Part B: The procedure of Part A is repeated with the exception that no sodium carbonate is added to the phenol. The results are tabulated in Table 2.
TABLE 2
Hydrogenation Cyclohexanol, CveloZIexanosle, Phenol, Time, Minutes Percent Percent Percent 60 O.3 'X,1 71.6 120 0.6 48.4 50.9 210 . 1.4 65.9 32.5 300 2.2 77.4 0.1 390 3.2 84.3 1.1 450 3.9 88.6 7.0
In addition, about 0.47 percent of cyclohexyl-cyclohexanone is found in the reaction mixture at the end of the experiment.
By comparison of Part A and Part B. it is clear that while in the prior art the in situ addition of an alkali metal promoter above a level of lt) ppm based on phenol caused loss of selectively. the catalyst of the present invention continued to improve in selectivitv with addition of sodium carbonate to the phenol at 93() ppm. which corresponds to 100 ppm of sodium. The unexpected element of the present invention lies in the apparent interaction of the promotor with the present unique catalyst in combination with the relatively low reaction temperature.
Example 2
The procedure of Example 1. Part A. is repeated with the exception that 10() ppm of sodium in the form of sodium hvdroxide is added to the reaction mixture in place of the sodium carbonate. Results obtained are similar to thse obtained in Example 1. Part A.
Example 3
The procedure of Example 1. Part A. is repeated with the exception that 100 ppm of sodium in the form of sodium phenate is added to the reaction mixture in place of the sodium carbonate. Results obtained are similar to those obtained in Example 1. Part A.
Example 4
This example demonstrates one effective method of preparing the catalyst of the present invention. However. the method of this example is relatively expensive as compared with the procedure of Example 5.
About 150 parts of a commercially available 5 percent palladium-on-carbon catalyst is used as starting material. A slurry of the commercially available palladium catalyst in an aqueous solution of sodium hydroxide is prepared and the slurry is then evaporated to dryness in accordance with the procedure of U. S. Patent 3,076,810. The resulting catalyst preferably contains 2,500-10,000 ppm of sodium. About 150 parts of the sodium-promoted.
palladium-on-carbon catalyst is thoroughly mixed with 1850 parts of cyclohexanone and this mixture is passed at the rate of 2000 parts per hour through a continuous centrifuge which operates at 3800 revolutions per minute. In accordance with this procedure, part of the catalyst consisting of the finer particles passes out of the centrifuge with the cyclohexanone.
The catalyst collected in the centrifuge has a size distribution of 98 to 99 percent greater than 4 microns, with substantially all particles in the range 4 to 150 microns; the palladium content is 0.6 to 1.2 percent, and the sodium content is 0.25 to 0.40 percent. This catalyst is suitable for use in the process of this invention. The finer catalyst particles may be recovered from the cyclohexanone by conventional procedures; the finer catalyst particles are unsuitable for use in the process of this invention.
Example 5
About 150 parts of commercially available charcoal catalyst support having particle size distribution of 30 percent less than 1() microns, 67 percent in the range 10 to 100 microns, and 3 percent greater than 100 microns is thoroughly mixed with 1850 parts of cyclohexanone, and this mixture is passed through a continuous centrifuge which operates at 3800 revolutions per minute. By this procedure, part of the charcoal particles consisting of the finer particles, passes out of the centrifuge with the cyclohexanone. The charcoal particles collected in the centrifuge, after drying, consist of about 100 parts of particles having diameters of 10 to 100 microns and a surface area of about 1000 m2/gram. To 100 parts of the resulting charcoal is added 1000 parts of aqueous palladium chloride solution containing 5 parts palladium and 3 parts hydrochloric acid. The solution is gradually neutralized with a sodium carbonate solution up to pH = 1.5. The mixture is stirred and then filtered. The solids are dried at l()()0C. for 8 hours following which they are impregnated with 80 parts of a solution containing 5 parts of sodium carbonate. After drying at 100"C-120"C. the solids are placed into a cylindrical reactor which is flushed with hydrogen at 140"C. This catalyst is suitable for use in the present invention.
Example 6
This example demonstrates the feasibility of continuously operating the hydrogenation process of the present invention. The phenol used was similar to that used in Example 1.
The first of a series of five agitated hydrogenation vessels is charged with 45.694 parts per hour of phenol, 1.3 to 2.0 parts of sodium carbonate. and 1.200 parts per hour of a sodium-promoted, palladium-on-carbon catalyst having a sodium content of 0.25 - 0.40 percent, said catalyst containing about 0.93 percent palladium on carbon particles having diameters of about 5 to 150 microns and a surface area of about 100() m-/gram. About 67 percent of the palladium on the catalyst is present as elemental palladium. Each hydrogenation vessel is connected in series so that the reaction mixture flows through the five vessels in about 3.1 hours. the hydrogen being charged to the first vessel. The pressure is between 80 and 200 psig. The temperature in each vessel is as follows 179"C. in the first vessel; 168"C. in the second vessel; 166"C. in the third vessel: 164"C. in the fourth vessel, and 162"C. in the fifth vessel. It is noteworthy for reasons of safety that the temperature in each vessel is less than 10 C. above the atmospheric boiling point of the reaction mixture present in the vessel. About 24.570 parts per hour of distillate. primarily cyclohexanone, is separated from the last three vessels; this distillate is rectified to provide substantially pure cyclohexanone. The reaction mass flowing from the fifth reaction vessel is fed to a continuous centrifuge. wherein the catalyst is separated from the crude cyclohexanone; the catalyst is recycled in the process. The crude cvclohexanone is rectified to recover substantially pure cyclohexanone which may be combined with the cyclohexanone recovered as described above.
In this continuous operation carried out for several davs. cyclohexanone recovery is 42,856 parts per hour. Also recovered is 684 parts per hour of cyclohexanol. 1481 parts per hour of phenol. and 211 parts per hour of higher boiling by-products. Only 3 parts per hour of make-up catalyst is required in the process. Similar results are obtained when an equivalent amount of sodium as sodium hydroxide or sodium phenate is substituted for the sodium carbonate added to the process in the phenol.
Example 7
The procedure of Example 6 is followed except that the reaction temperature in each of the reaction vessels is further reduced for reasons of increased safety. i.e.. the reaction temperature is reduced to 1730C. in the first vessel, 166"C. in the second vessel, 162"C. in the third vessel, 159"C. in the fourth vessel, and 156"C. in the fifth vessel. Regarding safety in operation, it is important that the temperature in each reactor is maintained at or below the atmospheric boiling point of the reaction mixture present in the reactor. The phenol is fed to the first vessel at a rate of 45,550 parts per hour, together with 2 parts per hour of sodium carbonate and 1,200 parts per hour of a sodium-promoted palladium-on-carbon catalyst having a sodium content of about 0.35 percent, said catalyst containing about 0.9 percent palladium on carbon particles having diameters of about 3 to 32 microns and a surface area of about 1000 m-/gram. A commercially available sodium-promoted palladium-on-carbon catalyst containing abut 1 percent sodium and about 5 percent palladium is added to the recycled catalyst as make-up catalyst at the rate of about 2,5 parts per hour. The make-up catalyst contains about 16.5 volume percent of particles finer than 3 microns in diameter, but most of these finer particles are removed from the process in the crude cyclohexanone recovered in the centrifuge. A sample of the make-up catalyst has the following size analysis.
Size Range Percent of
Microns Total Volume
1.26 to 1.59 1.5
1.59 to 2.00 2.0
2.00 to 2.52 4.0
2.52 to 3.17 9.0
3.17 to 4.00 11.5 4.0(l to 5.04 13.5
5.04 to 6.35 12.5
6.35 to 8.00 14.0
8.00 to 10.08 13.0 10.08 to 12.7 10.0 12.7 to 16.0 5.0 16.0 to 10.2 5 20.2 to 25.4 1.0 25.4 to 32.0 0.5
In this example. average yield of cyclohexanone over a one month test period is 98 percent of theory based on phenol fed to the process. Cyclohexanol is produced at a verv low rate of about 610 parts per hour. At the end of the test period. the recycling catalyst contains about 0.45 percent sodium and about 0.9 percent palladium. A sample of the recycling catalyst has the following size analysis.
Size Range Percent of
Microns Total Volume
1.26 to 1.59 0.5
1.59 to 2.00 0.5
2.00 to 2.52 0.5
2.52 to 3.17 0.5
3.17 to 4.00 1.5
4.00 to 5.04 11.0
5.04 to 6.35 24.0
6.35 to 8.00 23.5
8.00 to 10.08 16.5 10.08 to 12.7 10.0 12.7 to 16.0 6.0 16.0 to 10.2 3.5 20.2 to 25.4 1.5 25.4 to 32.0 0.5 It will be noted that the make-up catalyst shows a fairly normal distribution in size range while the recycling catalyst shows a shift toward larger particles and a skewed distribution.
We postulate that said shift toward larger catalyst particles in combination with the in situ promoter tend to promote rapid and selective hydrogenation of the phenol to cyclohexanone, i.e.. produces high yields of cyclohexanone and low yields of cyclohexanol and other by-products.
WHAT WE CLAIM IS: 1. A process for producing cyclohexanone comprising hydrogenating phenol by contacting hydrogen with phenol at a temperature of 135"C to 185"C in the presence of a palladium catalyst, composed of palladium-coated carbon particles. which have diameters of 3 to 300 microns and a surface area of 100 to 2000 m-/gram. said phenol containing an in situ promoter selected from alkali metal hydroxides. carbonates. phenates, bicarbonates and nitrates, in an amount from 10 to 3()0 ppm. calculated as alkali metal of said in situ promoter.
2. The process of Claim 1 wherein the palladium is coated on carbon particles having diameters of 4 to 150 microns and a surface area of 500 to 1500 m- gram.
3. The process of Claim l or 2 wherein 3() to 75 percent of the palladium catalyst is elemental palladium.
4. A process according to Claim 1 for producing cyclohexanone comprising passing hydrogen in contact with phenol in the presence of a palladium catalyst promoted by sodium in an amount of 2500 to l(J.()()0 ppm. based on the weight of the catalyst, at a temperature of 145"C to 185"C. said catalyst being composed of palladium-coated carbon particles. said carbon particles having diameters of 4 to 150 microns and a surface area of 500 to 1500 m2/gram. said phenol containing a small amount of an in sint promotor selected from sodium hydroxide, sodium carbonate. and sodium phenMe. said small amount being
11 to 150 ppm. in terms of sodium of said in sint promoter.
5. A process according to Claim l for producing cyclohexanone with a palladium
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (6)
1.59 to 2.00 0.5
2.00 to 2.52 0.5
2.52 to 3.17 0.5
3.17 to 4.00 1.5
4.00 to 5.04 11.0
5.04 to 6.35 24.0
6. Cyclohexanone when produced by a process according to any preceding Claim.
6.35 to 8.00 23.5
8.00 to 10.08 16.5 10.08 to 12.7 10.0 12.7 to 16.0 6.0 16.0 to 10.2 3.5 20.2 to 25.4 1.5 25.4 to 32.0 0.5 It will be noted that the make-up catalyst shows a fairly normal distribution in size range while the recycling catalyst shows a shift toward larger particles and a skewed distribution.
We postulate that said shift toward larger catalyst particles in combination with the in situ promoter tend to promote rapid and selective hydrogenation of the phenol to cyclohexanone, i.e.. produces high yields of cyclohexanone and low yields of cyclohexanol and other by-products.
WHAT WE CLAIM IS: 1. A process for producing cyclohexanone comprising hydrogenating phenol by contacting hydrogen with phenol at a temperature of 135"C to 185"C in the presence of a palladium catalyst, composed of palladium-coated carbon particles. which have diameters of 3 to 300 microns and a surface area of 100 to 2000 m-/gram. said phenol containing an in situ promoter selected from alkali metal hydroxides. carbonates. phenates, bicarbonates and nitrates, in an amount from 10 to 3()0 ppm. calculated as alkali metal of said in situ promoter.
2. The process of Claim 1 wherein the palladium is coated on carbon particles having diameters of 4 to 150 microns and a surface area of 500 to 1500 m-ígram.
3. The process of Claim l or 2 wherein 3() to 75 percent of the palladium catalyst is elemental palladium.
4. A process according to Claim 1 for producing cyclohexanone comprising passing hydrogen in contact with phenol in the presence of a palladium catalyst promoted by sodium in an amount of 2500 to l(J.()()0 ppm. based on the weight of the catalyst, at a temperature of 145"C to 185"C. said catalyst being composed of palladium-coated carbon particles. said carbon particles having diameters of 4 to 150 microns and a surface area of 500 to 1500 m2/gram. said phenol containing a small amount of an in sint promotor selected from sodium hydroxide, sodium carbonate. and sodium phenMe. said small amount being
11 to 150 ppm. in terms of sodium of said in sint promoter.
5. A process according to Claim l for producing cyclohexanone with a palladium
catalyst and with an alkali metal promoter therefor, substantially as herein described.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US74453876A | 1976-11-24 | 1976-11-24 | |
US81539777A | 1977-07-13 | 1977-07-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1563044A true GB1563044A (en) | 1980-03-19 |
Family
ID=27114327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB43143/77A Expired GB1563044A (en) | 1976-11-24 | 1977-10-17 | Production of cyclohexanone |
Country Status (6)
Country | Link |
---|---|
CA (1) | CA1109855A (en) |
DE (1) | DE2752291A1 (en) |
FR (1) | FR2372136A1 (en) |
GB (1) | GB1563044A (en) |
IT (1) | IT1143838B (en) |
NL (1) | NL7712893A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5886232A (en) * | 1995-03-06 | 1999-03-23 | Bayer Aktiengesellschaft | Process for preparing substituted cyclohexanones |
US6015927A (en) * | 1997-06-30 | 2000-01-18 | Bayer Aktiengesellschaft | Process for preparing cyclohexanones by hydrogenation of the corresponding phenols (II) |
US6046365A (en) * | 1997-06-30 | 2000-04-04 | Bayer Aktiengesellschaft | Process for preparing cyclohexanones by hydrogenation of the corresponding phenols (I.) |
US9481625B2 (en) | 2013-04-05 | 2016-11-01 | Mitsui Chemicals, Inc. | Process for producing cyclohexanone compound |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI66019C (en) * | 1977-12-19 | 1984-08-10 | Unilever Nv | FOERFARANDE FOER SELEKTIV HYDRERING AV TRIGLYCERIDOLJA |
JPS5681305A (en) * | 1979-12-06 | 1981-07-03 | Nippon Zeon Co Ltd | Hydrogenation of conjugated diene type polymer |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3076810A (en) * | 1960-06-15 | 1963-02-05 | Allied Chem | Process for the production of cyclohexanone |
FR1292101A (en) * | 1961-06-13 | 1962-04-27 | Allied Chem | Production of cyclohexanone by catalytic hydrogenation of phenol |
GB1316820A (en) * | 1970-06-05 | 1973-05-16 | Ljubarsky G D Stretlets M M | Method of producing cyclohexanone |
GB1332211A (en) * | 1971-02-05 | 1973-10-03 | Leuna Werke Veb | Process for the production of cyclohexanone by catalytic hydro genation of phenol |
-
1977
- 1977-09-16 CA CA286,935A patent/CA1109855A/en not_active Expired
- 1977-10-17 GB GB43143/77A patent/GB1563044A/en not_active Expired
- 1977-10-17 IT IT69315/77A patent/IT1143838B/en active
- 1977-11-23 DE DE19772752291 patent/DE2752291A1/en not_active Withdrawn
- 1977-11-23 NL NL7712893A patent/NL7712893A/en not_active Application Discontinuation
- 1977-11-23 FR FR7735268A patent/FR2372136A1/en active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5886232A (en) * | 1995-03-06 | 1999-03-23 | Bayer Aktiengesellschaft | Process for preparing substituted cyclohexanones |
US6015927A (en) * | 1997-06-30 | 2000-01-18 | Bayer Aktiengesellschaft | Process for preparing cyclohexanones by hydrogenation of the corresponding phenols (II) |
US6046365A (en) * | 1997-06-30 | 2000-04-04 | Bayer Aktiengesellschaft | Process for preparing cyclohexanones by hydrogenation of the corresponding phenols (I.) |
US9481625B2 (en) | 2013-04-05 | 2016-11-01 | Mitsui Chemicals, Inc. | Process for producing cyclohexanone compound |
Also Published As
Publication number | Publication date |
---|---|
FR2372136A1 (en) | 1978-06-23 |
NL7712893A (en) | 1978-05-26 |
FR2372136B1 (en) | 1981-06-26 |
IT1143838B (en) | 1986-10-22 |
DE2752291A1 (en) | 1978-06-01 |
CA1109855A (en) | 1981-09-29 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |