CA1098888A - Production of phenols and catalyst therefor - Google Patents
Production of phenols and catalyst thereforInfo
- Publication number
- CA1098888A CA1098888A CA311,277A CA311277A CA1098888A CA 1098888 A CA1098888 A CA 1098888A CA 311277 A CA311277 A CA 311277A CA 1098888 A CA1098888 A CA 1098888A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- alkali metal
- zirconium
- oxidation
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 150000002989 phenols Chemical class 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000012808 vapor phase Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 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 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims 1
- 150000001559 benzoic acids Chemical class 0.000 claims 1
- 229930003836 cresol Natural products 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic carboxylic acids Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Abstract of the Disclosure A catalyst comprised of oxidized copper, zirconium and an alkali metal is employed for oxidizing an aromatic carboxylic acid to the corresponding phenol; e. g., benzoic acid to phenol.
Description
~G~9~3~ 5t8 This invention relates to the production of phenols, and more particularly to the oxidation of aromatic carboxylic acids to phenols and catalyst therefor.
In U.S. Patent Nos. 2,727,026 and 2,852,567, there are described proeesses for producing phenols from aromatic carboxylic acids whieh employ a catalyst including copper oxide. The present invention is directed to an improved pro-cess and catalyst for oxidizing an aromatie carboxylic acid to a phenol.
In accordance with one aspect of the present invention there is provided a catalyst of oxidized copper, zirconium and an alkali metal.
In aceordance with another aspect of the present invention, there is provided an improved catalytic process for oxidizing an aromatic carboxylie acid having at least one carboxyl yroup substituted on the aromatic nucleus to the corresponding phenol in which the catalyst is comprised of oxidized copper, zireonium and an alkali metal. The alkali metal is preferably sodium, potassium or lithium.
The catalyst is referred to as being oxidized copper, zirconium and an alkali metal, and such catalyst con-tains such metals and oxygen. The metals may be present as a mixture of the oxides of copper, zireonium and an alkali metal or as a complex thereof, and sueh terminology encompas-ses such mixtures and complexes~
More particularly, the catalyst of the oxidized copper, zirconium and an alkali metal can be employed in the absenee or presence of a suitable support material. Thus, for example, the catalyst may be in the form of pellets, extrudates, etc. or supported on a support material, having a surface area of no greater than 50 m2/g; preferably a-alumina.
T he catalyst includes the three components in an amount effective to eatalyze the oxidation of an aromatic carboxylic ~ 9~8~
contains the three components in a Cu/Zr/alkali metal atomic ratio in the range of 1/o.05 to 1/0.1 to 5, with the preferred range of 1/0.2 to 0.5/0.5 to 2.5.
The catalyst may be prepared by a variety of pro~
cedures known iII the art. Thus, for example, the catalyst can be supported on a suitable support by an impregnation or spray drying technique. ~lternatively, the three catalyst components can be produced in the form o~ pellets, extrudates, etc. In preparing a supported catalyst by impregnation, for example, water soluble salts of zirconium and copper, such as nitrates, are dissolved in water and the solution employed to impregnate a suitable support, such as alpha-alumina.
The impregnatedisupport is dried and calcined to oxidi~e the copper and zirconium. The xesulting catalyst is then treated with an aqueous solution of an alkali metal salt, e.g., the hydroxide, followed by drying and calcination to effect oxidation.
In accordance with another aspect of the present invention, the hereinabove described catalyst of oxidized copper, zirconium and an alkali metal is employed as the catalyst in the oxidation of an aromatic carboxylic acid to the corresponding phenol. The aromatic carboxylic acid has at least one carboxyl group substituent on the aromatic nucleus, which is generally a benzene or naphthalene nucleus. The aromatic nucleus may al~o include more than one carboxyl substituent group or may include other substituent groups, such as alkyl, halo, etc. Carboxyl group precursors, i.e., nitrile and amide, may be employed instead of a carboxyl group. The preferred starting materials are the mono carboxylic acids of benzene and alkyl benzenes.
The oxidation is effected with molecular oxygen which can be provided as such or in admixture with other gases; e.g., as air. The oxygen is employed in at least stoichiometric pro-portions; however, lesser or greater amounts could be emploved.
In yeneral, oxygen is employed in an amount to provide an oxy~en to carboxyl groups mole ratio of from about 0.2:1 to 10:1, and prefera~ly from 0.5:1 to 5:1.
The reaction is generally effected in the vapor phase in the presence of steam as a diluent. ~he steam also functions to minimize the production of esters that result from the reaction of the carboxylic acid and the product phenol.
The steam is generally provided in an amount corresponding to a steam/carboxyl group mole ration of 5:1 to 500:1 and prefer-ably 10 1 to 100:1.
The oxidation is effected at temperatures of from about 200 to 400c, and preferably from 250 to 350C. The oxidation is generally effected at pressures above atmospheric pressure, with the pressure generally being from about 2 to 20 atmospheres.
The catalytic oxidation can be readily effected by ~ the use of any one of a wide variety of vapor-solid contact systems, e.g., employing the catalyst as a fixed or fluidized bed or in a transfer line type of contact system. The above means for e~fecting the reaction and others should he apparent to those skilled in the art from the present teachings.
The invention will be further described with respect to the following examples:
EXAMPLE I
Production of Ca*alyst _ 12.0 ~ (0.05 mol) Cu (NO3)2~ 3H2O and 18.0 g (0.025 mol) Zr~ (NO3)~. 5 H2O were dissolved in 30 g of water and heated to 70-80C. The solution was used to impregnate 100 g of a low surfa~e area alpha-alumina (Carborundum* SA~T 99, 4-8 mesh). The wet catalyst was dried and calcined at 750C for two hours, during which time the nitrates decomposed to their corresponding oxides. This catalyst (lOO g) was treated with resultin~ catalyst was dried and calcined at 500 C for approx-imately 16 hours. The finished catalyst had the following composition (wt.~): 4.0% CuO, 3.0% ZrO2, 3.6% K2O remainder alumina.
The activity and selectivity of the catalyst in Example I for producing phenol from benzoic acid were measured in a ~ixed bed reactor. The reactor was a ]acketed 1' x 1"
dia. 316 stainless steel tube. Boiling Dowtherm* was used in 110 the jacket ~or temperature control. The feed was prepared by metering water through a heater at reactor pressure, passing the steam so produced through a benzoic acid saturator main-tained at a temperature reguired to yive the desired benzoic acid/water ratio, and then mixing this stream with the desired 115 amount o~ air. The reactor contained 60 g of catalyst.
Operating conditions and r_sul~s are given in Table I.
.
I
~9~88~
~ ~ ~ ,_ d~( ~ . . I
~1 ~ r~ U~ ~ I
o ~ X
~o ~: r~
a N r~ o O
~C
a ,~ O
t~ o o o O o o U~ ~
~ ..
,01 ~o ~ r~ ~D
P u~
t~
~.
`~, cn ~ ~
n~ o o o cn ~1 ~ ~ o o 1 h ~ ~ ~I
h tD Int~l O ~ O
~i .,1 D~ .~
E3 ~1 0 o a~ :~ ~ I~
O
~ E~
: . _ U I
a~
.
o o S~
~' P;
U~ ~ O
~ O
a) tn ~1 o LO
O ~1 _, . . _ . . _ .
~ ,_1 0 ~ l l l 3~g88~
The present invention is particularly advantageous in that it provides for improved selectivity. In addition, it provides a more economic method for converting aromatic carbox-120 ylic acids to phenols. This advantage derives from:1. Lower cost reactor system (vapor phase reactor vs.
liquid phase molten salt reactor).
In U.S. Patent Nos. 2,727,026 and 2,852,567, there are described proeesses for producing phenols from aromatic carboxylic acids whieh employ a catalyst including copper oxide. The present invention is directed to an improved pro-cess and catalyst for oxidizing an aromatie carboxylic acid to a phenol.
In accordance with one aspect of the present invention there is provided a catalyst of oxidized copper, zirconium and an alkali metal.
In aceordance with another aspect of the present invention, there is provided an improved catalytic process for oxidizing an aromatic carboxylie acid having at least one carboxyl yroup substituted on the aromatic nucleus to the corresponding phenol in which the catalyst is comprised of oxidized copper, zireonium and an alkali metal. The alkali metal is preferably sodium, potassium or lithium.
The catalyst is referred to as being oxidized copper, zirconium and an alkali metal, and such catalyst con-tains such metals and oxygen. The metals may be present as a mixture of the oxides of copper, zireonium and an alkali metal or as a complex thereof, and sueh terminology encompas-ses such mixtures and complexes~
More particularly, the catalyst of the oxidized copper, zirconium and an alkali metal can be employed in the absenee or presence of a suitable support material. Thus, for example, the catalyst may be in the form of pellets, extrudates, etc. or supported on a support material, having a surface area of no greater than 50 m2/g; preferably a-alumina.
T he catalyst includes the three components in an amount effective to eatalyze the oxidation of an aromatic carboxylic ~ 9~8~
contains the three components in a Cu/Zr/alkali metal atomic ratio in the range of 1/o.05 to 1/0.1 to 5, with the preferred range of 1/0.2 to 0.5/0.5 to 2.5.
The catalyst may be prepared by a variety of pro~
cedures known iII the art. Thus, for example, the catalyst can be supported on a suitable support by an impregnation or spray drying technique. ~lternatively, the three catalyst components can be produced in the form o~ pellets, extrudates, etc. In preparing a supported catalyst by impregnation, for example, water soluble salts of zirconium and copper, such as nitrates, are dissolved in water and the solution employed to impregnate a suitable support, such as alpha-alumina.
The impregnatedisupport is dried and calcined to oxidi~e the copper and zirconium. The xesulting catalyst is then treated with an aqueous solution of an alkali metal salt, e.g., the hydroxide, followed by drying and calcination to effect oxidation.
In accordance with another aspect of the present invention, the hereinabove described catalyst of oxidized copper, zirconium and an alkali metal is employed as the catalyst in the oxidation of an aromatic carboxylic acid to the corresponding phenol. The aromatic carboxylic acid has at least one carboxyl group substituent on the aromatic nucleus, which is generally a benzene or naphthalene nucleus. The aromatic nucleus may al~o include more than one carboxyl substituent group or may include other substituent groups, such as alkyl, halo, etc. Carboxyl group precursors, i.e., nitrile and amide, may be employed instead of a carboxyl group. The preferred starting materials are the mono carboxylic acids of benzene and alkyl benzenes.
The oxidation is effected with molecular oxygen which can be provided as such or in admixture with other gases; e.g., as air. The oxygen is employed in at least stoichiometric pro-portions; however, lesser or greater amounts could be emploved.
In yeneral, oxygen is employed in an amount to provide an oxy~en to carboxyl groups mole ratio of from about 0.2:1 to 10:1, and prefera~ly from 0.5:1 to 5:1.
The reaction is generally effected in the vapor phase in the presence of steam as a diluent. ~he steam also functions to minimize the production of esters that result from the reaction of the carboxylic acid and the product phenol.
The steam is generally provided in an amount corresponding to a steam/carboxyl group mole ration of 5:1 to 500:1 and prefer-ably 10 1 to 100:1.
The oxidation is effected at temperatures of from about 200 to 400c, and preferably from 250 to 350C. The oxidation is generally effected at pressures above atmospheric pressure, with the pressure generally being from about 2 to 20 atmospheres.
The catalytic oxidation can be readily effected by ~ the use of any one of a wide variety of vapor-solid contact systems, e.g., employing the catalyst as a fixed or fluidized bed or in a transfer line type of contact system. The above means for e~fecting the reaction and others should he apparent to those skilled in the art from the present teachings.
The invention will be further described with respect to the following examples:
EXAMPLE I
Production of Ca*alyst _ 12.0 ~ (0.05 mol) Cu (NO3)2~ 3H2O and 18.0 g (0.025 mol) Zr~ (NO3)~. 5 H2O were dissolved in 30 g of water and heated to 70-80C. The solution was used to impregnate 100 g of a low surfa~e area alpha-alumina (Carborundum* SA~T 99, 4-8 mesh). The wet catalyst was dried and calcined at 750C for two hours, during which time the nitrates decomposed to their corresponding oxides. This catalyst (lOO g) was treated with resultin~ catalyst was dried and calcined at 500 C for approx-imately 16 hours. The finished catalyst had the following composition (wt.~): 4.0% CuO, 3.0% ZrO2, 3.6% K2O remainder alumina.
The activity and selectivity of the catalyst in Example I for producing phenol from benzoic acid were measured in a ~ixed bed reactor. The reactor was a ]acketed 1' x 1"
dia. 316 stainless steel tube. Boiling Dowtherm* was used in 110 the jacket ~or temperature control. The feed was prepared by metering water through a heater at reactor pressure, passing the steam so produced through a benzoic acid saturator main-tained at a temperature reguired to yive the desired benzoic acid/water ratio, and then mixing this stream with the desired 115 amount o~ air. The reactor contained 60 g of catalyst.
Operating conditions and r_sul~s are given in Table I.
.
I
~9~88~
~ ~ ~ ,_ d~( ~ . . I
~1 ~ r~ U~ ~ I
o ~ X
~o ~: r~
a N r~ o O
~C
a ,~ O
t~ o o o O o o U~ ~
~ ..
,01 ~o ~ r~ ~D
P u~
t~
~.
`~, cn ~ ~
n~ o o o cn ~1 ~ ~ o o 1 h ~ ~ ~I
h tD Int~l O ~ O
~i .,1 D~ .~
E3 ~1 0 o a~ :~ ~ I~
O
~ E~
: . _ U I
a~
.
o o S~
~' P;
U~ ~ O
~ O
a) tn ~1 o LO
O ~1 _, . . _ . . _ .
~ ,_1 0 ~ l l l 3~g88~
The present invention is particularly advantageous in that it provides for improved selectivity. In addition, it provides a more economic method for converting aromatic carbox-120 ylic acids to phenols. This advantage derives from:1. Lower cost reactor system (vapor phase reactor vs.
liquid phase molten salt reactor).
2. Elimination of a difficult to dispose of waste stream.
The conventional process must draw off a slip stream from the 125 molten mass to maintain catalyst activity. This slip stream contains heavy meta7s and organics which cannot be simply in-cinerated for disposal~
The conventional process must draw off a slip stream from the 125 molten mass to maintain catalyst activity. This slip stream contains heavy meta7s and organics which cannot be simply in-cinerated for disposal~
3. Waste heat recovery. The reaction is highly exother-mic. The vapor phase reaction is conducted in a temperature 130 range approximately 100C higher than the liquid phase reaction, making it possible to recover the heat of reaction (e.g., as high pressure steam) at a more efficient temperature level.
4. The potential for higher yieids when producing alkyl-substituted phenols (e.g., cresols). These are less volatile 135 than phenol and, therefore, are more difficult to strip out of a liquid phase. It is well known that if the phenols are not removed from the liquid phase, they will further react and ultimately produce tars.
Claims (21)
1. A catalyst, comprising oxidized copper, zirconium and an alkali metal.
2. The catalyst of Claim 1 wherein the copper: zirconium:
alkali metal atomic ratio is from 1:0.05 to 1:0.1 to 5.
alkali metal atomic ratio is from 1:0.05 to 1:0.1 to 5.
3. The catalyst of Claim 2 wherein the oxidized copper, zirconium and alkali metal is supported on a support having a surface area of no greater than 50 m2/g.
4. The catalyst of Claim 3 wherein the support is of alumina.
5. The catalyst of Claim 1 wherein the copper: zirconium:
alkali metal atomic ratio is from 1:0.2 to 0.5:0.5 to 2.5.
alkali metal atomic ratio is from 1:0.2 to 0.5:0.5 to 2.5.
6. The catalyst of Claim 2 wherein the alkali metal is sodium.
7. The catalyst of Claim 2 wherein the alkali metal is potassium.
8. In a process for catalytically oxidizing with oxygen an aromatic carboxylic acid having at least one carboxyl group substituted on the aromatic nucleus to the corresponding phenol, the improvement comprising:
effecting said oxidation with a catalyst as defined in Claim 1.
effecting said oxidation with a catalyst as defined in Claim 1.
9. The process of Claim 8 wherein the copper: zirconium:
alkali metal atomic ratio is from 1:0.05 to 1:0.1 to 5.
alkali metal atomic ratio is from 1:0.05 to 1:0.1 to 5.
10. The process of Claim 9 wherein the oxidation is effected in the vapor phase at a temperature of from 200° to 400°C.
11. The process of Claim 10 wherein the oxidation is effected at a pressure above atmospheric pressure.
12. The process of Claim 11 wherein the oxidation is effected with an oxygen to carboxyl group mole ratio of from 0.2:1 to 10:1.
13. The process of Claim 12 wherein the oxidation is effected in the presence of steam to provide a steam to carboxyl group mole ratio of from 5:1 to 500:1.
14. The process of Claim 11 wherein the aromatic nucleus is benzene.
15. The process of Claim 14 wherein the aromatic carboxy-lic acid is an alkyl substituted benzoic acid to produce a cresol.
16. The process of Claim 14 wherein the aromatic carboxy-lic acid is benzoic acid to produce phenol.
17. The process of Claim 11 wherein the oxidized copper, zirconium and alkali metal is supported on a support having a surface area of no greater than 50 m2/g.
18. The process of Claim 17 wherein the support is alumina.
19. The process of Claim 14 wherein the alkali metal is potassium.
20. The process of Claim 19 wherein the oxidized copper, zirconium and alkali metal is supported on a support having a surface area of no greater than 50 m2/g.
21. The process of Claim 20 wherein the support is .alpha. - alumina.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85304077A | 1977-11-21 | 1977-11-21 | |
| US853,040 | 1977-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1098888A true CA1098888A (en) | 1981-04-07 |
Family
ID=25314866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA311,277A Expired CA1098888A (en) | 1977-11-21 | 1978-09-13 | Production of phenols and catalyst therefor |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5920384B2 (en) |
| AU (1) | AU520114B2 (en) |
| CA (1) | CA1098888A (en) |
| DE (1) | DE2844195C2 (en) |
| FI (1) | FI64751C (en) |
| FR (1) | FR2409086A1 (en) |
| GB (1) | GB1602669A (en) |
| IT (1) | IT1106056B (en) |
| NL (1) | NL7810528A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0040452B1 (en) * | 1980-05-16 | 1984-08-29 | Stamicarbon B.V. | Method for the preparation of substituted or unsubstituted phenol and catalysts therefor |
| US4390736A (en) * | 1980-11-26 | 1983-06-28 | Sumitomo Chemical Company, Limited | Process for producing phenols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB978918A (en) * | 1962-09-21 | 1965-01-01 | Shell Internationale Res Maatc | A process for converting benzene carboxylic acids into phenolic compounds |
-
1978
- 1978-05-30 GB GB24190/78A patent/GB1602669A/en not_active Expired
- 1978-09-13 CA CA311,277A patent/CA1098888A/en not_active Expired
- 1978-09-18 AU AU39929/78A patent/AU520114B2/en not_active Expired
- 1978-10-11 DE DE2844195A patent/DE2844195C2/en not_active Expired
- 1978-10-11 JP JP53125016A patent/JPS5920384B2/en not_active Expired
- 1978-10-20 NL NL7810528A patent/NL7810528A/en not_active Application Discontinuation
- 1978-10-26 FI FI783262A patent/FI64751C/en not_active IP Right Cessation
- 1978-11-03 IT IT51770/78A patent/IT1106056B/en active
- 1978-11-15 FR FR7832229A patent/FR2409086A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2409086A1 (en) | 1979-06-15 |
| DE2844195C2 (en) | 1985-02-14 |
| AU3992978A (en) | 1980-03-27 |
| NL7810528A (en) | 1979-05-23 |
| JPS5472789A (en) | 1979-06-11 |
| FR2409086B3 (en) | 1981-09-04 |
| GB1602669A (en) | 1981-11-11 |
| FI64751C (en) | 1984-01-10 |
| FI64751B (en) | 1983-09-30 |
| IT1106056B (en) | 1985-11-11 |
| JPS5920384B2 (en) | 1984-05-12 |
| AU520114B2 (en) | 1982-01-14 |
| DE2844195A1 (en) | 1979-05-23 |
| IT7851770A0 (en) | 1978-11-03 |
| FI783262A (en) | 1979-05-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |