GB2048263A - Preparing p-aminophenol - Google Patents
Preparing p-aminophenol Download PDFInfo
- Publication number
- GB2048263A GB2048263A GB8012453A GB8012453A GB2048263A GB 2048263 A GB2048263 A GB 2048263A GB 8012453 A GB8012453 A GB 8012453A GB 8012453 A GB8012453 A GB 8012453A GB 2048263 A GB2048263 A GB 2048263A
- Authority
- GB
- United Kingdom
- Prior art keywords
- alumina
- catalyst
- platinum
- nitrobenzene
- hydrogenation
- 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.)
- Granted
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- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 57
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 239000012431 aqueous reaction media Substances 0.000 claims abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001679 gibbsite Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 208000029618 autoimmune pulmonary alveolar proteinosis Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J23/42—Platinum
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- 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
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
A method for preparing p- aminophenol, which comprises hydrogenating nitrobenzene in an acidic aqueous reaction medium in the presence of a catalyst comprising platinum supported on gamma- alumina.
Description
SPECIFICATION
Preparing p-Aminophenol
This invention relates to a method for the preparation of p-aminophenol.
p-Aminophenol (PAP) is an important chemical intermediate used in the preparation of the analgesic, acetaminophen (APAP). Anumber of other derivatives having a wide variety of industrial applications may also be prepared from PAP.
An important commercial method for the preparation of PAP involves the catalytic hydrogenation of nitrobenzene in an acid aqueous medium. Conventionally, the hydrogenation is carried out in the presence of a 10%-i 3% sulfuric acid solution containing a small amount of a surfactant, such as dodecyltrimethylammonium chloride, and utilizing a platinum-on-carbon catalyst. The reaction is complex and yields, in addition to the principal product, PAP, a significant amount of aniline and smaller amounts of other impurities.
In any commerical process which utilizes a platinum catalyst, recovery of the platinum from the spent catalyst is an important economic factor. While the carbon-supported platinum catalysts commonly used in the nitrobenzene/PAP process are reasonably satisfactory from the point of view of their primary function, i.e., the conversion of nitrobenzene to PAP, they leave much to be desired from the point of view of platinum recovery from the spent catalyst. As a rule, such recovery depends on combustion of the carbon to separate it from the platinum. Experience has shown such recovery to be only about 6065% efficient. In addition, the spent carbonaceous catalyst is rather unpleasant to handle.
The term "alumina" covers a considerable variety of specific entities having varying physicochemical properties. The chemical compositions of various types of alumina run from trihydrates, Al(OH)3, through monohydrates, AIOOH, to the anhydrous oxide, At203. The matter is further complicated by the existence of different crystalline forms having essentially the same gross chemical composition. Further, in addition to the three more or less well defined degrees of hydration suggested by the chemical formulas given above, there exist a number of "transition aluminas", identifiable by crystallographic and other physico-chemical criteria. The matter is still further complicated by the intermingling of two or more systems of of nomenclature.To illustrate, one crystalline entity having the nominal composition of Al(OH)3 is known variously as alpha-alumina trihydrate, gibbsite and hydrargyllite. Similarly, one crystalline entity having the nominal composition represented by AIOOH is known as alpha-alumina oxide hydroxide, alph-alumina monohydrate or boehmite. The end product of the thermal degradation of all the forms of hydrated alumina is Awl203, known as alpha-alumina or corundum. The term "activated alumina" has been applied broadly to the transition aluminas.The whole matter of interrelationships of the various types of "alumina" is discussed in the Kirk-Othmer "Encyclopedia of Chemical Technology", 3rd Ed. Vol. 2, pp. 218-244 (John Wiley 8 Sons, New York) 1978, which is incorporated herein by reference.
Alumina-supported platinum catalysts have been used in such large scale applications as oxidation catalysts process involving the hydrogenation of nitrobenzene. For example, U.S. Patnet 3,715,397 suggests the platinum supported on alpha-alumina may be a useful catalyst in the hydrogenation of nitrobenzene to PAP in an aqueous sulfuric acid reaction medium. Similarly, U.S.
Patent 3,694,509 suggests that a catalyst consisting of platinum supported on alumina is useful in the catalytic hydrogenation of nitrobenzene to phenylhydroxylamine in a neutral aqueous/alcoholic medium.
U.S. Patent 3,472,897 suggests the use of a catalyst consisting of platinum supported on pure etaalumina in the preparation of aniline by the hydrogenation of nitrobenzene in glacial acetic acid.
Similarly, U.S. Patnet 3,253,039 suggests the use of a catalyst consisting of platinum supported on activated alumina in the same reaction.
N.M. Popova et al. (Chem. Abs. 72: 104294b/1 970) used a catalyst consisting of mixed platinum and palladium supported on aluminum oxide in the hydrogenation of nitrobenzene in water of ethanol.
In accordance with the present invention, the hydrogenation of nitrobenzene to PAP in an acidic aqueous medium is carried out utilizing is supported platinum catalyst in which the support is the transition alumina known as gamma-alumina. Gamma-alumina is the first transition phase encountered in the calcination of boehmite (alpha-alumina monohydrate) to alpha-alumina (corundum). It is formed by calcining boehmite at temperatures in the range of 500--8500C. Preferably, the gamma-alumina support has a specific surface area of at least 200 m2/g.
Platinum is readily recoverable from spent Pt/gamma-alumina catalysts by immersing the spent catalyst in a strongly alkaline solution such as a solution of sodium hydroxide, to dissolve the gammaalumina. The undissolved platinum may then be filtered off. Recovery yields of about 8085% are ordinarily achievable. Alpha-alumina is not readily soluble under the same conditions.
The invention is further illustrated by the following Example.
EXAMPLE
I. Supported platinum catalysts were prepared using as supports alpha-alumina and gammaalumina. The gamma-alumina was prepared by calcining boehmite powder (48% less than 45 microns, 9% larger than 90 microns) at 11 000F (5930C) for two hours. The cooled product was screened through a U.S. Standard No. 325 sieve.
The characteristics of this gamma-alumina and of the alpha-alumina also used as a support are set forth in Table 1.
Table 1 Characteristics of Alumina Supports
Characteristic Alpha-Alumina Gamma-Alumina Specific surface area 5.7 230
(m2/g) (BET)
Bulk Density (g/cc) 0.83 0.62
Loss on Ignition (%) 0.16 7.77
Iron (Fe) (%) 0.061 O.D03
Sulfur (S) (%) 0.007 0.009
Filter Speed (sec) 143 191
Proportion Passing U.S.
No. 325 Sieve All All
Ave. Particle Size (microns) 23 23
II. Platinum was deposited on the alpha- and gamma-alumina supports by the following method:
A portion of the alumina (48.5g) was slurried in water (500ml) at 220C. Chloroplatinic acid solution (1 00 ml. containing 1.5 g Pt) was added dropwise to the stirred slurry during a period of 10 minutes. The slurry was stirred and additional 10 minutes, then vacuum filtered. Without washing, the filter cake was dired 1 6 hours at 1 500C.
III. The platinum deposit was reduced to metallic platinum as follows: The Dry platinum/alumina composition was packed into a quartz tube (1" diameter) and the tube was purged with hydrogen (100 ml/min.) for 10 minutes. Hydrogen (100 ml/min.) was then passed through the tube at 3500C for 30 minutes. The catalyst was cooled under hydrogen, then the tube was purged with nitrogen (100 ml/min.) for 10 minutes, and the catalyst was discharged from the tube under nitrogen.
A second batch of Pt/gamma-alumina catalyst (B) was prepared by the procedure described above for the first batch (A).
The supported catalysts had the characteristics tabulated in Table 2.
Table 2
Characteristics of Supported Catalysts
Support
Characteristic AlphaAlumina Gamma-Alumina
A B
Pt. (% w/w) 2.93 2.88
Pt. Dispersion (%) 10.5 53.1 36.4
Specific Surface Area (m2/g) 7 229 229 Iron (Fe) (%) O.D04 0.008 - Mean particle diameter (microns) 25 32
Loss on Ignition (%) 0.33 2.71 7.01
IV. The catalysts described above were used in the catalytic hydrogenation of nitrobenzene to PAP by
the method described below, the hydrogenation being interrupted prior to the consumption of all the
nitrobenzene, as described in U.S. Patent 3,383,416.
A mixture of distilled water (650 ml), dodecyltrimethyl-ammonium chloride, (2 ml) and Pt/alumina
catalyst containing 7.5 mg of Pt, in a 2 liter reaction vessel equipped for pressure hydrogenation, was flushed with nitrogen, then heated to 700 C. under hydrogen. With vigorous agitation, sulfuric acid (80 g of 9598% reagent grade/Sp. Gr. 1.84) was added during a period of 2-3 minutes, the temperature rising to 87--880C. Nitrobenzene (108 g) was added rapidly, the hydrogenation was carried out at 87-900C. at pressures slightly above atmospheric (6-1 0 inches of water).After 5-6 hours the hydrogenation was interrupted and the aqueous and nitrobenzene phases were separated, the catalyst remaining suspended in the nitrobenzene phase. The concentrations of p-aminophenol and aniline, respectively, in the aqueous phase were determined by high pressure liquid chromatography. Significant data are tabulated in Table 3.
Table 3
Reaction Products of Catalytic Hydrogenation of N itrobenzene Product Concentration in
Catalyst Run No. Hydrogenation Time (hrs.) Aqueous Phase (mg/ml)
PAP Aniline Pt/alpha-alumina 1 6 15.9 2.3 " 2 5.25 6.6 1.1 Pt/gammaoalumina (B) 3 6 853 24.3 " 4 5 82.0 25.0 Pt/C* 5 6 81.0 16.0 6 6 6 81.5 14.7 * Runs 5ss utilized, for comparison a platinum-on-carbon catalyst that had shown good
pe-rformance in the commercial production of PAP from nitrobenzene.
Experience has shown that the performance of a catalyst, as evaluated by the method outlined above, may be considered acceptable if the yield of PAP exceeds 50 mg/ml and the PAP/aniline ratio is greater than 3.0.
Claims (8)
1. A method for preparing p-aminophenol, which comprises hydrogenating nitrobenzene in an acidic aqueous reaction medium in the presence of a catalyst comprising platinum supported on gamma-alumina.
2. A method according to claim 1 wherein the catalyst has been prepared by depositing platinum on a support prepared by calcining boehmite at a temperature of 5000C to 8500C.
3. A method according to claim 2 wherein the boehmite is calcined at a temperature of about 5930C.
4. A method according to any preceding claim wherein the catalyst support has a specific surface area of at least 200m2/g.
5. A method according to claim 4 wherein the support has a specific surface area of about 230m2/g.
6. A method according to any preceding claim wherein the catalyst contains from 1 to 10% Pt.
7. A method according to claim 6 wherein the catalyst contains from 3 to 5% Pt.
8. A method according to any preceding claim wherein the hydrogenation is interrupted prior to the consumption of all the nitrobenzene.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3377879A | 1979-04-27 | 1979-04-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2048263A true GB2048263A (en) | 1980-12-10 |
| GB2048263B GB2048263B (en) | 1983-05-25 |
Family
ID=21872387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8012453A Expired GB2048263B (en) | 1979-04-27 | 1980-04-15 | Preparing p-aminophenol |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS55145644A (en) |
| BE (1) | BE882994A (en) |
| CA (1) | CA1139317A (en) |
| DE (1) | DE3015881A1 (en) |
| DK (1) | DK173680A (en) |
| ES (1) | ES490886A0 (en) |
| FI (1) | FI801264A (en) |
| FR (1) | FR2455029A1 (en) |
| GB (1) | GB2048263B (en) |
| GR (1) | GR67288B (en) |
| IT (1) | IT1128522B (en) |
| LU (1) | LU82401A1 (en) |
| NL (1) | NL8002325A (en) |
| NO (1) | NO149472C (en) |
| PH (1) | PH14780A (en) |
| PT (1) | PT71098A (en) |
| SE (1) | SE8002783L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3362485D1 (en) * | 1982-01-29 | 1986-04-17 | Mallinckrodt Inc | Process for preparing p-aminophenol and alkyl substituted p-aminophenol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3265735A (en) * | 1964-06-15 | 1966-08-09 | Frontier Chemical Company | Manufacture of para-chloroaniline and para-aminophenol |
-
1980
- 1980-04-09 GR GR61627A patent/GR67288B/el unknown
- 1980-04-14 PH PH23893A patent/PH14780A/en unknown
- 1980-04-14 SE SE8002783A patent/SE8002783L/en not_active Application Discontinuation
- 1980-04-15 PT PT71098A patent/PT71098A/en unknown
- 1980-04-15 GB GB8012453A patent/GB2048263B/en not_active Expired
- 1980-04-21 FI FI801264A patent/FI801264A/en not_active Application Discontinuation
- 1980-04-22 IT IT48483/80A patent/IT1128522B/en active
- 1980-04-22 NL NL8002325A patent/NL8002325A/en not_active Application Discontinuation
- 1980-04-23 DK DK173680A patent/DK173680A/en active IP Right Grant
- 1980-04-24 CA CA000350576A patent/CA1139317A/en not_active Expired
- 1980-04-24 DE DE19803015881 patent/DE3015881A1/en not_active Withdrawn
- 1980-04-25 ES ES490886A patent/ES490886A0/en active Granted
- 1980-04-25 NO NO801221A patent/NO149472C/en unknown
- 1980-04-25 FR FR8009431A patent/FR2455029A1/en active Pending
- 1980-04-25 LU LU82401A patent/LU82401A1/en unknown
- 1980-04-25 BE BE0/200383A patent/BE882994A/en not_active IP Right Cessation
- 1980-04-26 JP JP5608680A patent/JPS55145644A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2455029A1 (en) | 1980-11-21 |
| NO149472C (en) | 1984-04-25 |
| JPS55145644A (en) | 1980-11-13 |
| PT71098A (en) | 1980-05-01 |
| SE8002783L (en) | 1980-10-28 |
| DE3015881A1 (en) | 1980-11-06 |
| LU82401A1 (en) | 1980-07-31 |
| NL8002325A (en) | 1980-10-29 |
| DK173680A (en) | 1980-10-28 |
| GR67288B (en) | 1981-06-29 |
| BE882994A (en) | 1980-08-18 |
| CA1139317A (en) | 1983-01-11 |
| NO149472B (en) | 1984-01-16 |
| IT8048483A0 (en) | 1980-04-22 |
| ES8102087A1 (en) | 1980-12-16 |
| ES490886A0 (en) | 1980-12-16 |
| IT1128522B (en) | 1986-05-28 |
| PH14780A (en) | 1981-12-09 |
| NO801221L (en) | 1980-10-28 |
| GB2048263B (en) | 1983-05-25 |
| FI801264A (en) | 1980-10-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |