CA2362261A1 - Hydroperoxide decomposition process - Google Patents
Hydroperoxide decomposition process Download PDFInfo
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- CA2362261A1 CA2362261A1 CA002362261A CA2362261A CA2362261A1 CA 2362261 A1 CA2362261 A1 CA 2362261A1 CA 002362261 A CA002362261 A CA 002362261A CA 2362261 A CA2362261 A CA 2362261A CA 2362261 A1 CA2362261 A1 CA 2362261A1
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- chhp
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- hydroperoxide
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing 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
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- 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 Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
An improved process for decomposing alkyl or aromatic hxdroperoxides to form a decomposition reaction mixture containing the corresponding alcohol and ketone. The improvement relates to decomposing the hydroperoxide by contacting the hydroperoxide with a catalitic amount of a heterogenous catalyst comprised of gold, wherein one or more additional metals selected from Periodic Group VIII is/are also present with gold. Moreover, the catalysts are optinally supported on a suitable support member, such as SiO2, Al2O3, carbon, zirconia, MgO or TiO2. The process may also optionally be run in the presence of hydrogen gas.
Description
TITLE
HYDROPEROXIDE DECOMPOSITION PROCESS
FIELD OF THE INVENTION
The invention generally relates to an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone. In particular, the invention relates to decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogenous catalyst comprised of gold, wherein one or more additional metals selected from Periodic Group VIII is/are also present with gold.
BACKGROUND OF THE INVENTION
Industrial processes for the production of mixtures of cyclohexanol and cyclohexanone from cyclohexane are currently of considerable commercial significance and are well described in the patent literature. In accordance with typical industrial practice, cyclohexane is oxidized to form a reaction mixture containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is decomposed, optionally in the presence of a catalyst, to form a reaction mixture containing cyclohexanol and cyclohexanone. In the industry, such a mixture is known as a K/A (ketone/alcohol) mixture, and can be readily oxidized to produce adipic acid, which is an important reactant in processes for preparing certain 2o condensation polymers, notably polyamides. Due to the large volumes of adipic acid consumed in these and other processes, improvements in processes for producing adipic acid and its precursors can be used to provide beneficial cost advantages.
Druliner et al., U.S. Patent No. 4,326,084, disclose an improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. The improvement involves the use of certain transition metal complexes of 1,3-bis(2-pyridylimino)isoindolines as catalysts for cyclohexane oxidation and CHHP decomposition. According to this patent, these catalysts 3o demonstrate longer catalyst life, higher CHHP conversion to K and A, operability at lower temperatures (80-160°C), and reduced formation of insoluble metal-containing solids, relative to results obtained with certain cobalt(II) fatty acid salts, e.g., cobalt 2-ethylhexanoate.
Druliner et al., U.S. Patent No. 4,503.257, disclose another improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. This improvement involves the use of Co304, Mn02; or Fe304 applied to a suitable solid support as catalysts for cyclohexane oxidation ~: -: ~ ~~. ~~, PCT/ ~ ~..
CA 02362261 2001-08-07 , r6a' < . -, ~- ~. ,, v.
and CHHP decomposition at a temperature from about 80°C to about 130°C, in the presence of molecular oxygen.
Sanderson et al., U.S. Patent No. 5,414,163, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of titanic, zirconia, or mixtures thereof.
Sanderson et al., U.S. Patent Nos. 5,414,141, 5,399,794 and 5,401,889, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of palladium with gold as a dispersing agent supported on alumina.
Druliner et al., U.S. provisional application 60/025,368 filed September 3, 1996 (now PCT US97/15332 filed September 2, 1997), disclose decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogenous catalyst of Zr, Nb, Hf and Ti hydroxides or oxides. Preferably, the catalyst is supported on Si02, A1203, carbon or Ti02. Alumina is a preferred support.
1 S WO A-98/34894 discloses a process for decomposing hypoperoxides to their corresponding alcohol and ketone.
Further improvements and options are needed for hydroperoxide decomposition to KJA mixtures in order to overcome the deficiencies inherent in the prior art. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows.
SUMMARY OF THE INVENTION
In accordance with the present invention, an improved process is provided in which a hydroperoxide is decomposed to form a decomposition reaction mixture containing a corresponding alcohol and ketone. The improvement comprises decomposing hydroperoxide by contacting a hydroperoxide with a catalytic amount of a catalytic amount of a heterogenous catalyst comprised of gold, wherein one or more additional metals selected from Periodic Crroup VIII
islare also present with gold. Moreover, the catalysts are optionally supported on a suitable support member, such as Si02, A12O3, carbon, zirconia, Mg0 or Ti02.
Preferably the additional metal is Pt or Pd. The process may optionally be run in the presence of hydrogen gas.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides-an improved process for conducting a hydroperoxide decomposition step in an isadustrial process in which an alkyl or aromatic compound is oxidized to form a mixture of the corresponding alcohol and ketone. In particular, cyclohexane can be oxidized to form a mixture containing cyclohexanol (A) and cyclohexanone (K). The industrial process AMENDED SHEET
' CA 02362261 2001-08-07 ~~~~~~ rt, ~, PCT/ ~ ~ -, involves two steps: first, cyclohexane is oxidized, forming a reaction mixture containing CHHP; second, CHHP is decomposed, forming a mixture containing K
2?
AMENDED SHEET
'~.'~ ~- ,~ . ~ y ";
and A. As previously mentioned, processes for the oxidation of cyclohexane are well known in the literature and available to those skilled in the art.
Advantages of the present heterogenous catalytic process, relative to processes employing homogenous metal catalysts, such as metal salts or metal/ligand mixtures, include longer catalyst life, improved yields of useful products, and the absence of soluble metal compounds.
The improved process can also be used for the decomposition of other alkane or aromatic hydroperoxides, for example, t-butyl hydroperoxide, cyclododecylhydroperoxide and cumene hydroperoxide.
The CHHP decomposition process can be performed under a wide variety of conditions and in a wide variety of solvents, including cyclohexane itself.
Since CHHP is typically produced industrially as a solution in cyclohexane from catalytic oxidation of cyclohexane, a convenient and preferred solvent for the decomposition process of the invention is cyclohexane. Such a mixture can be used as received from the first step of the cyclohexane oxidation process or after some of the constituents have been removed by known processes such as distillation or aqueous extraction to remove carboxylic acids and other impurities.
The preferred concentration of CHHP in the CHHP decomposition feed mixture can range from about 0.5% by weight to 100% (i.e., neat). In the industrially practiced route, the preferred range is from about 0.5% to about 3%
by weight.
Suitable reaction temperatures for the process of the invention range from about 80°C to about 170°C. Temperatures from about 110°C
to about 130°C are typically preferred. Reaction pressures can preferably range from about 69 kPa to about 2760 kPa (10-400 psi) pressure, and pressures from about 276 kPa to about 1380 kPa (40-200 psi) are more preferred. Reaction time varies in inverse relation to reaction temperature, and typically ranges from about 2 to about 30 minutes.
As noted previously, the heterogenous catalysts of the invention include Au, Ag, Cu (including, but not limited to, Au, Ag and Cu sol-gel compounds) and certain non-Au/Ag/Cu sol-gel compounds, preferably applied to suitable solid supports. The inventive process may also be performed using Au, Ag or Cu in the presence of other metals (e.g., Pd). The metal to support percentage can vary from about 0.01 to about 50 percent by weight, and is preferably about 0.1 to about 10 wt. percent. Suitable, presently preferred supports include Si02 (silica), A1203 (alumina), C (carbon), Ti02 (titania), Mg0 (magnesia) or Zr02 (zirconia).
Zirconia and alumina are particularly preferred supports, and Au supported on alumina is a particularly preferred catalyst of the invention.
Some of the heterogenous catalysts of the invention can be obtained already prepared from manufacturers, or they can be prepared from suitable starting materials using methods known in the art. These methods can include sol-gel techniques as described in more detail below for preparing both Au/Ag/Cu sol-gel compounds and other non-Au/Ag/Cu sol-gel compounds. Supported gold catalysts can be prepared by any standard procedure known to give well-dispersed gold, such as evaporative techniques or coatings from colloidal dispersions.
In particular, ultra-fine particle sized gold is preferred. Such small particulate gold (often smaller than l Onm) can be prepared according to Haruta, 1o M., "Size-and Support-Dependency in the Catalysis of Gold", Catalysis Today (1997) 153-166 and Tsubota et al., Preparation of Catalysts V, pp. 695-704 ( 1991 ). Such gold preparations produce samples that are purple-pink in color instead of the typical bronze color associated with gold and result in highly dispersed gold catalysts when placed on a suitable support member. These highly dispersed gold particles typically are from about 3 nm to about 15 nm in diameter.
The catalyst solid support, including Si02, A1203, carbon, MgO, zirconia, or Ti02, can be amorphous or crystalline, or a mixture of amorphous and crystalline forms. Selection of an optimal average particle size for the catalyst supports will depend upon such process parameters as reactor residence time and 2o desired reactor flow rates. Generally, the average particle size selected will vary from about 0.005 mm to about 5 mm. Catalysts having a surface area larger than 10 m2/g are preferred since increased surface area of the catalyst has a direct correlation with increased decomposition rates in batch experiments. Supports having much larger surface areas can also be employed, but inherent brittleness of high-surface area catalysts, and attendant problems in maintaining an acceptable particle size distribution, will establish a practical upper limit upon catalyst support surface area. A preferred support is alumina; more preferred is a,-alumina and y alumina.
A "sol-gel technique" is a process wherein a free flowing fluid solution, "sol", is first prepared by dissolving suitable precursor materials such as colloids, alkoxides or metal salts in a solvent. The "sol" is then dosed with a reagent to initiate reactive polymerization of the precursor. A typical example is tetraethoxyorthosilicate (TEOS) dissolved in ethanol. Water, with trace acid or base as catalyst to initiate hydrolysis, is added. As polymerization and crosslinking proceeds, the free flowing ''sol" increases in viscosity and can eventually set to a rigid "gel". The "gel" consists of a crosslinked network of the desired material which encapsulates the original solvent within its open porous structure. The "gel" may then be dried, typically by either simple heating in a flow of dry air to produce a xerogel or the entrapped solvent may be removed by displacement with a supercritical fluid such as liquid C02 to produce an aerogel.
These aerogels and xerogels may be optionally calcined at elevated temperatures (>200°C) which results in products which typically have very porous structures and concomitantly high surface areas.
In practice of the invention, the catalysts can be contacted with CHHP by formulation into a catalyst bed, which is arranged to provide intimate contact between catalysts and reactants. Alternatively, catalysts can be slurried with reaction mixtures using techniques known in the art. The process of the invention 1o is suitable for batch or for continuous CHHP decomposition processes. These processes can be performed under a wide variety of conditions.
Adding air or a mixture of air and inert gases to CHHP decomposition mixtures provides higher conversions of process reactants to K and A, since some cyclohexane is oxidized directly to K and A, in addition to K and A being formed by CHHP decomposition. This ancillary process is known as "cyclohexane participation", and is described in detail in Druliner et al., U.S. Patent No. 4,326,084, the entire contents of which are incorporated by reference herein.
Other gases may also be added or co-fed to the reaction mixture as needed.
Inert gases such as nitrogen may also be added to the reaction alone or in combination 2o with other gases.
The results of the CHHP decomposition reaction, such as the K/A ratio or conversion rate, can be adjusted by choice of catalyst support, gases added to the reaction mixture, or metals added to the heterogeneous catalysts of the invention.
Preferably, metals added to the heterogeneous catalysts of the invention are for use as promoters, synergist additives, or co-catalysts are selected from Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
Most preferred is Pd and Pt.
One preferred gas that can be added to the reaction mixture is hydrogen.
An advantage of the addition of hydrogen is that the K/A ratio can be varied according to need. The addition of hydrogen can also convert impurities or by-products of the reactions, such as benzene, to more desirable products.
The process of the present~invention is further illustrated by the following non-limiting examples. In the examples, all temperatures are in degrees Celsius and all percentages are by weight unless otherwise indicated.
EXPERIMENTS
Experiment 1 ~1.4% Au on Carbon ~ g of 20-3~ mesh (0.~-0.85 mm) charcoal carbon (EM Science. Cherry Hill, N~ was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 0.1 g gold trichloride in 10 mL
water containing 1 mL concentrated HCI. The slurry was stirred for 1 ~ minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 2 ~1.4% Au on Silica 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 0.1 g gold trichloride in 10 mL water containing 1 mL concentrated HCI. The slurry was stirred for 1 S minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 3 ~14% Au on Silica 5 g of <2 micron silica gel with surface area 450 m2/g and pore volume 1.6 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g gold trichloride in 10 mL water containing 1 mL concentrated HCI. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 4 - Plain Silica Control 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 10 mL
water containing 1 mL concentrated HC1. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C
for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP
decomposition catalyst.
Experiment 5 ~1.4% Au on a-Alumina 5 g of 6-12 mesh a-alumina spheres (Calsicat, Erie, PA) was slurried into a solution of 0.1 g gold trichloride in 10 mL water containing 1 mL
concentrated HCI. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 6 ~13% A~ on Silica g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 5 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g silver nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined another 1 hour in flowing hydrogen (100 mL/min) and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 7 ~ 4.5% Cu on Silica 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g copper nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined another 1 hour in flowing hydrogen (100 mL/min) and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Unlike Experiments 1-7, Experiments 8-13 were carned out according to the general gold deposition technique of Tsubota et al., Preparation of Catalysts V, pp. 695-704 (1991) to produce ultra-fine gold particles. These supported catalysts were purple/pink in color compared to the bronze/gold (higher loadings) or brown/grey (lower loadings) supported catalysts of Experiments 1-7.
Experiment 8 ~1 % Au on MAO
10 g of powdered - 200 mesh Mg0 (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
HYDROPEROXIDE DECOMPOSITION PROCESS
FIELD OF THE INVENTION
The invention generally relates to an improved catalytic process for decomposing alkyl or aromatic hydroperoxides to form a mixture containing the corresponding alcohol and ketone. In particular, the invention relates to decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogenous catalyst comprised of gold, wherein one or more additional metals selected from Periodic Group VIII is/are also present with gold.
BACKGROUND OF THE INVENTION
Industrial processes for the production of mixtures of cyclohexanol and cyclohexanone from cyclohexane are currently of considerable commercial significance and are well described in the patent literature. In accordance with typical industrial practice, cyclohexane is oxidized to form a reaction mixture containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is decomposed, optionally in the presence of a catalyst, to form a reaction mixture containing cyclohexanol and cyclohexanone. In the industry, such a mixture is known as a K/A (ketone/alcohol) mixture, and can be readily oxidized to produce adipic acid, which is an important reactant in processes for preparing certain 2o condensation polymers, notably polyamides. Due to the large volumes of adipic acid consumed in these and other processes, improvements in processes for producing adipic acid and its precursors can be used to provide beneficial cost advantages.
Druliner et al., U.S. Patent No. 4,326,084, disclose an improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. The improvement involves the use of certain transition metal complexes of 1,3-bis(2-pyridylimino)isoindolines as catalysts for cyclohexane oxidation and CHHP decomposition. According to this patent, these catalysts 3o demonstrate longer catalyst life, higher CHHP conversion to K and A, operability at lower temperatures (80-160°C), and reduced formation of insoluble metal-containing solids, relative to results obtained with certain cobalt(II) fatty acid salts, e.g., cobalt 2-ethylhexanoate.
Druliner et al., U.S. Patent No. 4,503.257, disclose another improved catalytic process for oxidizing cyclohexane to form a reaction mixture containing CHHP, and for subsequently decomposing the resulting CHHP to form a mixture containing K and A. This improvement involves the use of Co304, Mn02; or Fe304 applied to a suitable solid support as catalysts for cyclohexane oxidation ~: -: ~ ~~. ~~, PCT/ ~ ~..
CA 02362261 2001-08-07 , r6a' < . -, ~- ~. ,, v.
and CHHP decomposition at a temperature from about 80°C to about 130°C, in the presence of molecular oxygen.
Sanderson et al., U.S. Patent No. 5,414,163, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of titanic, zirconia, or mixtures thereof.
Sanderson et al., U.S. Patent Nos. 5,414,141, 5,399,794 and 5,401,889, disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over catalytically effective amounts of palladium with gold as a dispersing agent supported on alumina.
Druliner et al., U.S. provisional application 60/025,368 filed September 3, 1996 (now PCT US97/15332 filed September 2, 1997), disclose decomposing a hydroperoxide by contacting it with a catalytic amount of a heterogenous catalyst of Zr, Nb, Hf and Ti hydroxides or oxides. Preferably, the catalyst is supported on Si02, A1203, carbon or Ti02. Alumina is a preferred support.
1 S WO A-98/34894 discloses a process for decomposing hypoperoxides to their corresponding alcohol and ketone.
Further improvements and options are needed for hydroperoxide decomposition to KJA mixtures in order to overcome the deficiencies inherent in the prior art. Other objects and advantages of the present invention will become apparent to those skilled in the art upon reference to the detailed description which hereinafter follows.
SUMMARY OF THE INVENTION
In accordance with the present invention, an improved process is provided in which a hydroperoxide is decomposed to form a decomposition reaction mixture containing a corresponding alcohol and ketone. The improvement comprises decomposing hydroperoxide by contacting a hydroperoxide with a catalytic amount of a catalytic amount of a heterogenous catalyst comprised of gold, wherein one or more additional metals selected from Periodic Crroup VIII
islare also present with gold. Moreover, the catalysts are optionally supported on a suitable support member, such as Si02, A12O3, carbon, zirconia, Mg0 or Ti02.
Preferably the additional metal is Pt or Pd. The process may optionally be run in the presence of hydrogen gas.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides-an improved process for conducting a hydroperoxide decomposition step in an isadustrial process in which an alkyl or aromatic compound is oxidized to form a mixture of the corresponding alcohol and ketone. In particular, cyclohexane can be oxidized to form a mixture containing cyclohexanol (A) and cyclohexanone (K). The industrial process AMENDED SHEET
' CA 02362261 2001-08-07 ~~~~~~ rt, ~, PCT/ ~ ~ -, involves two steps: first, cyclohexane is oxidized, forming a reaction mixture containing CHHP; second, CHHP is decomposed, forming a mixture containing K
2?
AMENDED SHEET
'~.'~ ~- ,~ . ~ y ";
and A. As previously mentioned, processes for the oxidation of cyclohexane are well known in the literature and available to those skilled in the art.
Advantages of the present heterogenous catalytic process, relative to processes employing homogenous metal catalysts, such as metal salts or metal/ligand mixtures, include longer catalyst life, improved yields of useful products, and the absence of soluble metal compounds.
The improved process can also be used for the decomposition of other alkane or aromatic hydroperoxides, for example, t-butyl hydroperoxide, cyclododecylhydroperoxide and cumene hydroperoxide.
The CHHP decomposition process can be performed under a wide variety of conditions and in a wide variety of solvents, including cyclohexane itself.
Since CHHP is typically produced industrially as a solution in cyclohexane from catalytic oxidation of cyclohexane, a convenient and preferred solvent for the decomposition process of the invention is cyclohexane. Such a mixture can be used as received from the first step of the cyclohexane oxidation process or after some of the constituents have been removed by known processes such as distillation or aqueous extraction to remove carboxylic acids and other impurities.
The preferred concentration of CHHP in the CHHP decomposition feed mixture can range from about 0.5% by weight to 100% (i.e., neat). In the industrially practiced route, the preferred range is from about 0.5% to about 3%
by weight.
Suitable reaction temperatures for the process of the invention range from about 80°C to about 170°C. Temperatures from about 110°C
to about 130°C are typically preferred. Reaction pressures can preferably range from about 69 kPa to about 2760 kPa (10-400 psi) pressure, and pressures from about 276 kPa to about 1380 kPa (40-200 psi) are more preferred. Reaction time varies in inverse relation to reaction temperature, and typically ranges from about 2 to about 30 minutes.
As noted previously, the heterogenous catalysts of the invention include Au, Ag, Cu (including, but not limited to, Au, Ag and Cu sol-gel compounds) and certain non-Au/Ag/Cu sol-gel compounds, preferably applied to suitable solid supports. The inventive process may also be performed using Au, Ag or Cu in the presence of other metals (e.g., Pd). The metal to support percentage can vary from about 0.01 to about 50 percent by weight, and is preferably about 0.1 to about 10 wt. percent. Suitable, presently preferred supports include Si02 (silica), A1203 (alumina), C (carbon), Ti02 (titania), Mg0 (magnesia) or Zr02 (zirconia).
Zirconia and alumina are particularly preferred supports, and Au supported on alumina is a particularly preferred catalyst of the invention.
Some of the heterogenous catalysts of the invention can be obtained already prepared from manufacturers, or they can be prepared from suitable starting materials using methods known in the art. These methods can include sol-gel techniques as described in more detail below for preparing both Au/Ag/Cu sol-gel compounds and other non-Au/Ag/Cu sol-gel compounds. Supported gold catalysts can be prepared by any standard procedure known to give well-dispersed gold, such as evaporative techniques or coatings from colloidal dispersions.
In particular, ultra-fine particle sized gold is preferred. Such small particulate gold (often smaller than l Onm) can be prepared according to Haruta, 1o M., "Size-and Support-Dependency in the Catalysis of Gold", Catalysis Today (1997) 153-166 and Tsubota et al., Preparation of Catalysts V, pp. 695-704 ( 1991 ). Such gold preparations produce samples that are purple-pink in color instead of the typical bronze color associated with gold and result in highly dispersed gold catalysts when placed on a suitable support member. These highly dispersed gold particles typically are from about 3 nm to about 15 nm in diameter.
The catalyst solid support, including Si02, A1203, carbon, MgO, zirconia, or Ti02, can be amorphous or crystalline, or a mixture of amorphous and crystalline forms. Selection of an optimal average particle size for the catalyst supports will depend upon such process parameters as reactor residence time and 2o desired reactor flow rates. Generally, the average particle size selected will vary from about 0.005 mm to about 5 mm. Catalysts having a surface area larger than 10 m2/g are preferred since increased surface area of the catalyst has a direct correlation with increased decomposition rates in batch experiments. Supports having much larger surface areas can also be employed, but inherent brittleness of high-surface area catalysts, and attendant problems in maintaining an acceptable particle size distribution, will establish a practical upper limit upon catalyst support surface area. A preferred support is alumina; more preferred is a,-alumina and y alumina.
A "sol-gel technique" is a process wherein a free flowing fluid solution, "sol", is first prepared by dissolving suitable precursor materials such as colloids, alkoxides or metal salts in a solvent. The "sol" is then dosed with a reagent to initiate reactive polymerization of the precursor. A typical example is tetraethoxyorthosilicate (TEOS) dissolved in ethanol. Water, with trace acid or base as catalyst to initiate hydrolysis, is added. As polymerization and crosslinking proceeds, the free flowing ''sol" increases in viscosity and can eventually set to a rigid "gel". The "gel" consists of a crosslinked network of the desired material which encapsulates the original solvent within its open porous structure. The "gel" may then be dried, typically by either simple heating in a flow of dry air to produce a xerogel or the entrapped solvent may be removed by displacement with a supercritical fluid such as liquid C02 to produce an aerogel.
These aerogels and xerogels may be optionally calcined at elevated temperatures (>200°C) which results in products which typically have very porous structures and concomitantly high surface areas.
In practice of the invention, the catalysts can be contacted with CHHP by formulation into a catalyst bed, which is arranged to provide intimate contact between catalysts and reactants. Alternatively, catalysts can be slurried with reaction mixtures using techniques known in the art. The process of the invention 1o is suitable for batch or for continuous CHHP decomposition processes. These processes can be performed under a wide variety of conditions.
Adding air or a mixture of air and inert gases to CHHP decomposition mixtures provides higher conversions of process reactants to K and A, since some cyclohexane is oxidized directly to K and A, in addition to K and A being formed by CHHP decomposition. This ancillary process is known as "cyclohexane participation", and is described in detail in Druliner et al., U.S. Patent No. 4,326,084, the entire contents of which are incorporated by reference herein.
Other gases may also be added or co-fed to the reaction mixture as needed.
Inert gases such as nitrogen may also be added to the reaction alone or in combination 2o with other gases.
The results of the CHHP decomposition reaction, such as the K/A ratio or conversion rate, can be adjusted by choice of catalyst support, gases added to the reaction mixture, or metals added to the heterogeneous catalysts of the invention.
Preferably, metals added to the heterogeneous catalysts of the invention are for use as promoters, synergist additives, or co-catalysts are selected from Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
Most preferred is Pd and Pt.
One preferred gas that can be added to the reaction mixture is hydrogen.
An advantage of the addition of hydrogen is that the K/A ratio can be varied according to need. The addition of hydrogen can also convert impurities or by-products of the reactions, such as benzene, to more desirable products.
The process of the present~invention is further illustrated by the following non-limiting examples. In the examples, all temperatures are in degrees Celsius and all percentages are by weight unless otherwise indicated.
EXPERIMENTS
Experiment 1 ~1.4% Au on Carbon ~ g of 20-3~ mesh (0.~-0.85 mm) charcoal carbon (EM Science. Cherry Hill, N~ was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 0.1 g gold trichloride in 10 mL
water containing 1 mL concentrated HCI. The slurry was stirred for 1 ~ minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 2 ~1.4% Au on Silica 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 0.1 g gold trichloride in 10 mL water containing 1 mL concentrated HCI. The slurry was stirred for 1 S minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 3 ~14% Au on Silica 5 g of <2 micron silica gel with surface area 450 m2/g and pore volume 1.6 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium (100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g gold trichloride in 10 mL water containing 1 mL concentrated HCI. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 4 - Plain Silica Control 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 10 mL
water containing 1 mL concentrated HC1. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C
for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP
decomposition catalyst.
Experiment 5 ~1.4% Au on a-Alumina 5 g of 6-12 mesh a-alumina spheres (Calsicat, Erie, PA) was slurried into a solution of 0.1 g gold trichloride in 10 mL water containing 1 mL
concentrated HCI. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 6 ~13% A~ on Silica g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 5 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g silver nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined another 1 hour in flowing hydrogen (100 mL/min) and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 7 ~ 4.5% Cu on Silica 5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100 mL/min) at 400°C for 1 hour. This material was then slurried into a solution of 1.0 g copper nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry was stirred for 15 minutes at room temperature and then evaporated to dryness on a rotary evaporator. The recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined another 1 hour in flowing hydrogen (100 mL/min) and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Unlike Experiments 1-7, Experiments 8-13 were carned out according to the general gold deposition technique of Tsubota et al., Preparation of Catalysts V, pp. 695-704 (1991) to produce ultra-fine gold particles. These supported catalysts were purple/pink in color compared to the bronze/gold (higher loadings) or brown/grey (lower loadings) supported catalysts of Experiments 1-7.
Experiment 8 ~1 % Au on MAO
10 g of powdered - 200 mesh Mg0 (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hour, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 9 ~1 % Au on ~~-Alumina g of powdered - 60 mesh ~y-alumina (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium 5 carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst. The resulting catalyst was to purple/pink in color and had a gold particle size of 8nm as determined by x-ray diffraction (XRD).
Experiment 10 ~1% Au on Silica 10 g of silica + 8 mesh granules (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 11 ~1% Au on Titanic 10 g of powdered - 325 mesh titanic (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 7.0 with sodium carbonate solution and then 1.5 g sodium citrate was added. After stirnng for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 400°C for S hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 12 ~1% Au on Zirconia 10 g - 325 mesh zirconia (Calsicat #96F-88A, Erie, PA) was slurried into a solution of 0.2 g gold chloride in 50 mL water and 1 drop conc. HCI. The slurry was stirred gently as the pH was adjusted to 9.6 with O.1M sodium carbonate solution. The slurry was stirred gently while 0.69 g sodium citrate solid was slowly added and then stirred for 2 further hours. After filtering and washing well with distilled water; the solid was calcined in flowing air for 5 hours at 250°C.
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium 5 carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst. The resulting catalyst was to purple/pink in color and had a gold particle size of 8nm as determined by x-ray diffraction (XRD).
Experiment 10 ~1% Au on Silica 10 g of silica + 8 mesh granules (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium carbonate solution and then 0.69 g sodium citrate was added. After stirring for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 11 ~1% Au on Titanic 10 g of powdered - 325 mesh titanic (Alfa Aesar, Ward Hill, MA) was slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 7.0 with sodium carbonate solution and then 1.5 g sodium citrate was added. After stirnng for 2 hours at room temperature the solid was recovered by filtration and washed well with distilled water. The recovered solid was calcined in flowing air (100 mL/min) at 400°C for S hours, cooled and then stored in tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 12 ~1% Au on Zirconia 10 g - 325 mesh zirconia (Calsicat #96F-88A, Erie, PA) was slurried into a solution of 0.2 g gold chloride in 50 mL water and 1 drop conc. HCI. The slurry was stirred gently as the pH was adjusted to 9.6 with O.1M sodium carbonate solution. The slurry was stirred gently while 0.69 g sodium citrate solid was slowly added and then stirred for 2 further hours. After filtering and washing well with distilled water; the solid was calcined in flowing air for 5 hours at 250°C.
Experiment 13 ~1 % Au and 0.1 % Pd on Alumina g - 60 mesh y-alumina was slurried into a solution of 0.2 g gold and 0.02 g palladium tetraamine chloride in 50 mL water and one drop of conc. HCI.
The slurry was stirred gently as the pH was adjusted to 9.6 with O.1M sodium 5 carbonate solution. The slurry was again stirred gently while 0.69 g sodium citrate solid was slowly added and then stirred for 2 further hours. After filtering and washing well with distilled water, the solid was calcined in flowing air for 5 hours at 250°C .
EXAMPLES
to Examples 1-22 were run in batch reactor mode, in stirred 3.5 mL glass vials, sealed with septa and plastic caps. Vials were inserted into a block aluminum heater/stirrer apparatus that holds up to 8 vials. Stirring was done using Teflon~-coated stir bars. Each vial was first charged with 1.5 mL of n-octane or undecane solvent, approximately 0.005 or 0.01 g of a given crushed catalyst, a stir bar and the vial was sealed. Vials were stirred and heated approximately 10 minutes to assure that the desired reaction temperature of 125°C had been attained. Next, at the start of each example, 30 ~L of a stock solution of CHHP
and TCB(1,2,4-trichlorobenzene) or CB (chlorobenzene), GC (gas chromatography internal standard, were injected. Stock solutions consisted of 2o mixtures of about 20 wt % TCB or CB in CHHP. The CHHP source contained up to 2.0 wt % of combined cyclohexanol and cyclohexanone. Vials were removed from the aluminum heater/stirrer after a 0.5 to 10 minute period and were allowed to cool to ambient temperature.
In Examples 1-10 (Table I) vials were analyzed directly for the amount of CHHP remaining, using a 15 m DB-17 capillary column with a 0.32 mm internal diameter. The liquid phase of the column was comprised of (50 wt% phenyl) methyl polysiloxane. The column was obtained from J. and W. Scientific, Folsum, California.
GC analyses for the amounts of CHHP in each solution were calculated using the equation:
wt. % CHHP = (area % CHHP/area % TCB) x wt. % TCB x R.F.~HHP
R.F.~HHP (GC response factor for CHHP) was determined from calibration solutions containing known amounts of CHHP and TCB, and was calculated from the equation:
wt. % CHHP/area % CHHP
R.F.~HHP = ~, % TCB/area % TCB
The slurry was stirred gently as the pH was adjusted to 9.6 with O.1M sodium 5 carbonate solution. The slurry was again stirred gently while 0.69 g sodium citrate solid was slowly added and then stirred for 2 further hours. After filtering and washing well with distilled water, the solid was calcined in flowing air for 5 hours at 250°C .
EXAMPLES
to Examples 1-22 were run in batch reactor mode, in stirred 3.5 mL glass vials, sealed with septa and plastic caps. Vials were inserted into a block aluminum heater/stirrer apparatus that holds up to 8 vials. Stirring was done using Teflon~-coated stir bars. Each vial was first charged with 1.5 mL of n-octane or undecane solvent, approximately 0.005 or 0.01 g of a given crushed catalyst, a stir bar and the vial was sealed. Vials were stirred and heated approximately 10 minutes to assure that the desired reaction temperature of 125°C had been attained. Next, at the start of each example, 30 ~L of a stock solution of CHHP
and TCB(1,2,4-trichlorobenzene) or CB (chlorobenzene), GC (gas chromatography internal standard, were injected. Stock solutions consisted of 2o mixtures of about 20 wt % TCB or CB in CHHP. The CHHP source contained up to 2.0 wt % of combined cyclohexanol and cyclohexanone. Vials were removed from the aluminum heater/stirrer after a 0.5 to 10 minute period and were allowed to cool to ambient temperature.
In Examples 1-10 (Table I) vials were analyzed directly for the amount of CHHP remaining, using a 15 m DB-17 capillary column with a 0.32 mm internal diameter. The liquid phase of the column was comprised of (50 wt% phenyl) methyl polysiloxane. The column was obtained from J. and W. Scientific, Folsum, California.
GC analyses for the amounts of CHHP in each solution were calculated using the equation:
wt. % CHHP = (area % CHHP/area % TCB) x wt. % TCB x R.F.~HHP
R.F.~HHP (GC response factor for CHHP) was determined from calibration solutions containing known amounts of CHHP and TCB, and was calculated from the equation:
wt. % CHHP/area % CHHP
R.F.~HHP = ~, % TCB/area % TCB
CHHP Decomp. = 100 x [1-(area % CHHP/area % 1'CB) final/
(area % CHHP/area % TCB initial]
In Examples 1-10 (Table I) the initial concentrations of CHHP in each vial were approximately 2.2 wt %. The GC wt % CHHP;";tial ~d CHHP f~ai numbers are only approximate because the amount of TCB per g solution ratios used in GC
calculations were arbitrarily all made equal to 0.25 mg TCB/ g solution. Since an unheated sample of 1.5 mL n-octane and 30 ~L CHHP/TCB solution was analyzed with each set of CHHP decomposition product vials made from the same CHHP/TCB solution, accurate changes in CHHP/TCB ratios could be calculated.
Examples 11-13 (Table II), and Examples 14-16 (Table III), give batch t-butylhydroperoxide (t-Bu00H) and % cumenehydroperoxide (Cumene00H) decomposition results, respectively for 1% Au/Carbon and 10% Au/Si02 catalysts. Analyses for t-Bu00H and Cumene00H were done using a well known iodometric titration procedure, described in Comprehensive Analytical Chemistry, Elsevier Publishing Company, New York, Eds. C. L. Wilson, p. 756, 1960. Starting and product solutions of t-Bu00H and Cumene00H in n-octane, followed by adding excess KI/ acetic acid solution, were stirred in sealed vials at ambient temperature for 10 minutes and were titrated with 0.1 M Na2S203 solution for amounts of I2 liberated by the t-Bu00H and Cumene00H present.
Examples 17-22 (Tables IV&V) were run as described for Examples 1-10 except that the reaction was run at 150°C and chlorobenzene was used as a GC
internal standard in place of TCB and undecane was used in place of n-octane solvent. In Tables IV and V, the amount of initial CHHP and final CHHP in the reaction was determined by calculating the area of the CHHP GC peak divided by the area of the chlorobenzene GC peak (area % CHHP/area % CB).
TABLE
Method I ReactionTime,Wt% Wt% % CHHP
EX.Catalyst of Approx. CHHP CHHP
Wt% Temp.,min. initialfinalDecomp.
Prep CHHP C
1 1.4% Au/Carbon, Exp. 2.2 125 10 0.4070.22145.7 0.0100 1 2 1.4% Au/Carbon, Exp. 2.2 125 10 0.5370.28147.7 0.0103 I
3 1.4% Au/Si02, Exp. 2.2 125 10 0.4070.3913.9 0.0101 2 4 1.4% Au/Si02, Exp. 2.2 125 10 0.5370.43019.9 0.0101 2 14% Au/Si02, Exp. 2.2 125 10 0.4070.15462.2 0.0102 3 6 14% Au/Si02, Exp. 2.2 125 10 0.4070.13167.8 0.0104 3 7 0% Au/Si02, 0.0103Exp. 2.2 125 10 0.4070.3796.9 8 1.4% Au/A1203, Exp. 2.2 125 10 0.5370.44916.4 0.0102 5 9 13% Ag/Si02> Exp. 2.2 125 10 0.4070.24539.8 0.0102 6 4.5% Cu/Si02, Exp. 2.2 125 10 0.4070.11970.8 0.0103 7 TABLE II
Wt% Wt%
MethodReactionTime,t-Bu00Ht-Bu00H% t-Bu00H
EX.Catalyst, g of Temp., min. initialfinal Decomp.
prep. C
11 1.4% Au/Carbon, Exp. 125 10 0.35 0.20 44 0.0102 1 12 14% Au/Si02, Exp. 125 10 0.35 0.18 48 0.0102 3 13 none 125 10 0.35 0.33 5 TABLE III
Wt% Wt%
t-Cumene-t-Cumene-% t-Cumene-Method ReactionTime,(OOH) (OOH) (OOH) EX. Catalyst, g of prep. Temp., min. initial final Decomp.
C
14 1.4% Au/Carbon, 0.0103125 10 0.55 0.32 42 Exp. 1 14% Au/Si02, 0.0103 125 10 0.55 0.30 45 Exp. 3 16 none 125 10 0.55 0.54 2 TABLE
IV
Approx. CHHP/CHHP/
MethodWt% ReactionTime,CB CB % CHHP
EX.Catalyst of CHHP Temp., min.initialfinalDecomp.
Prep C
17 1 %Au/MgO, 0.0102 Exp. 2.2 150 5 3.41 3.29 3.5 18 1%Au/y-A1203, 0.0120Exp. 2.2 150 5 3.41 0 100 19 I%Au/Si02, 0.0101 Exp. 2.2 150 5 3.41 0.91 73.3 20 1%Au/Ti02, 0.0106 Exp. 2.2 150 5 3.41 2.26 33.6 21 1 % Au/Zr02, 0.0054 Exp. 2 150 0.5 5.26 4.68 11.1 22 1% Au, 0.1% Pd/A1203,Exp. 2 150 0.5 4.82 3.01 37.5 0.0051 13 Examples 23-39 were run in a liquid full plug flow reactor, 30 inches (76 cm) with a '/a inch (0.64 cm) diameter. Inlet and exit pressure was 150 psig (1.03 MPa gauge) controlled with a back pressure regulator. The catalysts were all prepared as in Experiment 13 on 2 mm spheres with the appropriate metal salts and type of alumina, with the exception that reduction was performed by flowing H2 at 150°C instead of sodium citrate. The feed consisted of 1.6%
CHHP in cyclohexane, about 1 % K and 2 % A, and varying amounts of water and acid impurities consisting of monobasic and dibasic acids which would be to typical of those produced in cyclohexane oxidation such as adipic acid, succinic acid, formic acid, and hydroxycaproic acid, in approximately equal amounts.
Analyses were performed on CHHP, K, and A by gas chromatography.
Cyclohexane, CHHP, K, and A were obtained from E. I. du Pont de Nemours and Company, Wilmington, DE. The K/A ratio obtained after conversion of cyclohexylhydroperoxide over the catalyst was calculated using the equation:
(mols K in product) - (mols K in feed) (mols A in product) - (mols A in feed) TABLE V
Ex. Catalyst %CHHP Conv. K/A
23 1 %Au-0.1 %Pd/y-A120364 1.1 24 1 %Au-0.1 %Pt/y-A120364 1. I
1 %Au-0.1 %Ru/y-A120321 I .01 26 1 %Au-0.1 %Ni/Y-A120334 1.00 27 I %Au-0.1 %Co/y-A120345 1.02 28 1 %Au-0. I %Pd/a-A120367 I .91 29 1 %Au-0.1 %Pt/a-A120368 1.84 ~"~.4~ ~ .~ ~ .. 3 ~
~_, ~ .y; PCT/
,~ ,..- [3fi5~
TABLE VI
Gas, %CHHP Feed Exit Benzene, Ex.Catalyst sccm Conv. IUA Benzene, ppm ppm 30 !%Au-O.I%Pd/OC-A12030 60 I.63- _ 3 1 %Au-0. L %Pd/ac-AI203N2, 62 1.74- -! 75 32 1 %Au-0. ! %Pd/oc-AH2, 78 0.47- -33 1%Au-0.1%Pd/OC-AI203H2, 66 0.61- -34 I %Au-0.1 %Pd/CC-AI203H2, 61 0.73- -35 1%Au-0.1%Pd/y-A1203H2, 51 0.31- -36 1%Au-0.1%Pd/aC-AI203H2, - - 5140 4828 .
37 1%Au-0.I%Pd/0G-AI2030 - - 5140 5140 38 1%Au-0.18%Pt/a-A12030 51 1.84- _ 39 1%Au-0.18%Pt/oc.-A1203H2, 73 0.41- -i3 AMENDED SbEET
N .r
(area % CHHP/area % TCB initial]
In Examples 1-10 (Table I) the initial concentrations of CHHP in each vial were approximately 2.2 wt %. The GC wt % CHHP;";tial ~d CHHP f~ai numbers are only approximate because the amount of TCB per g solution ratios used in GC
calculations were arbitrarily all made equal to 0.25 mg TCB/ g solution. Since an unheated sample of 1.5 mL n-octane and 30 ~L CHHP/TCB solution was analyzed with each set of CHHP decomposition product vials made from the same CHHP/TCB solution, accurate changes in CHHP/TCB ratios could be calculated.
Examples 11-13 (Table II), and Examples 14-16 (Table III), give batch t-butylhydroperoxide (t-Bu00H) and % cumenehydroperoxide (Cumene00H) decomposition results, respectively for 1% Au/Carbon and 10% Au/Si02 catalysts. Analyses for t-Bu00H and Cumene00H were done using a well known iodometric titration procedure, described in Comprehensive Analytical Chemistry, Elsevier Publishing Company, New York, Eds. C. L. Wilson, p. 756, 1960. Starting and product solutions of t-Bu00H and Cumene00H in n-octane, followed by adding excess KI/ acetic acid solution, were stirred in sealed vials at ambient temperature for 10 minutes and were titrated with 0.1 M Na2S203 solution for amounts of I2 liberated by the t-Bu00H and Cumene00H present.
Examples 17-22 (Tables IV&V) were run as described for Examples 1-10 except that the reaction was run at 150°C and chlorobenzene was used as a GC
internal standard in place of TCB and undecane was used in place of n-octane solvent. In Tables IV and V, the amount of initial CHHP and final CHHP in the reaction was determined by calculating the area of the CHHP GC peak divided by the area of the chlorobenzene GC peak (area % CHHP/area % CB).
TABLE
Method I ReactionTime,Wt% Wt% % CHHP
EX.Catalyst of Approx. CHHP CHHP
Wt% Temp.,min. initialfinalDecomp.
Prep CHHP C
1 1.4% Au/Carbon, Exp. 2.2 125 10 0.4070.22145.7 0.0100 1 2 1.4% Au/Carbon, Exp. 2.2 125 10 0.5370.28147.7 0.0103 I
3 1.4% Au/Si02, Exp. 2.2 125 10 0.4070.3913.9 0.0101 2 4 1.4% Au/Si02, Exp. 2.2 125 10 0.5370.43019.9 0.0101 2 14% Au/Si02, Exp. 2.2 125 10 0.4070.15462.2 0.0102 3 6 14% Au/Si02, Exp. 2.2 125 10 0.4070.13167.8 0.0104 3 7 0% Au/Si02, 0.0103Exp. 2.2 125 10 0.4070.3796.9 8 1.4% Au/A1203, Exp. 2.2 125 10 0.5370.44916.4 0.0102 5 9 13% Ag/Si02> Exp. 2.2 125 10 0.4070.24539.8 0.0102 6 4.5% Cu/Si02, Exp. 2.2 125 10 0.4070.11970.8 0.0103 7 TABLE II
Wt% Wt%
MethodReactionTime,t-Bu00Ht-Bu00H% t-Bu00H
EX.Catalyst, g of Temp., min. initialfinal Decomp.
prep. C
11 1.4% Au/Carbon, Exp. 125 10 0.35 0.20 44 0.0102 1 12 14% Au/Si02, Exp. 125 10 0.35 0.18 48 0.0102 3 13 none 125 10 0.35 0.33 5 TABLE III
Wt% Wt%
t-Cumene-t-Cumene-% t-Cumene-Method ReactionTime,(OOH) (OOH) (OOH) EX. Catalyst, g of prep. Temp., min. initial final Decomp.
C
14 1.4% Au/Carbon, 0.0103125 10 0.55 0.32 42 Exp. 1 14% Au/Si02, 0.0103 125 10 0.55 0.30 45 Exp. 3 16 none 125 10 0.55 0.54 2 TABLE
IV
Approx. CHHP/CHHP/
MethodWt% ReactionTime,CB CB % CHHP
EX.Catalyst of CHHP Temp., min.initialfinalDecomp.
Prep C
17 1 %Au/MgO, 0.0102 Exp. 2.2 150 5 3.41 3.29 3.5 18 1%Au/y-A1203, 0.0120Exp. 2.2 150 5 3.41 0 100 19 I%Au/Si02, 0.0101 Exp. 2.2 150 5 3.41 0.91 73.3 20 1%Au/Ti02, 0.0106 Exp. 2.2 150 5 3.41 2.26 33.6 21 1 % Au/Zr02, 0.0054 Exp. 2 150 0.5 5.26 4.68 11.1 22 1% Au, 0.1% Pd/A1203,Exp. 2 150 0.5 4.82 3.01 37.5 0.0051 13 Examples 23-39 were run in a liquid full plug flow reactor, 30 inches (76 cm) with a '/a inch (0.64 cm) diameter. Inlet and exit pressure was 150 psig (1.03 MPa gauge) controlled with a back pressure regulator. The catalysts were all prepared as in Experiment 13 on 2 mm spheres with the appropriate metal salts and type of alumina, with the exception that reduction was performed by flowing H2 at 150°C instead of sodium citrate. The feed consisted of 1.6%
CHHP in cyclohexane, about 1 % K and 2 % A, and varying amounts of water and acid impurities consisting of monobasic and dibasic acids which would be to typical of those produced in cyclohexane oxidation such as adipic acid, succinic acid, formic acid, and hydroxycaproic acid, in approximately equal amounts.
Analyses were performed on CHHP, K, and A by gas chromatography.
Cyclohexane, CHHP, K, and A were obtained from E. I. du Pont de Nemours and Company, Wilmington, DE. The K/A ratio obtained after conversion of cyclohexylhydroperoxide over the catalyst was calculated using the equation:
(mols K in product) - (mols K in feed) (mols A in product) - (mols A in feed) TABLE V
Ex. Catalyst %CHHP Conv. K/A
23 1 %Au-0.1 %Pd/y-A120364 1.1 24 1 %Au-0.1 %Pt/y-A120364 1. I
1 %Au-0.1 %Ru/y-A120321 I .01 26 1 %Au-0.1 %Ni/Y-A120334 1.00 27 I %Au-0.1 %Co/y-A120345 1.02 28 1 %Au-0. I %Pd/a-A120367 I .91 29 1 %Au-0.1 %Pt/a-A120368 1.84 ~"~.4~ ~ .~ ~ .. 3 ~
~_, ~ .y; PCT/
,~ ,..- [3fi5~
TABLE VI
Gas, %CHHP Feed Exit Benzene, Ex.Catalyst sccm Conv. IUA Benzene, ppm ppm 30 !%Au-O.I%Pd/OC-A12030 60 I.63- _ 3 1 %Au-0. L %Pd/ac-AI203N2, 62 1.74- -! 75 32 1 %Au-0. ! %Pd/oc-AH2, 78 0.47- -33 1%Au-0.1%Pd/OC-AI203H2, 66 0.61- -34 I %Au-0.1 %Pd/CC-AI203H2, 61 0.73- -35 1%Au-0.1%Pd/y-A1203H2, 51 0.31- -36 1%Au-0.1%Pd/aC-AI203H2, - - 5140 4828 .
37 1%Au-0.I%Pd/0G-AI2030 - - 5140 5140 38 1%Au-0.18%Pt/a-A12030 51 1.84- _ 39 1%Au-0.18%Pt/oc.-A1203H2, 73 0.41- -i3 AMENDED SbEET
N .r
Claims (13)
1. An improved process for decomposing a hydroperoxide to form a decomposition reaction mixture containing a corresponding alcohol and ketone, the improvement comprising decomposing a hydroperoxide by contacting the hydroperoxide with a catalytic amount of a heterogeneous catalyst comprised of gold, wherein 0 to 18% of one or more additional metals selected from the group consisting of Pt, Ru, Ni, and Co are also present with gold.
2. The process according to Claim 1 wherein the heterogeneous catalyst is supported on a catalyst support member.
3. The process according to Claim 2 wherein the catalyst support member is selected from the group consisting of SiO2, A1 2O3, carbon, TiO2, MgO, and zirconia.
4. The process according to Claim 1 wherein the hydroperoxide is cyclohexylhydroperoxide.
5. The process according to Claim 1 or Claim 2 wherein the decomposition reaction temperature is from 80°C to 170°C, and decomposition reaction pressure is from 69 kPa to 2760 kPa.
6. The process according to Claim 5 wherein the reaction pressure is from 276 kPa to 1380 kPa.
7. The process according to Claim 1 or Claim 2 wherein the reaction mixture contains from 0.5 to 100 percent by weight cyclohexyl hydroperoxide.
8. The process according to Claim 1 or Claim 2 wherein the process is run in the presence of cyclohexane.
9. The process according to Claim 1 or Claim 2 wherein the process is run in the presence of added oxygen.
10. The process according to Claim 3 wherein the gold is supported on A1 2O3.
11. The process according to Claim 10 wherein the gold is from 0.1 to 10 wt. percent of the catalyst and support member.
12. The process according to Claim 2 wherein the gold is present on the support member as well-dispersed particles having a diameter from 3 nm to 15 nm.
13. The process according to Claim 1 wherein the process is run in the presence of hydrogen.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1999/005228 WO2000053550A1 (en) | 1999-03-10 | 1999-03-10 | Hydroperoxide decomposition process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2362261A1 true CA2362261A1 (en) | 2000-09-14 |
Family
ID=22272330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002362261A Abandoned CA2362261A1 (en) | 1999-03-10 | 1999-03-10 | Hydroperoxide decomposition process |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1159240A1 (en) |
| JP (1) | JP2002539097A (en) |
| KR (1) | KR20020018999A (en) |
| CN (1) | CN1337930A (en) |
| AU (1) | AU2903199A (en) |
| BR (1) | BR9917285A (en) |
| CA (1) | CA2362261A1 (en) |
| CZ (1) | CZ20013106A3 (en) |
| MX (1) | MXPA01009075A (en) |
| PL (1) | PL357043A1 (en) |
| SK (1) | SK12312001A3 (en) |
| WO (1) | WO2000053550A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10244996A1 (en) * | 2002-09-26 | 2004-04-01 | Basf Ag | Catalyst for the catalytic oxidation of hydrogen chloride |
| JP2004181358A (en) * | 2002-12-03 | 2004-07-02 | Nippon Shokubai Co Ltd | Gold-carrying catalyst for liquid phase reaction and method for producing carboxylic acid ester |
| JP4578820B2 (en) * | 2004-02-19 | 2010-11-10 | トヨタ自動車株式会社 | Method for producing gold catalyst and method for using the same |
| US7081552B2 (en) * | 2004-08-17 | 2006-07-25 | Solutia Inc. | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide |
| CN100364663C (en) * | 2006-04-07 | 2008-01-30 | 浙江大学 | Supported nano Au catalyst and method for preparing the same |
| PT104862A (en) | 2009-12-07 | 2011-06-07 | Univ Tras Os Montes E Alto Douro | HYBRID VANADIUM CATALYSTS AND THEIR USE IN SELECTIVE OXIDATION PROCESSES OF CYCLOALCANES |
| WO2013012203A2 (en) * | 2011-07-15 | 2013-01-24 | 주식회사 엘지화학 | Method of preparing cumyl alcohol and method of preparing phenol, acetone and alpha methyl styrene |
| CN111655660A (en) * | 2018-01-30 | 2020-09-11 | 巴斯夫欧洲公司 | Process for oxidizing cycloalkanes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9100521A (en) * | 1991-03-25 | 1992-10-16 | Stamicarbon | PROCESS FOR PREPARING AN ALKANON AND / OR ALKANOL. |
| US5399794A (en) * | 1993-11-12 | 1995-03-21 | Texaco Chemical Inc. | Use of supported palladium/gold catalysts in the preparation of tertiary butyl alcohol from tertiary butyl hydroperoxide |
| EA002422B1 (en) * | 1997-02-11 | 2002-04-25 | Е.И.Дюпон Де Немур Энд Компани | Hydroperoxide decomposition process |
-
1999
- 1999-03-10 CA CA002362261A patent/CA2362261A1/en not_active Abandoned
- 1999-03-10 MX MXPA01009075A patent/MXPA01009075A/en unknown
- 1999-03-10 JP JP2000603993A patent/JP2002539097A/en active Pending
- 1999-03-10 WO PCT/US1999/005228 patent/WO2000053550A1/en not_active Application Discontinuation
- 1999-03-10 SK SK1231-2001A patent/SK12312001A3/en not_active Application Discontinuation
- 1999-03-10 PL PL99357043A patent/PL357043A1/en unknown
- 1999-03-10 KR KR1020017011432A patent/KR20020018999A/en not_active Application Discontinuation
- 1999-03-10 BR BR9917285-2A patent/BR9917285A/en not_active Application Discontinuation
- 1999-03-10 CN CN99816427A patent/CN1337930A/en active Pending
- 1999-03-10 EP EP99909950A patent/EP1159240A1/en not_active Withdrawn
- 1999-03-10 CZ CZ20013106A patent/CZ20013106A3/en unknown
- 1999-03-10 AU AU29031/99A patent/AU2903199A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CZ20013106A3 (en) | 2002-05-15 |
| SK12312001A3 (en) | 2002-02-05 |
| AU2903199A (en) | 2000-09-28 |
| MXPA01009075A (en) | 2002-03-27 |
| KR20020018999A (en) | 2002-03-09 |
| EP1159240A1 (en) | 2001-12-05 |
| PL357043A1 (en) | 2004-07-12 |
| WO2000053550A1 (en) | 2000-09-14 |
| CN1337930A (en) | 2002-02-27 |
| BR9917285A (en) | 2001-12-26 |
| JP2002539097A (en) | 2002-11-19 |
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