WO2011051642A1 - Hydrocarbon selective oxidation with heterogenous gold catalysts - Google Patents
Hydrocarbon selective oxidation with heterogenous gold catalysts Download PDFInfo
- Publication number
- WO2011051642A1 WO2011051642A1 PCT/GB2009/051461 GB2009051461W WO2011051642A1 WO 2011051642 A1 WO2011051642 A1 WO 2011051642A1 GB 2009051461 W GB2009051461 W GB 2009051461W WO 2011051642 A1 WO2011051642 A1 WO 2011051642A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- gold
- hydrocarbon
- methane
- hydrogen peroxide
- Prior art date
Links
Classifications
-
- 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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
Definitions
- This invention relates to processes and catalysts that convert Ci-C 8 hydrocarbons to a corresponding alcohol, such as methane to methanol, using a supported heterogeneous gold catalyst
- a 247 (2003) 269 reported the selective oxidation of methane using in situ generated hydrogen peroxide and a Pd/C and Cu(CH 3 COO) 2 catalyst system in the presence of trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAA) as solvents.
- Pd/C is an in situ H 2 0 2 generator
- Cu(CH 3 COO) 2 is the oxidation catalyst.
- the reaction conditions were 80 °C, 5 ml_ solvent and total pressure of 47.64 atm (71.4% CH 4 , 14.3% H 2 , 14.3% 0 2 ).
- the inventors have recognized that an environmentally benign and economically attractive solution could be the use of 0 2 and H 2 0 2 as oxidants and the use of non-toxic solvents, such as water. Recently it has been shown by Qiang Yuan et a/., Adv. Synth. Catal. 349 (2007) 1199, that it is possible to oxidize methane in an aqueous medium using metal chlorides and H 2 0 2 , wherein the catalytic system was based on the use of hydrogen peroxide in water using homogeneous transition metal chlorides (e.g.
- This method has several process disadvantages which include the homogeneous catalysts are highly soluble in water and therefore pose a separation problem from recycle and reuse. It would be highly preferable to use a heterogeneous catalyst that could be recovered and reused. In addition, these homogeneous catalysts show undesirable selectivities toward highly oxidized carbon species such as formic acid and C0 2. It is desired to have significantly higher selectivities for these oxidation reactions.
- This invention in one broad respect, is a process for forming an alcohol from a hydrocarbon, such as methanol from methane.
- the first process embodiment involves contacting hydrogen peroxide and a Ci-C 8 hydrocarbon in the presence of a heterogeneous catalyst in a liquid solution to convert the Ci-C 8 hydrocarbon to a corresponding Ci-C 8 alcohol, wherein the heterogeneous catalyst comprises gold on a solid support.
- liquid solution it is meant any medium that is a liquid under the process conditions.
- the hydrocarbon can be fed, with or without other diluent, as either a gas or a liquid to the reaction, preferably at pressures from 1 atmospheres (atm), to 140 atm (101 - 14185 kPa)more preferably from 8 atm to 100 atm (810 - 10132 kPa), most preferably from 20 atm to 70 atm (2026 - 8106 kPa). That is, the process is conducted to maintain such pressures.
- a heterogeneous catalyst means one that is not being solubilized in the liquid solution.
- the liquid solution is an aqueous media (e.g., distilled water).
- the heterogeneous gold catalyst activates a hydrocarbon and H 2 0 2 mixture to form a corresponding alcohol at temperatures preferably of from 0 °C to 200 °C, more preferably from 10°C to 100 °C, and most preferably from 30 °C to 90 °C.
- those heterogeneous gold catalysts can oxidize methane to methanol in water using hydrogen peroxide at temperatures as low as 30 °C thereby advantageously circumventing the need for high temperatures to activate methane where selectivity losses to CO or C0 2 are observed.
- the in situ generation of hydrogen peroxide at temperatures preferably from 0 °C to 200 °C, more preferably from 10 to 100 °C, and most preferably from 30 °C to 90 °C activates methane to form methanol over the gold comprising catalysts.
- the hydrocarbon is fed, with or without other diluent as either a gas or a liquid to the reaction, preferably at pressures from 1 atm to 140 atmospheres (atm), more preferably from 8 to 100 atm, and most preferably from 20 atm to 70 atm. It was found that adding palladium or copper to the gold comprising catalyst improved yields and selectivity to the desired alcohol.
- this invention is a process for the production of an alcohol by contacting the hydrocarbon with a heterogeneous catalyst comprising gold.
- a heterogeneous catalyst comprising gold.
- Other metals may be added to gold as a promoter to facilitate conversion of the hydrocarbon to desired products.
- the addition of copper or palladium to the gold increased the alcohol selectivity of the catalyst.
- a catalyst based on gold and palladium when contacting hydrogen peroxide and a Ci-C 8 hydrocarbon in the presence of the heterogeneous catalyst in a liquid solution converts the Ci-C 8 hydrocarbon to primarily the corresponding Ci-C 8 alcohol.
- the reaction temperature can be in the range from 30 °C to 90 °C; the process can be conducted under a total system pressure of from 1 atm to 140 atm; the hydrocarbon can be methane, ethane, propane, or a combination thereof (any combination of methane, ethane, and propane); the process can be conducted such that the hydrocarbon that is not in solution is at least partially in the gas phase at a pressure of up to 100 atm; the liquid solution can contain at least 90% water; the catalyst can contain gold and palladium; the catalyst can contain gold, palladium, and copper; the support can be composed of carbon, titania, ceria, iron oxide, copper oxide, silica, alumina, or a combination thereof; the catalyst can be prepared by impregnation, sol immobilization, chemical vapor infiltration, or a combination thereof; the catalyst can be calcined to increase the selectivity to the alcohol; the catalyst can contain gold in an amount of from 0.5 to 10 percent by weight based on the
- This invention relates to processes and catalysts that convert Ci-C 3 hydrocarbons to a corresponding alcohol, such as methane to methanol, using a supported heterogeneous gold or promoted-gold catalyst.
- the hydrocarbons used in the practice of this invention generally contain from 1 to 8 carbon atoms (i.e., Ci-C 8 ).
- the hydrocarbons can be saturated or unsaturated, cyclic or linear or any combination thereof.
- the hydrocarbon is methane.
- the hydrocarbon is cyclohexane.
- the hydrocarbon is octane.
- the hydrocarbons are selected such that in the practice of this invention a given hydrocarbon will react to form an alcohol. Mixtures of hydrocarbons can be used as the feedstock in the practice of this invention.
- hydrogen peroxide is used directly, without formation in situ.
- hydrogen peroxide can be used as an aqueous mixture, as is commonly available commercially.
- the hydrogen peroxide can be employed in concentrated form, or can be diluted with additional water or other suitable solvent such as methanol.
- the amount of hydrogen peroxide used is effective to at least partially oxidize the hydrocarbon to its corresponding alcohol. Typically the amount of hydrogen peroxide used will be sufficient to maximize the amount of hydrocarbon being oxidized to its corresponding alcohol, without over- oxidation of the resulting product.
- the hydrocarbon can be feed, with or without other diluent, as either a gas or a liquid to the reaction medium containing the aqueous hydrogen peroxide solution, preferably at pressures from 1 atm to 140atm, more preferably from 8 atm to 100 atm, most preferably from 20 atm to 70 atm.
- the heterogeneous gold catalyst activates a hydrocarbon and H 2 0 2 mixture to form a corresponding alcohol at temperatures preferably from 0 °C to 200 °C, more preferably from 10 °C to 100 °C, and most preferably from 30°C to 90 °C.
- the second embodiment of this process generates hydrogen peroxide in the aqueous media in situ from hydrogen and a source of oxygen.
- Any source of hydrogen can be used in the process of this invention such as is available commercially as well as, for example, molecular hydrogen obtained from the dehydrogenation of hydrocarbons and alcohols.
- any source of oxygen can be employed, including air or pure oxygen.
- any amounts of hydrogen and oxygen can be employed in the process provided that the amount is sufficient to produce hydrogen peroxide in the desired quantities to achieve the desired conversion of hydrocarbon to a corresponding alcohol.
- the hydrogen peroxide is generated through the use of a heterogeneous catalyst in the liquid phase.
- in situ it is meant that the hydrogen peroxide is produced within the reactor simultaneous (contemporaneously) with the oxidation of the hydrocarbon.
- an aqueous media is placed in suitable reactor, wherein the aqueous media includes the catalyst.
- the hydrogen/oxygen mixture is typically mixed with methane and an optional diluent and pressurized up to a total pressure preferably from 1 to 140 atmospheres (atm), more preferably from 8 to 100 atm, most preferably from 20 to 70 atm.
- a ratio of H 2 :0 2 from 1 :5 to 5: 1 with optional diluent are useful from forming the in situ hydrogen peroxide, more preferably ratios of H 2 :0 2 from 1 :3 to 3: 1 are useful, and most preferably H 2 :0 2 ratios of 1 :2 to 2: 1 are useful. It is advisable to employ H 2 :0 2 ratios with appropriate hydrocarbon and diluent pressure to avoid using explosive mixtures.
- the particular pressure for H 2 , 0 2 , gaseous hydrocarbon and diluent used in a given reaction can vary depending on for example the equipment, the phase of hydrocarbon reactant , the hydrogen/oxygen ratio, and concentration of hydrocarbon either in the gas phase or present in any diluent (e.g. in an aqueous media).
- a reaction temperature is maintained preferably from 0 °C to 200 °C, more preferably from 10 °C to 100 °C, and most preferably from 30 °C to 90 °C.
- the catalysts used in any process embodiment herein are heterogeneous gold- containing catalysts.
- the catalysts can contain other metals such as copper and palladium, for example, to facilitate in situ production of hydrogen peroxide and/or alkane oxidation.
- the catalyst contains gold and palladium.
- the catalyst contains gold and copper.
- the catalyst contains gold, palladium, and copper.
- the gold can be supported on a variety of materials, including but not limited to carbon, ceria, iron oxide, copper oxide, silica, titania, and alumina supports. It is further embodied that copper oxide or hydroxide may be used as a support for gold or palladium.
- the catalysts may be formed into a variety of shapes and sizes and by a variety of methods.
- the support may be combined with a binder into extrudate or pellets for added strength and durability.
- the catalysts can be made using a variety of well known methods.
- a solution is used to load a metal onto a solid support.
- an aqueous gold solution is formed from a suitable salt such as HAuCI 4 .
- another metal may be added to solution.
- palladium may be added such as through use of palladium chloride (PdCI 2 ).
- the aqueous solution's temperature, concentration, pH, and other variables can be adjusted depending on the desired characteristics of the final catalyst.
- the concentration of gold and other metal or metals can be adjusted relative to each other and relative to the amount of solid support being used in order to produce a final catalyst with the desired metal loading and relative composition on the support.
- the support is slowly added to the aqueous metal solution, with stirring, to form a suspension where the metals are incorporated on the support.
- the catalyst may thereafter be dried and/or calcined, if desired, at a temperature of from 100 to 600 °C, though the temperature may vary depending on the composition of the catalyst.
- the catalyst can be formed by a variety of other well known techniques, such as impregnation to incipient wetness, deposition precipitation (with or without urea), sol immobilization, and chemical vapor deposition as shown in the examples.
- the catalysts generally contain gold in amounts from preferably 0.001 to 10 percent by weight based on the total weight of the catalyst, more preferably in the range of 1 to 5 percent by weight, and most preferably in the range of 2 to 3 percent.
- the catalysts generally contain palladium in amounts from preferably 0.001 to 10 percent by weight based on the total weight of the catalyst, more preferably in the range of 1 to 5 percent by weight, and most preferably in the range of 2 to 3 percent.
- the catalyst can include copper in amounts of from preferably 0.001 to 10 percent by weight, more preferably in the range of 1 to 5 percent and most preferably in the range of 2 to 3 percent. If other metals such as promoters are present, they are typically in an amount of from 0.001 to 5 percent by weight of the total catalyst.
- the amount of catalyst employed in a given reaction can vary widely.
- the catalyst can be used in any amount that provides conversion (oxidation) of at least a portion of the hydrocarbon to be converted into a corresponding alcohol. It is possible to employ two or more catalysts in the practice of this invention, which might achieve a specific result that is unachievable with a single catalyst.
- Titania (P25, 99.5%) was supplied by Degussa, ceria and alumina were supplied by Aldrich. All reactive compositions in this work have been analyzed as using the following procedures: The gas mixture of the reactor was removed using a gas sampling bag and analysis was performed using gas chromatography. The liquid-phase products were analyzed by High performance liquid chromatography (HPLC), H nuclear magnetic resonance (NMR). D 2 0 was used as the lock reference. In the case of H NMR analysis, a sealed capillary tube was prepared with a solution of TMS (tetramethylsilane) and CHCI 3 (chloroform).
- H 2 0 2 yield was determined by titration of aliquots of the final filtered solution with acidified Ce(S0 4 ) 2 solutions were standardized against (NH 4 ) 2 Fe(S0 4 ) 2 -6H 2 0 using ferroin as indicator.
- Example 1 Preparation of a Au/Ti0 2 catalyst by impregnation
- the Au/Ti0 2 catalyst is prepared by impregnation of an aqueous solution HAuCI 4 .3H 2 0 onto the necessary amount of Ti0 2 (Degussa, P25) support to achieve a final loading of 2.5% by weight.
- the gold solution is prepared by adding 5 grams of HAuCI 4 -3H 2 0 to 250 mL deionized water with vigorous stirring. After the complete dissolution of the gold salt, 1.9 grams of the support is added very slowly into 5 ml of the solution and continuously stirred until it became homogeneous. The slurry is kept in the oven for 16 hrs at 1 10 °C. This catalyst is designated herein as catalyst E1.
- Example 2 Liquid phase oxidation of methane with hydrogen peroxide using a Au/Ti0 2 catalyst
- the catalytic oxidation of methane is carried out using a stainless-steel autoclave (Parr reactor) containing a Teflon liner vessel with total volume of 50 ml.
- a measured amount of the catalyst from Example 1 E1 corresponding to 10 ⁇ 5 mol of metal is added into the Teflon vessel, which was pre-charged with a 10 ml solution of distilled water and the desired amount of H 2 0 2 (50 wt% H 2 0 2 , 0.005 mol of H 2 0 2 ).
- the total volume of the reaction solution is 10 ml.
- the system is pressurized with methane to a fixed pressure (440 psi, 0.05 mol) after air in the reactor is removed with the reactant (purging 3 times with methane at 200 psi, 13.61 bar).
- the autoclave is heated to 90 °C. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 2 hours. At the end of the reaction the autoclave is cooled with ice to a temperature of 12 °C to minimize the methanol volatility and loss. Products are subsequently analyzed and the results are shown in Table 1.
- Example 2.1 Liquid phase oxidation of methane with hydrogen peroxide using a calcined Au/Ti02 catalyst.
- Example 2 The oxidation process of Example 2 is repeated with the following modifications. Fresh catalyst E1 is calcined at 400 °C for 3 hours in static air before use in the reaction. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 4 hours. Products are subsequently analyzed and the results are shown in Table 1 . An improved methanol selectivity is observed.
- Example 3 Preparation of a AuPd/Ti0 2 catalyst by impregnation
- the AuPd/Ti0 2 catalyst is prepared by impregnation of aqueous solutions of PdCI 2 and HAuCI 4 -3H 2 0 onto the necessary amount of Ti0 2 (Degussa, P25) support to achieve a final loading of 5% wt (2.5wt%Au-2.5wt%Pd) by weight.
- the gold solution is prepared by adding 5 grams of HAuCI 4 -3H 2 0 to 250 ml. deionized water.
- the Pd precursor (0.083 grams) is dissolved into 5 ml of the gold solution with vigorous stirring. After the complete dissolution of the salts, 1.9 grams of the support is added very slowly into the 5 ml of the solution and continuously stirred until it became homogeneous. The slurry is kept in the oven for 16 hrs at 1 10 °C.
- This catalyst is designated herein as catalyst E3.
- Example 4 Liquid phase oxidation of methane with hydrogen peroxide using a
- Example 2 The oxidation process of Example 2 is carried out using the catalyst E3 of Example 3. Products are subsequently analyzed and the results are shown in Table 1.
- Example 5 Preparation of a AuPdCu/Ti0 2 catalyst by impregnation
- the AuPdCu/Ti0 2 catalyst is prepared by impregnation of aqueous solutions of PdCI 2 , CuCI 2 and HAuCI 4 3H 2 0 onto the necessary amount of Ti0 2 (Degussa, P25) support to achieve a final loading of 7.5% wt (2.5wt%Au-2.5wt%Pd-2.5wt%Cu) by weight.
- the gold solution is prepared by adding 5 grams of HAuCI 4 -3H 2 0 to 250 mL deionized water.
- the Pd precursor (0.083 grams) is dissolved into 5 ml of the gold solution with vigorous stirring.
- Example 6 Liquid phase oxidation of methane with hydrogen peroxide using a
- Example 2 The oxidation process of Example 2 is carried out using the catalyst E5 of Example 5 with the following modifications.
- Fresh catalyst E5 is calcined at 400 °C for 3 hours in static air before use in the reaction.
- the reaction temperature used is 50 " C. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 0.5 hours. Products are subsequently analyzed and the results are shown in Table 1 .
- Example 7 Liquid phase oxidation of methane with hydrogen peroxide using a calcined AuPd/Ti0 2 catalyst
- Example 2 The oxidation process of Example 2 is repeated with the following modifications.
- Fresh catalyst E4 is calcined at 400 °C for 3 hours in static air before use in the reaction. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 0.5 hours. Products are subsequently analyzed and the results are shown in Table 1 .
- Example 7.1 Liquid phase oxidation of methane with hydrogen peroxide using a calcined AuPd/Ti0 2 catalyst at lower temperatures
- Example 2 The oxidation process of Example 2 is repeated with the following modifications. Fresh catalyst E4 is used, and the reaction temperature is 50 °C. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 0.5 hours. The catalyst is still quite active despite the very low temperature. Products are subsequently analyzed and the results are shown in Table 1.
- Example 8 Liquid phase oxidation of methane with hydrogen peroxide at higher pressures
- Example 2 The oxidation process of Example 2 is repeated with the following modifications.
- Fresh catalyst E4 is used, and is calcined at 400 °C for 3 hours in static air before use in the reaction.
- the reaction temperature used is 50 °C, while the methane pressure is increased to 50 atmospheres. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 0.5 hours. Products are subsequently analyzed and the results are shown in Table 1. It is evident that more alcohol product is formed at higher methane pressures.
- a 2.5 wt. % Au/C catalyst is prepared by the method of Example 1 where the Ti0 2 support is substituted for carbon (Aldrich, G60). The dried Au/C catalyst is calcined at 400 °C for 3 hours in static air before use in the reaction. This catalyst is designated herein as catalyst E9. .Products are subsequently analyzed and the results are shown in Table 1.
- Example 10 Liquid phase oxidation of methane with hydrogen peroxide using a Au/C catalyst
- Example 2 The oxidation process of Example 2 is repeated with the following modifications. Fresh catalyst of E9 is used at a final reaction temperature of 50 °C. Once the reaction temperature is attained the solution is vigorously stirred at 1500 rpm and maintained at the reaction temperature for 4 hours. Products are subsequently analyzed and the results are shown in Table 1.
- Example 11 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Ti0 2 catalyst.
- the catalytic oxidation of methane is carried out using a stainless-steel autoclave (Parr reactor) containing a Teflon vessel with total volume of 50 ml.
- Fresh catalyst E4 is calcined at 400 °C for 3 hours in static air, and a measured amount corresponding to 10 ⁇ 5 mol of metal is added into the Teflon vessel, which is pre-charged with a 10 ml solution of distilled water.
- the total volume of the reaction solution is 10 ml.
- the autoclave is purged three times with 5%/H 2 /N 2 (7.8 atm) and then filled successively with 5%H 2 /N 2 (5.4 atm), 25%0 2 /N 2 (2.2 atm) and CH 4 (24 atm).
- Example 12 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Ti0 2 catalyst at lower temperatures
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature was 50 °C.
- Fresh catalyst E4 that is calcined at 400 °C for 3 hours in static air is used. Products are subsequently analyzed and the results are shown in Table 2.
- Example 13 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Ti0 2 and lower temperature
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- Fresh catalyst E4 is calcined at 400 °C for 3 hours in static air and used, but with a reaction temperature of 30 °C.
- C0 2 is added as the diluent.
- the autoclave is purged three times with 5%/H 2 /C0 2 (7.8 atm) and then filled successively with 5%H 2 /C0 2 (21.8 atm), 25%0 2 /C0 2 (8.7 atm) and CH 4 (24 am).
- the total pressure is 55.5 atm.
- the total reaction time is altered to be 4 hours. Gas phase C0 2 after reaction could not be measured for experiments with C0 2 as diluent. Products are subsequently analyzed and the results are shown in Table 2.
- Example 13.1 Liquid phase oxidation of methane with gas-phase 0 2 , and diluent using a AuPd/Ti0 2 .
- Example 1 1 The oxidation process of Example 1 1 was repeated with the following modifications.
- Fresh catalyst E4 that is calcined at 400 °C for 3 hours in static air and used at a reaction temperature of 50 °C.
- the autoclave is purged three times with 25%0 2 /C0 2 (7.8 atm) and then filled successively with 25%0 2 /C0 2 (9.0 atm) and CH 4 (24 atm).
- the total pressure is 36 atm.
- the total reaction time is altered to be 4 hours.
- Gas phase C0 2 after reaction could not be measured for experiments with C0 2 as diluent. No products are detected, demonstrating the necessity for H 2 to form the active hydrogen peroxide in solution. Products are subsequently analyzed and the results are shown in Table 2.
- Example 14 Preparation of a AuPd/Si0 2 catalyst by impregnation.
- catalyst E15 The preparation method of E3 is followed using Ce0 2 (99.9%, Aldrich) instead of Ti0 2 as the support material. The final result is a 2.5wt.%Au-2.5wt.%Pd/Ce0 2 catalyst. This material is calcined at 400 °C for 3 hours in static air before use in the reaction. This catalyst is designated herein as catalyst E15.
- Example 16 Preparation of a AuPd/AI 2 0 3 catalyst by impregnation.
- catalyst E16 The preparation method of E3 was followed using ⁇ - ⁇ 2 0 3 (99.7%, Aldrich) instead of Ti0 2 as the support material. The final result is a 2.5wt.%Au-2.5wt.%Pd/AI 2 0 3 catalyst. This material is calcined at 400 °C for 3 hours in static air before use in the reaction. This catalyst is designated herein as catalyst E16.
- Example 17 Preparation of a AuPd/C catalyst by impregnation.
- Example 18 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Si0 2 catalyst.
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature is 50 °C.
- Fresh catalyst E14 that is calcined at 400 °C for 3 hours in static air is used. Products are subsequently analyzed and the results are shown in Table 2.
- Example 19 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Ce0 2 catalyst.
- Example 20 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/y-AI 2 0 3 catalyst.
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature is 50 °C.
- Fresh catalyst E16 that is calcined at 400 °C for 3 hours in static air is used. Products are subsequently analyzed and the results are shown in Table 2.
- Example 21 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/C catalyst.
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature is 50 °C.
- Fresh catalyst E17 that is calcined at 400 °C for 3 hours in static air is used. Products are subsequently analyzed and the results are shown in Table 2.
- Example 22 Preparation of a AuPdCu/Ti0 2 catalyst by chemical vapor infiltration (CVI) and impregnation
- Fresh dried catalyst from example E3 (1 gram) is placed into a vacuum finger flask containing copper acetylacetonate (0.103 grams, Aldrich) and a stirrer bar under reduced pressure within the range of 10 ⁇ 3 mbar. Under vacuum, the volatile copper precursor is deposited on the AuPd/Ti0 2 catalyst to a nominal metal loading of 2.5wt% Cu. The final catalyst has a composition of 2.5%Au-2.5%Pd-2.5%Cu/Ti0 2 . Approximately 0.9 g of catalyst is recovered. This catalyst is designated herein as catalyst 22..
- Example 23 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using an impregnated AuPdCu/Ti0 2 catalyst.
- Example 23.1 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using an impregnated+CVI AuPdCu/Ti0 2 catalyst.
- Example 1 1 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature is 50 °C.
- Fresh catalyst E22 that is calcined at 400 °C for 3 hours in static air is used.
- a 10 mg catalyst charge is used in the reactor.
- Products are subsequently analyzed and the results are shown in Table 2. The result clearly show that the addition of Cu via CVI has produced a more active and selective catalyst as compared to Cu deposited by impregnation.
- Example 24 Preparation of a AuPd/Ti0 2 catalyst by sol immobilization
- An Au-Pd bimetallic sol (1 :1 molar ratio) is prepared using aqueous PdCI 2 and HAuCI 4 solutions of 1 .648 10 "4 M.
- the colloid is immobilized by adding Ti0 2 (Degussa P25).
- the solution is acidified to pH 1 by the addition of sulphuric acid under vigorous stirring.
- the amount of Ti0 2 (2 grams) added is calculated as having a total final metal loading of 1 % wt.
- the slurry is filtered, the catalyst washed thoroughly with distilled water and dried in air at 120 °C overnight. This catalyst is designated herein as catalyst E24.
- Example 25 Liquid phase oxidation of methane with gas-phase H 2 , 0 2 , and diluent using a AuPd/Ti0 2 catalyst prepared by sol immobilization.
- Example 2 The oxidation process of Example 1 1 is repeated with the following modifications.
- the reaction temperature is 50 °C.
- Fresh catalyst E24, 10 mg, is used without further treatment. Products are subsequently analyzed and the results are shown in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/393,560 US20120203035A1 (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
PCT/GB2009/051461 WO2011051642A1 (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
EP09748840.7A EP2493837B1 (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
CN200980162198.0A CN102648172B (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
BR112012009789A BR112012009789A2 (en) | 2009-10-29 | 2009-10-29 | process for the production of an alcohol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/GB2009/051461 WO2011051642A1 (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011051642A1 true WO2011051642A1 (en) | 2011-05-05 |
WO2011051642A8 WO2011051642A8 (en) | 2011-07-14 |
Family
ID=42314241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2009/051461 WO2011051642A1 (en) | 2009-10-29 | 2009-10-29 | Hydrocarbon selective oxidation with heterogenous gold catalysts |
Country Status (5)
Country | Link |
---|---|
US (1) | US20120203035A1 (en) |
EP (1) | EP2493837B1 (en) |
CN (1) | CN102648172B (en) |
BR (1) | BR112012009789A2 (en) |
WO (1) | WO2011051642A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013114330A1 (en) * | 2012-02-03 | 2013-08-08 | Invista Technologies S.A R.L. | Oxidation of cycloalkanes in the presence of a supported bimetallic gold - palladium catalyst |
WO2018206981A1 (en) * | 2017-05-12 | 2018-11-15 | University College Cardiff Consultants Ltd | Hydrocarbon oxidation |
US11572330B2 (en) | 2018-01-30 | 2023-02-07 | Basf Se | Method for oxidation of cycloalkanes |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011161276A1 (en) | 2010-06-25 | 2011-12-29 | University College Cardiff Consultants Limited | Selective oxidation of hydrocarbons using heterogeneous catalysts |
US10519084B2 (en) * | 2016-10-20 | 2019-12-31 | Wichita State University | Conversion of natural gas into clean liquid fuels |
CN107915581A (en) * | 2017-12-08 | 2018-04-17 | 西安近代化学研究所 | A kind of preparation method of 2,2,3,3,3 5 fluorine propyl alcohol |
CN111004091A (en) * | 2019-12-12 | 2020-04-14 | 西安近代化学研究所 | Method for preparing 4,4,5,5, 5-penta-fluoropentanol |
CN111644197A (en) * | 2020-05-15 | 2020-09-11 | 北京化工大学 | Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application |
CN114515572B (en) * | 2020-11-19 | 2024-01-26 | 中国石油化工股份有限公司 | Gold catalyst for directly synthesizing hydrogen peroxide and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1041046A (en) * | 1962-06-21 | 1966-09-01 | Ici Ltd | Oxidation of hydrocarbons and alcohols |
US20060293175A1 (en) * | 2005-06-24 | 2006-12-28 | Sheng Dai | Surface-stabilized gold nanocatalysts |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6906208B2 (en) * | 1999-09-07 | 2005-06-14 | Abb Lummus Global Inc. | Mesoporous material and use thereof for the selective oxidation of organic compounds |
US8202916B2 (en) * | 2004-07-29 | 2012-06-19 | Gas Technologies Llc | Method of and apparatus for producing methanol |
EP2017249A1 (en) * | 2007-07-19 | 2009-01-21 | Total Petrochemicals Research Feluy | Process for the selective oxidation of methane |
-
2009
- 2009-10-29 EP EP09748840.7A patent/EP2493837B1/en not_active Not-in-force
- 2009-10-29 WO PCT/GB2009/051461 patent/WO2011051642A1/en active Application Filing
- 2009-10-29 US US13/393,560 patent/US20120203035A1/en not_active Abandoned
- 2009-10-29 CN CN200980162198.0A patent/CN102648172B/en not_active Expired - Fee Related
- 2009-10-29 BR BR112012009789A patent/BR112012009789A2/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1041046A (en) * | 1962-06-21 | 1966-09-01 | Ici Ltd | Oxidation of hydrocarbons and alcohols |
US20060293175A1 (en) * | 2005-06-24 | 2006-12-28 | Sheng Dai | Surface-stabilized gold nanocatalysts |
Non-Patent Citations (6)
Title |
---|
GASIOR M ET AL: "Oxidation of CO and C3 hydrocarbons on gold dispersed on oxide supports", CATALYSIS TODAY, ELSEVIER, NL LNKD- DOI:10.1016/J.CATTOD.2004.03.021, vol. 91-92, 15 July 2004 (2004-07-15), pages 131 - 135, XP002336267, ISSN: 0920-5861 * |
KALVACHEV Y A ET AL: "Vapor-Phase Selective Oxidation of Aliphatic Hydrocarbons over Gold Deposited on Mesoporous Titanium Silicates in the Co-Presence of Oxygen and Hydrogen", JOURNAL OF CATALYSIS, ACADEMIC PRESS, DULUTH, MN, US LNKD- DOI:10.1006/JCAT.1999.2540, vol. 186, no. 1, 15 August 1999 (1999-08-15), pages 228 - 233, XP004443112, ISSN: 0021-9517 * |
LIGNIER ET AL: "Insight into the free-radical chain mechanism of gold-catalyzed hydrocarbon oxidation reactions in the liquid phase", CATALYSIS TODAY, ELSEVIER, NL LNKD- DOI:10.1016/J.CATTOD.2007.02.006, vol. 122, no. 3-4, 10 May 2007 (2007-05-10), pages 284 - 291, XP022068745, ISSN: 0920-5861 * |
M.D.HUGHES ET AL: "Tunable gold catalysts for selective hydroncarbon oxidation under mild conditions", NATURE, vol. 437, 2005, pages 1132 - 1135, XP009136486 * |
YI-JUN XU ET AL: "Selective conversion of cyclohexane to cyclohexanol and cyclohexanone using a gold catalyst under mild conditions", CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 101, no. 3-4, 1 June 2005 (2005-06-01), pages 175 - 179, XP019275159, ISSN: 1572-879X * |
ZHAO R ET AL: "A HIGHLY EFFICIENT OXIDATION OF CYCLOHEXANE OVER AU/ZSM-5 MOLECULAR SIEVE CATALYST WITH OXYGEN AS OXIDANT", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, CHEMICAL SOCIETY. LETCHWORTH, GB, vol. 7, 1 January 2004 (2004-01-01), pages 904/905, XP009071039, ISSN: 0022-4936 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013114330A1 (en) * | 2012-02-03 | 2013-08-08 | Invista Technologies S.A R.L. | Oxidation of cycloalkanes in the presence of a supported bimetallic gold - palladium catalyst |
CN104350032A (en) * | 2012-02-03 | 2015-02-11 | 英威达技术有限公司 | Oxidation of cycloalkanes in the presence of a supported bimetallic gold - palladium catalyst |
WO2018206981A1 (en) * | 2017-05-12 | 2018-11-15 | University College Cardiff Consultants Ltd | Hydrocarbon oxidation |
US10934236B2 (en) | 2017-05-12 | 2021-03-02 | University College Cardiff Consultants Ltd | Hydrocarbon oxidation |
US11572330B2 (en) | 2018-01-30 | 2023-02-07 | Basf Se | Method for oxidation of cycloalkanes |
Also Published As
Publication number | Publication date |
---|---|
WO2011051642A8 (en) | 2011-07-14 |
BR112012009789A2 (en) | 2019-09-24 |
EP2493837A1 (en) | 2012-09-05 |
EP2493837B1 (en) | 2014-04-23 |
US20120203035A1 (en) | 2012-08-09 |
CN102648172A (en) | 2012-08-22 |
CN102648172B (en) | 2014-11-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2493837B1 (en) | Hydrocarbon selective oxidation with heterogenous gold catalysts | |
Della Pina et al. | Selective oxidation using gold | |
Beckman | Production of H 2 O 2 in CO 2 and its use in the direct synthesis of propylene oxide | |
EP2671861B1 (en) | Selective oxidation of hydrocarbons using heterogeneous catalysts | |
US6040460A (en) | High productivity process to produce maleic anhydride from n-butane | |
TWI389843B (en) | Initiating a reaction between hydrogen peroxide and an organic compound | |
EP1443020B1 (en) | Integrated process for selective oxidation of organic compounds | |
KR20010109490A (en) | Catalyst and process for the direct synthesis of hydrogen peroxide | |
CN102079694B (en) | Preparation method of cyclohexanone from oxidation of cyclohexanol | |
EP2493838B1 (en) | Selective catalytic oxidation of c1-c3 alkanes | |
Wang et al. | Copper and manganese: two concordant partners in the catalytic oxidation of p-cresol to p-hydroxybenzaldehyde | |
CN101619048B (en) | Method for synthesizing propylene oxide | |
EP1080063A1 (en) | Method of preparing alkyl carboxylic acids by carboxylation of lower alkanes methane | |
US6028221A (en) | Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same | |
WO2016203283A1 (en) | Use of molybdenum and vanadium mixed oxides as catalysts for the oxidation of unsaturated alcohols into unsaturated carboxylic acids | |
US20100022786A1 (en) | Method for producing epoxy compound | |
US8901028B2 (en) | Selective hydrocarbon oxidation using heterogenous catalysts | |
CN115430418A (en) | Catalyst, preparation method thereof and method for preparing acetic acid by using catalyst | |
Qadir et al. | Transition metal-catalyzed hydrogenation of carbon dioxide in ionic liquids | |
JPS6113689B2 (en) | ||
WO2000006528A1 (en) | Process for producing adipic acid | |
WO2021062916A1 (en) | Method for catalytically synthesizing ketoisophorone using perovskite-type composite oxide | |
CN111393397A (en) | Preparation method of 2, 5-furandicarboxylic acid | |
JPH0121138B2 (en) | ||
Chowdhury et al. | Recent Developments in Gold Nanomaterial Catalysts for Oxidation Reaction through Green and Sustainable Routes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980162198.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09748840 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13393560 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009748840 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012009789 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012009789 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120426 |