CN1337930A - Hydroperoxide decomposition process - Google Patents
Hydroperoxide decomposition process Download PDFInfo
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- CN1337930A CN1337930A CN99816427A CN99816427A CN1337930A CN 1337930 A CN1337930 A CN 1337930A CN 99816427 A CN99816427 A CN 99816427A CN 99816427 A CN99816427 A CN 99816427A CN 1337930 A CN1337930 A CN 1337930A
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- chhp
- gold
- hydroperoxide
- catalyst
- decomposition
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- 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
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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
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- 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
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- 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
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- 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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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 the catalitic amount of a heterogenous catalyst comprised of gold, wherein one or more additional selected from Periodic Group Vlll is/are also present with gold. Moreover, the catalysts are optinally supported on a suitable support member, such as SiO, Al O, carbon, zirconia, MgO or TiO. The process may also optionally be run in the presence of hydrogen gas.
Description
Invention field
The present invention relates generally to be used to decompose a kind of improvement catalysis process that alkyl or aromatics hydroperoxy-form the mixture that contains correspondent alcohol and ketone.Especially, the present invention relates to by hydroperoxide are contacted with a kind of heterogeneous catalyst of being made up of gold of catalytic quantity, the method that hydroperoxide are decomposed, wherein one or more additional metals that are selected from period of element Table VIII family in addition that also exist with gold.
Background of invention
Now, the commercial run of being produced the mixture of hexalin and pimelinketone by hexanaphthene has the important commercial meaning, and patent documentation has abundant description to it.The typical industrial practice is that oxidizing ethyle alkyl forms the reaction mixture that contains cyclohexyl hydroperoxy-(CHHP).Gained CHHP chosen wantonly in the presence of a kind of catalyzer decomposed, form the reaction mixture that contains hexalin and pimelinketone.Industrial, such mixture a kind of K/A (ketone/alcohol) mixture of being known as, this mixture is very easy to be oxidized, produces hexanodioic acid, and hexanodioic acid is preparation some condensation polymer, particularly polymeric amide, a kind of critical reactants in the process.Owing in these and other method, consume a large amount of hexanodioic acids, improve the method for producing hexanodioic acid and precursor thereof, can obtain the benefit of favorable cost.
The slow people such as (druliner) of De Lulin is at US 4,326, discloses a kind of improvement catalysis process in 084, and promptly oxidizing ethyle alkyl produces the reaction mixture that contains CHHP, then gained CHHP is decomposed, and formation contains K and A mixture.This improvement relates to and utilizes 1, the catalyzer that some transition metal complex of two (the 2-pyridine imino-) isoindolines of 3-decomposes as cyclohexane oxidation and CHHP.According to this patent, with respect to the result who obtains with some lipid acid cobalt (II) salt such as 2 ethyl hexanoic acid cobalt, be converted into the transformation efficiency high service temperature low (80-160 ℃) of K and A and form the solid grain that contains insoluble petal few but these catalyzer show catalyst life length, CHHP.
The slow people such as (Druliher) of De Lulin is at US 4,503, discloses another kind of improvement catalysis process in 257, i.e. oxidizing ethyle alkyl produces and contains the CHHP reaction mixture, then gained CHHP is decomposed, and formation contains the mixture of K and A.This improvement relates to and utilizes the Co be carried on the appropriate carrier
3O
4, MnO
2, or Fe
3O
4As catalyzer, in the presence of the about 80-130 of temperature ℃ and molecular oxygen, carry out the oxidation of hexanaphthene and the decomposition of CHHP.
SANDERSON Cael people such as (Sanderson) is at US 5,414, discloses a kind of method that is prepared uncle-butanols in liquid phase by titanium dioxide, zirconium white or its mixture of catalytically effective amount by t-butyl peroxy hydrogen in 163.
SANDERSON Cael people such as (Sanderson) is at US 5,414, and 141,5,399,794 and 5,401, disclose in 889, in liquid phase,, prepared a kind of method of uncle-butanols by t-butyl peroxy hydrogen by the palladium and the gold that is carried on the aluminum oxide of catalytically effective amount as dispersion agent.
The United States Patent (USP) provisional application 60/025 that the slow people such as (Druliner) of De Lulin proposed on September 3rd, 1996,368 (now is PCT US97/15332, on September 2nd, 1997 proposed) in, disclose hydroperoxide are contacted with the heterogeneous catalyst of Zr, Nb, Hf and the Ti oxyhydroxide or the oxide compound of catalytic quantity, the method that hydroperoxide are decomposed.Preferably, this catalyzer is to be carried on SiO
2, Al
2O
3, carbon or TiO
2On.Aluminum oxide is a kind of preferred carrier.
In order to overcome this prior art inherent deficiency, must be that K/A mixture process is further improved and selects also to hydroperoxide decomposition.For those skilled in the art, with reference to following detailed description, can be more clear to other purpose of the present invention and benefit.
Summary of the invention
According to the present invention, a kind of improvement catalysis process is provided, wherein make hydroperoxide decomposition, form the decomposition reaction mixture that contains correspondent alcohol and ketone.This improvement comprises makes hydroperoxide contact with a kind of heterogeneous catalyst of being made up of gold of catalytic quantity, hydroperoxide decomposition, wherein one or more additional metals that are selected from the periodictable group VIII in addition that exist with gold.In addition, this catalyzer is optional to be supported on the appropriate carrier composition, such as at SiO
2, Al
2O
3, carbon, zirconium white, MgO or TiO
2On.
Preferably, this additional metals is Pt or Pd.This method also can be chosen wantonly under the condition that hydrogen exists and move.
Detailed description of preferred embodiments
The invention provides a kind of modification method of implementing the hydroperoxide decomposition step by commercial run, wherein alkyl or aromatic substance are carried out oxidation, form a kind of mixture of correspondent alcohol and ketone.Especially, oxidable hexanaphthene forms a kind of mixture that contains hexalin (A) and pimelinketone (K).Its industrial process comprises two steps: the first, and oxidizing ethyle alkyl generates the reaction mixture that contains CHHP; The second, decompose CHHP, generate a kind of mixture that contains K and A.As previously mentioned, the method for oxidizing ethyle alkyl is well-known in the document, and those skilled in the art are obtainable.
With respect to the method that adopts homogeneous phase metal catalyst such as metal-salt or metal/ligand mixture, the advantage of heterogeneous catalytic method is that catalyst life is long, the useful products yield is high and does not have soluble metal compound to exist at present.
This modification method also can be used for decomposing other alkane or aromatics hydroperoxy-, for example: tert-butyl hydroperoxy-, cyclo-dodecyl hydroperoxy-and cumene hydroperoxy-.
The decomposition course of CHHP can be under various conditions and is comprised with hexanaphthene itself with all kinds of SOLVENTS and to finish.Because industrial, so be a kind of convenience and preferred solvent for hexanaphthene in the decomposition course of the present invention generally by the catalyzed oxidation of hexanaphthene being produced the cyclohexane solution of CHHP.Such mixture can adopt by the cyclohexane oxidation process the first step and be accepted, or adopts that to deviate from some component by currently known methods later, such as adopting distillation or aqueous solution extraction method to deviate from carboxylic-acid and other impurity.
In the incoming mixture that CHHP decomposes, the preferred concentration of CHHP can be in the scope of 0.5%-100 weight % (being clean CHHP).For the method for industrial implementation, preferable range is about 0.5-3 weight %.
The suitable range of reaction temperature of the inventive method is about 80-170 ℃.Temperature generally is preferred about 110-130 ℃ scope.Reaction pressure can be preferably in the scope of about 69-2760kPa (10-400psi (pound/square inch)), and the scope of the about 276-1380kPa of pressure (40-200psi) is more preferred.Reaction times is inverse relation with temperature of reaction and changes, generally about 2-30 minute scope.
As previously mentioned, heterogeneous catalyst of the present invention comprises Au, Ag, Cu (including but not limited to Au, Ag and Cu sol-gel compound) and some non-Au/Ag/Cu sol-gel compound, preferably is carried on the appropriate carrier.The also available Au of method of the present invention, Ag or Cu exist at other metal (as Pd) and finish.The per-cent of metal pair carrier can change in the scope of about 0.01-50 weight %, the scope of preferably about 0.1-10 weight %.Preferred at present suitable carrier comprises SiO
2(silicon-dioxide), Al
2O
3(aluminum oxide), C (carbon), TiO
2(titanium oxide), MgO (magnesium oxide) or ZrO
2(zirconium white).Zirconium white and aluminum oxide are especially preferred carriers, and the load gold is the especially preferred a kind of catalyzer of the present invention on the aluminum oxide.
Some heterogeneous catalyst of the present invention, manufacturers makes, can therefrom buy, and maybe can adopt methods known in the art, is prepared with suitable parent material.These methods can comprise the following sol-gel process that more describes in detail, prepare Au/Ag/Cu sol-gel compound and other non-Au/Ag/Cu sol-gel compound.The catalyzer of load gold can prepare by any known standard method, draws finely dispersed gold, such as coating method with method of evaporation or by colloidal dispersion system.
Especially, the gold of ultra-fine size classification is preferred.This fine granular gold (10nm (nanometer) is following usually) can be according to Ha Luta (Haruta, M.) article " particle diameter in the golden katalysis-and carrier-dependency " (" catalysis today " (Catalysis Today), 36 (1997) 153-166) and level ground too method described in (Tsubota) people's " preparation of vanadium catalyst " (695-704 page or leaf (1991)) book of etc.ing prepare.Such gold prepares output and shows lilac sample, rather than the golden general bronze colour that is had, and can form the Au catalyst of high dispersing in the time of consequently on being placed on the appropriate carrier composition.The general diameter of golden particulate of these high dispersing is about 3-15nm.
This catalyst solid supports comprises SiO
2, Al
2O
3, carbon, MgO, zirconium white or TiO
2, can be unbodied, or crystallization shape, or mixture amorphous and crystallization shape.Processing parameter is depended in selection for the support of the catalyst optimal average particle size, such as logistics flow rate in reactor residence time and the purpose reactor.Generally, selected mean particle size can be in about 0.005-5mm range.Surface-area is greater than 10m
2The catalyzer of/g is preferred, and is directly related with the rate of decomposition increase in the batch experiment because catalyst surface area increases.The very large carrier of surface-area also can use, but high surface area catalyzer inherent fragility reaches the actual upper bound that the problem of following has determined the support of the catalyst surface-area in keeping acceptable size-grade distribution.Preferred vector is an aluminum oxide; Be more preferably Alpha-alumina and gama-alumina.
" sol-gel method " is a kind of by the suitable precursor material of dissolving, such as alkoxide in colloid, the solvent or metal-salt, prepares the i.e. method of " colloidal sol " of easy streaming fluid solution earlier.Then, this " colloidal sol " is added a kind of reagent, cause this precursor and carry out reactive polymeric.A typical example is the orthosilicic acid tetrem oxygen ester (TEOS) that is dissolved in the ethanol.Add entry, and add the acid of trace or alkali, cause hydrolysis as catalyzer.Because the carrying out of polymerization and crosslinking reaction, this runny " colloidal sol " viscosity increases, and finally is hardened to rigidity " gel ".Should " gel " promptly be made up of the cross-linked network of purpose material, this cross-linked network is encapsulated in initial solvent in its uncovered vesicular structure.Dry then be somebody's turn to do " gel " generally can adopt the simple method that heats in flow of dried air, produces a kind of xerogel, or passes through a kind of supercutical fluid such as liquid CO
2Replace, deviate from the solvent that is captured, produce a kind of aerogel.Aerogel and xerogel all can be chosen wantonly under high temperature (＞200 ℃) and carry out roasting, generally form abundant vesicular structure and follow the product of high surface area.
In the invention process, can make catalyst preparation is catalyst bed, contacts with CHHP, and arrangement can constitute close contact the between catalyzer and the reactant like this.In addition, can adopt methods known in the art to make catalyzer and reaction mixture become slurries.The inventive method is suitable for intermittence or the continuous decomposition course of CHHP.These methods can be finished under various conditions.
The mixture that adds air or air and rare gas element can make the reactant of process be converted into K and A reaches higher transformation efficiency to the CHHP decomposition of the mixture, because except that being decomposed to form by CHHP K and the A, the part hexanaphthene directly is oxidized to K and A in addition.This slave process is called as " hexanaphthene participation ", and De Lulin is slow to wait the people at US 4,326, this is had a detailed description in 084, and its full content is regarded it as reference herein.Other gas also can add or add in the reaction mixture together on demand.Rare gas element such as nitrogen also can add in the reaction separately, or can merge adding with other gas.
The result of CHHP decomposition reaction, such as K/A than or conversion rate, all can by to support of the catalyst, add to the gas in the reaction mixture, or add to the selection of the metal in the heterogeneous catalyst of the present invention and adjusted.
Preferably, add to the metal in the heterogeneous catalyst of the present invention, be used as auxiliary agent, synergistic effect additive, or promotor, all can be selected from the periodictable group VIII, be defined as Fe, Co, Ni, Ru Rh, Pd, Os, Ir, reach Pt at this.Most preferably be Pd and Pt.
A kind of preferred gas that can add in the reaction mixture is a hydrogen.The advantage of adding hydrogen is to change as required the ratio of K/A.Add hydrogen and also can make the by product of impurity or reaction be converted into better product, such as benzene.
The inventive method is also illustrated further by following non-restrictive example.In these embodiments, unless add in addition outside the explanation, all temperature are centigradetemperature, and all percentage ratios are by weight.
Experiment
Test the Au of load about 1.4% on 1 activated carbon
With (EM scientific company (EMScience, Cherry Hill NJ) provides) (100 ml/min) the 400 ℃ of following roastings 1 hour in the helium that flows of the gac of the 20-35 sieve mesh (0.5-0.85mm) of 5g.Then, with this material making beating becoming a kind of solution that the 1.0g gold trichloride is arranged in 10 ml waters that contain 1 milliliter of concentrated HCl.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour is then cooled off and is deposited in the bottle of tight gland, is used to carry out the test as the CHHP decomposition catalyst.
The Au of experiment 2 loads about 1.4% on silicon-dioxide
Get 5g+silica gel of 8 sieve meshes, its surface-area 300m
2/ g and pore volume 1cc/g (alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)), (100 ml/min) roasting is 1 hour in 400 ℃ of current downflow helium.Then, with this material making beating becoming a kind of solution that the 0.1g gold perchloride is arranged in 10 ml waters that contain 1 milliliter of concentrated HCl.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour is cooled off then and is left in the bottle of tight gland, is used to carry out the test as the CHHP decomposition catalyst.
The Au of experiment 3 loads about 14% on silicon-dioxide
Get 5g＜2 microns silica gel, its surface-area 450m
2/ g and pore volume 1.6cc/g (alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) roasting 1 hour in 400 ℃ of current downflow helium (100 ml/min).Then, with this material making beating becoming a kind of solution that the 1.0g gold trichloride is arranged in 10 ml waters that contain 1 milliliter of concentrated HCl.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour is cooled off then and is left in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
Experiment 4 simple silicon-dioxide controls
Get 5g+silica gel of 8 sieve meshes, its surface-area 300m
2/ g and pore volume 1cc/g (alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) (100 ml/min) roasting 1 hour in 400 ℃ of current downflow helium.Then, with this material making beating the becoming a kind of solution that contains 1 milliliter of dense HCl in 10 ml waters.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour is cooled off then, and is left in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
Test the Au of load about 1.4% on 5 Alpha-aluminas
(Ka Sekate company (calsicat, Erie, PA)) pulls an oar to a kind of solution of 0.1g gold trichloride is arranged in 10 ml waters that contain 1 milliliter of concentrated HCl to get the Alpha-alumina bead of the 6-12 sieve mesh of 5g.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour is cooled off then, and is left in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
The Ag of experiment 6 loads about 13% on silicon-dioxide
Get 5g+silica gel of 8 sieve meshes, its surface-area 300m
2/ g and pore volume 1cc/g (alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) (100 ml/min) roasting 1 hour in 400 ℃ of current downflow helium.Then, with this material making beating becoming a kind of solution that the 1.0g Silver Nitrate is arranged in 10 ml waters that contain 1 milliliter of dense HCl.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour, be cooled to 200 ℃ then, and roasting 1 hour again in flowing hydrogen (100 ml/min), leave in then in the bottle of tight gland, be used for testing as the CHHP decomposition catalyst.
The Cu of experiment 7 loads about 4.5% on silicon-dioxide
Get 5g+silica gel of 8 sieve meshes, its surface-area 300m
2/ g and pore volume 1cc/g (alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) (100 ml/min) roasting 1 hour in 400 ℃ of current downflow helium.Then, with this material making beating becoming a kind of solution that the 1.0g cupric nitrate is arranged in 10 ml waters that contain 1 milliliter of dense HCl.At room temperature stirred these slurries 15 minutes, then evaporate to dryness on rotatory evaporator.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow nitrogen 1 hour, make it to be cooled to 200 ℃ then, and roasting 1 hour again in flowing hydrogen (100 ml/min), and leave in the bottle of tight gland, be used for testing as the CHHP decomposition catalyst.
Experiment 8-13 is different from experiment 1-7, be according to the level ground too the general method of (Tsubota) the people's precipitation of gold of etc.ing carry out, see " preparation of vanadium catalyst " that 695-704 page or leaf (1991) is to produce the golden particulate of superfine.These carried catalysts are compared with copper/gold (high capacity amount) or brown/grey (low charge capacity) carried catalyst of experiment 1-7, are purple/pink.
The Au of experiment 8 loads about 1% on MgO
(alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) pulls an oar to a kind of solution of 0.2g gold perchloride is arranged in a kind of 50 ml waters that contain 1 milliliter of dense HCl to get the powdery MgO of-200 sieve meshes of 10g.Regulate the pH to 9.6 of these slurries with sodium carbonate solution, add the 0.69g Trisodium Citrate then.After at room temperature stirring 2 hours,, reclaim solid by filtering and use the distilled water thorough washing.The solid that (100 ml/min) roasting is reclaimed in 250 ℃ of current downflow air 5 hours makes it cooling then, and leaves in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
The Au of experiment 9 loads about 1% on gama-alumina
(alpha Ai Sa company (Alfa Aesar, Ward Hill, MA)) pulls an oar to a kind of solution of 0.2g gold perchloride is arranged in 50 ml waters that contain 1 milliliter of dense HCl to get the powdered gama-alumina of-60 sieve meshes of 10g.Regulate the pH to 9.6 of these slurries with sodium carbonate solution, add the 0.69g Trisodium Citrate then.After at room temperature stirring 2 hours,, reclaim solid by filtering and use the distilled water thorough washing.The solid that (100 ml/min) roasting is reclaimed in 250 ℃ of current downflow air 5 hours makes it cooling then, and leaves in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.The gained catalyzer is purple/pink, and X-ray diffraction (XRD) determines that its Au granularity is 8nm.
The Au of experiment 10 loads about 1% on silicon-dioxide
Get 10g+(alpha Ai Sa company (Alfa Aesar, WardHill, MA)) pulls an oar to a kind of solution of 0.2g gold perchloride is arranged in 50 ml waters that contain 1 milliliter of dense HCl for the pellet of 8 sieve meshes.Regulate the pH to 9.6 of these slurries with sodium carbonate solution, add the 0.69g Trisodium Citrate then.After at room temperature stirring 2 hours,, reclaim solid by filtering and use the distilled water thorough washing.The solid that (100 ml/min) roasting is reclaimed in 250 ℃ of current downflow air 5 hours makes it cooling then, and leaves in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
The Au of experiment 11 loads about 1% on titanium dioxide
(alpha Ai Sa company (AlfaAesar, Ward Hill, MA)) pulls an oar to a kind of solution of 0.2g gold perchloride is arranged in 50 ml waters that contain 1 milliliter of dense HCI to get the powdered titanium dioxide of-325 sieve meshes of 10g.Regulate the pH to 7.0 of these slurries with sodium carbonate solution, add the 1.5g Trisodium Citrate then.After at room temperature stirring 2 hours,, reclaim solid by filtering and use the distilled water thorough washing.The solid that (100 ml/min) roasting is reclaimed in 400 ℃ of current downflow air 5 hours makes it cooling then, and leaves in the bottle of tight gland, is used for testing as the CHHP decomposition catalyst.
The Au of experiment 12 loads about 1% on zirconium white
(Calsicat # 96F-88A, Erie PA), pull an oar to contain a kind of solution of 0.2g gold trichloride in 50 ml waters and 1 dense HCl to get the powdery zirconia of-325 sieve meshes of 10g.Stir these slurries gently, regulate pH to 9.6 with the 0.1M sodium carbonate solution simultaneously.Stir these slurries gently, add the 0.69g Trisodium Citrate simultaneously, then restir is 2 hours.In filtration and after with the distilled water thorough washing, (100 ml/min) 250 ℃ of these solids of following roasting are 5 hours in fluidizing air.
The Au of experiment 13 loads about 1% on aluminum oxide and 0.1% Pd
Get the gama-alumina of 10g-60 sieve mesh, pull an oar in 50 ml waters and dense HCl, containing a kind of solution of 0.2g gold and 0.02g Palladous chloride tetramine.Stir these slurries when regulating pH to 9.6 gently with the 0.1M sodium carbonate solution.Stir these slurries more gently and slowly add 0.69g Trisodium Citrate solid simultaneously, and then stirred 2 hours.In filtration and after with the distilled water thorough washing, this solid of roasting is 5 hours in 250 ℃ of current downflow air.
Embodiment
Embodiment 1-22 is the mode with batch reactor, in stirring 3.5 milliliters of vials, to carry out under barrier film and the plastic cap sealing.The vial insertion wherein can be supported in the aluminium block heated/stirred device equipment of 8 vials.Adopt the stirring rod of coating tetrafluoroethylene to stir.To at first pack into 1.5 milliliters octane or undecane solvent of each vial, about 0.005 or the given catalyzer that pulverizes of 0.01g, and one stirred rod, sealing glass bottle then.To the vial stirring heating about 10 minutes, guarantee that it reaches 125 ℃ of desired temperature of reaction.Then, when each embodiment begins, inject 30 microlitre CHHP and as the stock solution of interior target TCB of GC (gas-chromatography) (1,2, the 4-trichlorobenzene) or CB (chlorobenzene).Stock solution is made up of TCB or the CB mixture of about 20 heavy % in CHHP.The CHHP source comprises hybrid ring hexanol and the pimelinketone of as many as 2.0 heavy %.After 0.5 to 10 minute, from aluminothermy device/agitator, take out vial, and make it be cooled to envrionment temperature.
In embodiment 1-10 (Table I), adopt 15 Miho Dockyard B-17 capillary columns of 0.32 millimeter of internal diameter, CHHP residual quantity in the direct analysis vial.The liquid phase of this post is made up of (50 weight % phenyl) methyl polysiloxane.This post is that (J.And W.Scientific, Folsum California) obtain from the J.W. scientific company.
Gas chromatographic analysis to CHHP amount in each solution, adopt following formula to calculate:
CHHP weight %=(CHHP area %/TCB area %) * TCB weight % * R.F.
CHHP
R.F.
CHHP(gas chromatograph is for the response factor of CHHP) determined by calibration solution according to known CHHP and TCB amount, and calculated by following formula:
CHHP rate of decomposition %=100 * [1-(CHHP area/TCB area)
Finally/ (CHHP area %/TCB area %)
Initially]
In embodiment 1-10 (Table I), the about 2.2 weight % of CHHP starting point concentration in each vial.CHHP
InitiallyAnd CHHP
FinallyGC weight % (gas chromatographic analysis amount) just proximate because the quantity of used every gram solution TCB is than being to equal 0.25 mgTCB/g solution by it entirely and calculate arbitrarily in gas chromatographic analysis calculates.Because analysis to the not heated sample of the CHHP/TCB solution of 1.5 milliliters of octanes and 30 μ L, all be to use the CHHP degradation production vial of making by identical CHHP/TCB solution of respectively organizing to carry out, so the accurate variation of CHHP/TCB ratio is computable.
Embodiment 11-13 (Table II) and embodiment 14-16 (Table III) are respectively to 1%Au/ carbon and 10%Au/SiO
2Catalyzer, (uncle-BuOOH) and the decomposition result of cumene hydroperoxy-(CumeneOOH) are by crowd loading amount % to have enumerated t-butyl peroxy hydrogen.Analysis for uncle-BuOOH and CumeneOOH, adopt well-known iodometry to carry out, see " comprehensive analytical chemistry " (Comprehensive Analytical Chemistry that Weir inferior (C.L.Wilson) is write, Elsevier Publishing Company, New York, 756 pages, 1960) narrate in the book.Initial and the product solution in octane to uncle-BuOOH and CumeneOOH after adding excessive KI/ acetum, stirred 10 minutes in the sealing glass bottle at ambient temperature, used 0.1 M Na again
2S
2O
3In addition titration of solution is determined because the I that uncle-BuOOH and CumeneOOH existence discharge
2Quantity.
Embodiment 17-22 (Table IV and V)) undertaken by embodiment 1-10, but different be: be reflected under 150 ℃ and carry out, replace TCB as mark in the gas chromatograph, and replace octane as solvent with undecane with chlorobenzene.Reacting initial CHHP amount and react last CHHP amount in Table IV and V is to determine divided by the calculating of chlorobenzene gas chromatogram peak area (CHHP area %/CB area %) by CHHP gas chromatogram peak area.
Embodiment 23-39 carries out in the full plug flow reactor of liquid, long 30 inches 1/4 inch of (76 centimetres) diameters (0.64 centimetre) of this plug flow reactor.Control the pressure of inlet and outlet to 150psi (1.03 MPa gauge pressure) with back pressure regulator.Catalyzer is made 2 millimeters sphere by suitable metal-salt and the aluminum oxide type of experiment 13 described usefulness entirely, but exception is that reduction is down with the H that flows at 150 ℃
2Rather than finish with Trisodium Citrate.This charging is by 1.6%CHHP, about 1%K in the hexanaphthene and 2%A, and different water-contents and comprise monobasic and the sour impurity of diprotic acid is formed, these sour impurity are general all to be generated in the oxidation by the cyclohexane of equivalent roughly, such as hexanodioic acid, Succinic Acid, formic acid, and hydroxycaproic acid.To the analysis of CHHP, K and A, adopt vapor-phase chromatography to carry out.Hexanaphthene, CHHP, K, and A be that (E.I.du Pont deNemours and Company, Wilmington DE.) obtain from E.I.Du Pont Company.To the K/A ratio that the cyclohexyl hydroperoxy-reaches after transforming on the catalyzer, adopt following formula to calculate:
[(the mole number K in the product)-(the mole number K in the charging)]/[(the mole number A in the product)-(the mole number A in the charging)]
Though specific embodiments of the present invention are described in the above description, it will be appreciated by those skilled in the art that the present invention can have many improvement, replacement and rearrangement, and unlikely spirit of the present invention or the base attribute of departing from.Should be with reference to attached claim, rather than above-mentioned specification sheets, the scope of the invention represented.
Table I
Wt％ Wt％
The CHHP temperature of reaction time, the initial final 1 1.4%Au/ carbon that decomposes of % ℃ of branch of CHHP CHHP %CHHP embodiment method for preparing catalyst approximate weight, 0.0100 Exp.1 2.2 125 10 0.407 0.221 45.72 1.4%Au/ carbon, 0.0103 Exp.1,2.2 125 10 0.537 0.281 47.73 1.4%Au/SiO
2, 0.0101 Exp.2,2.2 125 10 0.407 0.391 3.94 1.4%Au/SiO
2, 0.0101 Exp.2,2.2 125 10 0.537 0.430 19.95 14%Au/SiO
2, 0.0102 Exp.3,2.2 125 10 0.407 0.154 62.26 14%Au/SiO
2, 0.0104 Exp.3,2.2 125 10 0.407 0.131 67.87 0%Au/SiO
2, 0.0103 Exp.4,2.2 125 10 0.407 0.379 6.98 1.4%Au/Al
2O
3, 0.0102 Exp.5,2.2 125 10 0.537 0.449 16.49 13%Ag/SiO
2, 0.0102 Exp.6,2.2 125 10 0.407 0.245 39.810 4.5%Cu/SiO
2, 0.0103 Exp, 7 2.2 125 10 0.407 0.119 70.8 Table II
Wt％ Wt％
The temperature of reaction time, t-BuOOH t-BuOOH %t-BuOOH embodiment catalyzer, initial final 11 1.4%Au/ activated carbon .0.0102 Exp.1,125 10 0.35 0.20 4412 14%Au/SiO that decompose of g preparation method ℃ branch
2, 0.0102 Exp.3 125 10 0.35 0.18 4813 does not have 125 10 0.35 0.33 5 Table III
Wt％ Wt％
t-Cumene- t-Cumene-?％t-Cumene-
The temperature of reaction time, (OOH) (OOH) (OOH) embodiment catalyzer, initial final 14 1.4%Au/ carbon, 0.0103 Exp.1,125 10 0.55 0.32 4215 14%Au/SiO of decomposing of g preparation method ℃ branch
2, 0.0103 Exp.3 125 10 0.55 0.30 4516 does not have 125 10 0.55 0.54 2
Table IV
Reaction CHHP/CHHP/
The CHHP temperature-time, initial final 17 1%Au/MgO, 0.0102 Exp.8, the 2.2 150 5 3.41 3.29 3.518 1%Au/ γ-Al of decomposing of % ℃ of branch of CB CB %CHHP embodiment method for preparing catalyst approximate weight
2O
3, 0.0120 Exp.9,2.2 150 5 3.41 0 10019 1%Au/SiO
2, 0.01 01 Exp.10,2.2 150 5 3.41 0.91 73.320 1%Au/TiO
2, 0.0106 Exp.11,2.2 150 5 3.41 2.26 33.621 1%Au/ZrO
2, 0.0054 Exp.12,2 150 0.5 5.26 4.68 11.122 1%Au, 0.1%Pd/Al
2O
3, 0.0051Exp.13 2 150 0.5 4.82 3.01 37.5 Table V embodiment catalyzer %CHHP transformation efficiency K/A23 1%Au-0.1%Pd/ γ-Al
2O
364 1.124 1%Au-0.1%Pt/ γ-Al
2O
364 1.125 1%Au-0.1%Ru/ γ-Al
2O
321 1.0126 1%Au-0.1%Ni/ γ-Al
2O
334 1.0027 1%Au-0.1%Co/ γ-Al
2O
345 1.0228 1%Au-0.1%Pd/ α-Al
2O
367 1.9129 1%Au-0.1%Pt/ α-Al
2O
368 1.84 Table VI
Gas, %CHHP benzene feed, outlet benzene, embodiment catalyzer sccm transformation efficiency K/A ppm ppm30 1%Au-0.1%Pd/ α-Al
2O
30 60 1.63--31 1%Au-0.1%Pd/ α-Al
2O
3N
2, 75 62 1.74--32 1%Au-0.1%Pd/ α-Al
2O
3H
2, 75 78 0.47--33 1%Au-0.1%Pd/ α-Al
2O
3H
2, 25 66 0.61--34 1%Au-0.1%Pd/ α-Al
2O
3H
2, 10 61 0.73--35 1%Au-0.1%Pd/ γ-Al
2O
3H
2, 75 51 0.31--36 1%Au-0.1%Pd/ α-Al
2O
3H
2, 75--5,140 482837 1%Au-0.1%Pd/ α-Al
2O
30--5,140 514038 1%Au-0.18%Pt/ α-Al
2O
30 51 1.84--39 1%Au-0.18%Pt/ α-Al
2O
3H
2, 75 73 0.41--
Claims (14)
1, a kind of hydroperoxide decomposition that is used for, generation contains the modification method of the decomposition reaction mixture of correspondent alcohol and ketone, this improvement comprises makes hydroperoxide contact with the heterogeneous catalyst of being made up of gold of catalytic quantity, these hydroperoxide are decomposed, wherein one or more additional metals that are selected from the periodictable group VIII in addition that exist with gold.
2, according to the process of claim 1 wherein that this heterogeneous catalyst is supported on a kind of support of the catalyst composition.
3, according to the method for claim 2, wherein this support of the catalyst composition is to be selected from SiO
2, Al
2O
3, carbon, TiO
2, MgO, and zirconium white.
4, according to the process of claim 1 wherein that these hydroperoxide are cyclohexyl hydroperoxy-s.
5, according to the method for claim 1 or 2, wherein decomposition reaction temperature is in about 80-170 ℃ scope, and decomposition reaction pressure is in about 69-2760kPa scope.
6, according to the method for claim 5, wherein this reaction pressure is in about 276-1380kPa scope.
7, according to the method for claim 1 or 2, wherein this reaction mixture contains the cyclohexyl hydroperoxide of about 0.5-100 weight %.
8, according to the method for claim 1 or 2, wherein this method is moved in the presence of hexanaphthene.
9, according to the method for claim 1 or 2, wherein this method is being added operation in the presence of the oxygen.
10, according to the method for claim 3, wherein gold is supported on the Al2O3.
11, according to the method for claim 10, wherein gold is about the 0.1-10 weight % of catalyzer and carrier components weight.
12, according to the method for claim 2, wherein gold is that abundant divided particles with the about 3-15nm of diameter is supported on the carrier components.
13, according to the process of claim 1 wherein that this additional metals is palladium or platinum.
14, according to the method for claim 1 or 2, wherein this method is carried out under the condition that hydrogen exists.
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 |
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| Publication Number | Publication Date |
|---|---|
| CN1337930A true CN1337930A (en) | 2002-02-27 |
Family
ID=22272330
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| CN99816427A Pending CN1337930A (en) | 1999-03-10 | 1999-03-10 | Hydroperoxide decomposition process |
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| 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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| CN111655660A (en) * | 2018-01-30 | 2020-09-11 | 巴斯夫欧洲公司 | Process for oxidizing cycloalkanes |
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| 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 |
| CN103562168B (en) * | 2011-07-15 | 2016-08-17 | Lg化学株式会社 | The preparation method of isopropylbenzene alcohol and the preparation method of phenol, acetone and AMS |
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| 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 |
| WO1998034894A2 (en) * | 1997-02-11 | 1998-08-13 | E.I. Du Pont De Nemours And Company | Hydroperoxide decomposition process |
-
1999
- 1999-03-10 SK SK1231-2001A patent/SK12312001A3/en not_active Application Discontinuation
- 1999-03-10 JP JP2000603993A patent/JP2002539097A/en active Pending
- 1999-03-10 CN CN99816427A patent/CN1337930A/en active Pending
- 1999-03-10 BR BR9917285-2A patent/BR9917285A/en not_active Application Discontinuation
- 1999-03-10 KR KR1020017011432A patent/KR20020018999A/en not_active Application Discontinuation
- 1999-03-10 WO PCT/US1999/005228 patent/WO2000053550A1/en not_active Application Discontinuation
- 1999-03-10 AU AU29031/99A patent/AU2903199A/en not_active Abandoned
- 1999-03-10 EP EP99909950A patent/EP1159240A1/en not_active Withdrawn
- 1999-03-10 CZ CZ20013106A patent/CZ20013106A3/en unknown
- 1999-03-10 CA CA002362261A patent/CA2362261A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111655660A (en) * | 2018-01-30 | 2020-09-11 | 巴斯夫欧洲公司 | Process for oxidizing cycloalkanes |
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| AU2903199A (en) | 2000-09-28 |
| SK12312001A3 (en) | 2002-02-05 |
| CA2362261A1 (en) | 2000-09-14 |
| CZ20013106A3 (en) | 2002-05-15 |
| EP1159240A1 (en) | 2001-12-05 |
| BR9917285A (en) | 2001-12-26 |
| MXPA01009075A (en) | 2002-03-27 |
| JP2002539097A (en) | 2002-11-19 |
| WO2000053550A1 (en) | 2000-09-14 |
| KR20020018999A (en) | 2002-03-09 |
| PL357043A1 (en) | 2004-07-12 |
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