CN102641734A - Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof - Google Patents
Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof Download PDFInfo
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Abstract
A catalyst for reactions of preparing corresponding alcohols by aryl hydrogen peroxide hydrogenation reduction is a supported precious-metal multicomponent alloy catalyst, wherein the precious metal active ingredients comprise two or more than two of Pt, Pd, Ru, Rh, Ir, Au or Os, and the active ingredients account for 0.1-5.0% of the total weight of the catalyst. When the multicomponent precious-metal alloy catalyst of the invention is used for alcohol preparation reactions by aryl hydrogen peroxide hydrogenation reduction, the conversion rate is up to 100%; the selectivity is more than 99%; and the conversion rate is still maintained to be 100% after continuous operation for 14 days. In addition, with the catalyst of the invention, the purpose of preparation of corresponding alcoholic solutions through direct hydrogenation of isopropyl benzene air oxidation fluid or diisopropyl benzene air oxidation fluid in the production process is realized; the hydrogenized alcoholic solutions can further used for synthesis of peroxides such as dicumyl peroxide and the like; and unnecessary processes such as product separation and purification and impurity pollution are prevented.
Description
Technical field
The present invention relates to a kind of pure Catalysts and its preparation method and application of hydroperoxides preparation that be used to reduce, especially relate to a kind of catalyst and application thereof that is used for cumene oxidation liquid or diisopropylbenzene (DIPB) oxidation liquid preparing alcohol by hydrogenating relative.
Background technology
Therefore organic peroxide has extremely strong oxidability, and many organic alcohol compound can prepare through reducing the method for corresponding hydroperoxides.As reduce hydrogen phosphide cumene (CHP) and can prepare corresponding α, alpha-alpha-dimethyl benzylalcohol (CA), this alcohol are again through condensation obtains cumyl peroxide (DCP) with hydrogen phosphide cumene.Cumyl peroxide is a kind of crystalline solid, is used for the cross-linking reaction process that polyethylene, haloflex, polystyrene, ethane-acetic acid ethyenyl etc. are produced in a large number.It is varied hydroperoxides to be reduced to the reducing agent of correspondent alcohol, like vulcanized sodium, and sodium sulfite, ferrous sulfate, hydrogen iodide etc.The advantage of this type reduction reaction is that principle is simple, and handling safety is reliable, control easily.Reducing agent especially vulcanized sodium can be reduced to α with hydrogen phosphide cumene easily, alpha-alpha-dimethyl benzylalcohol, and all about 98%, reaction equation is as follows for its conversion ratio and selectivity:
Use the vulcanized sodium reducing agent to prepare α, the technology of alpha-alpha-dimethyl benzylalcohol just has report as far back as 20 beginnings of the century, and present this technology is quite ripe, to such an extent as to the main manufacturer of China is still continued to use this traditional technical process.Yet along with the development of chemical industry, the shortcoming of this method comes out gradually: the vulcanized sodium that manufacturer must consume equivalent exchanges pure product for; The fund that must drop into a great deal of dispose with service procedure in the bulky equipment used; Also have to drop into corresponding human resources and move the production technology that this falls behind; During also being to produce, its fatal shortcoming generates the sulfate wastewater of equivalent simultaneously.Along with the concern to environmental problem of the deterioration of expanding economy, natural environment and government and various circles of society, the backward technology of this twentieth century of it can be asserted that still continuing to use at present will finish its historic mission.
The simplest way of dealing with problems is a catalytic hydrogenation, and is as follows:
More than reaction uses hydrogen as reducing agent, and the subsidiary product of generation is a water, is economic, practical, an eco-friendly reduction reaction process.
The reaction that the organic hydroperoxide catalytic hydrogenation prepares organic alcohol just has report the forties in last century, and catalyst activity component wherein comprises: Ni, Co, Pd, Pt etc.Transition metal Ni, components such as Co are because active hanging down need be reacted under higher relatively temperature and Hydrogen Vapor Pressure, and conversion ratio is low, poor selectivity.As the conversion ratio of the hydrogen phosphide cumene that uses 50 milliliter 53% of 1g raney ni catalysis reaction hydrogen phosphide cumene after 5 hours under 75 ℃ reaction temperature and 0.1MPa Hydrogen Vapor Pressure is less than 20%, α, and the selectivity of alpha-alpha-dimethyl benzylalcohol is less than 90%.Wherein main accessory substance is acetophenone and AMS, and these products mainly are that the concurrent decomposition of hydrogen phosphide cumene produces.It is thus clear that the activity of hydrogenation catalyst and the selectivity of target product are complementary.
In order to improve the selectivity of reaction; Be utilized in the catalystic converter system that to add the way that can generate organic amine impurity behind a small amount of organic amine or the hydrogenation be effective; The strong absorption of considering organic amine from the angle of mechanism can replace the organic alcohol that generates the reaction get off from catalyst surface, and the minimizing of catalyst surface target product holdup time can effectively suppress the generation that reduces side reaction.Yet the way of any artificial introducing impurity all must be further considered the change of follow-up product property or have to further consider loaded down with trivial details separation process.
In addition, the fuel factor of hydrogen phosphide cumene hydrogenation reaction is equivalent to the enthalpy of formation (the Δ H=-285.830kJmol of a mole of water
-1), the control of emitting for course of reaction of a large amount of reaction heat has brought difficulty.It is feasible using solvent such as methyl alcohol, benzene etc. under the condition of dilution, to carry out catalytic reaction; But the distillation of solvent and branch defection bring extra financial burden to commercial production; And solvent maybe be bigger to the negative effect of catalytic reaction, such as the about 2mg/L of content that analyzes thiophene in the purified petroleum benzin, the about 5mg/L of the content of sulphur in the chemical pure toluene; This impurity poisons metallic catalyst with the mode of equivalent chemical reaction, and the poisoning process is irreversible.
Summary of the invention
The objective of the invention is to deficiency, a kind of catalyst that aromatic radical hydrogen peroxide hydrogenating reduction prepares correspondent alcohol that is used for is provided to above-mentioned prior art.
The present invention also aims to provide the application of a kind of above-mentioned catalyst in the reaction of cumene oxidation liquid or diisopropylbenzene (DIPB) oxidation liquid preparing alcohol by hydrogenating relative.
Technical scheme of the present invention is following:
A kind ofly be used for the catalyst that aromatic radical hydrogen peroxide hydrogenating reduction prepares correspondent alcohol; Be carried noble metal multi-component alloys catalyst; Comprise active component and carrier; Said active component comprises two or more metals among Pt, Pd, Ru, Rh, Ir, Au or the Os, and said active component accounts for 0.1～5.0% of total catalyst weight.
Preferable, said active component accounts for 0.1～2.0% of total catalyst weight; Better, said active component accounts for 0.45～2.0% of total catalyst weight, so that hydrogenation reaction can steadily be carried out under higher reaction raw materials concentration.
Preferable, said active component comprises two kinds of metals among Pt, Pd, Ru, Rh, Ir, Au or the Os, the weight ratio of said two kinds of metals is (1～15): 1; Be preferably (1.3～5.4): 1.
Said carrier is selected from silica, sieve and silica-sesquioxide, activated alumina, gama-alumina or active carbon.
Preferable, said carrier is activated alumina or active carbon.Wherein, active carbon has resistance to water preferably.
The present invention also provides a kind of above-mentioned Preparation of catalysts method, may further comprise the steps:
(1) salt with two or more metals among Pt, Pd, Ru, Rh, Ir, Au or the Os is dissolved in the solvent, and regulating the pH value is 3.5～4.5;
(2) by said proportioning, in step 1 gained solution, add said carrier, places that evaporation obtains catalyst precarsor except that desolvating after 4.5～5.5 hours;
(3) with gained precursor in the step 2 after 100～120 ℃ of dryings, under hydrogen atmosphere, be warming up to 450～500 ℃ of roastings, obtain noble metal multi-component alloys catalyst.
In the step (1): said solvent is water or ethanol, and the adjusting of the pH value of said noble metal to be to generate active component degree of being precipitated as, and can adopt 10% hydrochloric acid or nitric acid to carry out the adjusting of pH value, requires to make solubilization of active ingredient even.
In the step (2): the consumption of said carrier and solution can be confirmed by equi-volume impregnating conventional in this area.
In the step (3): the speed of said intensification is unsuitable too fast, is advisable with 1～3 ℃/min.
The above-mentioned carried noble metal multicomponent catalyst that is provided among the present invention can be used for the reaction that catalytic hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol.
Further; The reaction that described hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol; For the hydrogenating reduction hydrogen phosphide cumene prepares α, the reaction of alpha-alpha-dimethyl benzylalcohol, perhaps be between hydrogenating reduction (or to)-preparation of diisopropylbenzene (DIPB) list hydroperoxides between (or to)-isopropyl-α; The reaction of alpha-alpha-dimethyl benzylalcohol, perhaps be between the reaction of (or to)-two-(2-hydroxyl-2-propyl group) benzene between the preparation of (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase.
Further, the reaction that described hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol, adopting the solution of aromatic radical hydrogen peroxide is raw material, in hydrogenation process, need not separate, and directly uses.
Described hydrogenating reduction hydrogen phosphide cumene prepares α, and the reaction of alpha-alpha-dimethyl benzylalcohol is a raw material with hydrogen phosphide cumene solution; Said hydrogen phosphide cumene solution is the mixture that isopropylbenzene forms after air oxidation, comprises following components in weight percentage:
Hydrogen phosphide cumene 10～53%;
Isopropylbenzene 44～89%;
Oxidation reaction by-products 1～3%.
In the above-mentioned oxidation liquid, said oxidation reaction by-products comprises acetophenone and/or AMS; Promptly comprise acetophenone and AMS simultaneously, perhaps comprise a kind of in acetophenone and the AMS.
In the above-mentioned catalytic reaction, can use the concentration of organic alcohol, aromatic hydrocarbons, alkane equal solvent conditioned reaction material.But control for the convenience and the reaction temperature of production process; Preferred isopropylbenzene or the α of using among the present invention; Alpha-alpha-dimethyl benzylalcohol is regulated Determination of Cumene Hydroperoxide Concentration in the said cumene oxidation liquid, makes that Determination of Cumene Hydroperoxide Concentration is 10～25% in the reaction mass.Same; Preferred use in the middle of the oxidation liquid that diisopropylbenzene (DIPB) regulates said diisopropylbenzene (DIPB) among the present invention (or to)-diisopropylbenzene (DIPB) list hydroperoxides and between the concentration of (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase, make that hydroperoxide concentration is 10～25% in the reactant liquor.
Between described hydrogenating reduction (or to)-diisopropylbenzene (DIPB) list hydroperoxides and between the reaction of (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase, be to be raw material with diisopropylbenzene (DIPB) oxidation liquid; Said diisopropylbenzene (DIPB) oxidation liquor is the mixture that diisopropylbenzene (DIPB) forms after air oxidation, comprises following components in weight percentage:
Between (or to)-diisopropylbenzene (DIPB) list hydroperoxides 25～35%;
Between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase 5～10%
Diisopropylbenzene (DIPB) 54～70%;
Oxidation reaction by-products 0～2%.
The reaction that said hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol comprises step: said benzene aromatic radical hydrogen peroxide is reacted with hydrogen in the presence of catalyst, and said reacting in fixed bed reactors or the agitated reactor carried out, and process conditions are following:
Reaction temperature: 35～75 ℃;
Reaction pressure: 0.10～5Mpa;
Liquid hourly space velocity (LHSV): 2.0～6.0h
-1
Hydrogen/molar equivalent: 1～50: 1.
In the above-mentioned technology: said hydrogen/molar equivalent is the mol ratio of amount of hydrogen in reaction and said aromatic radical hydrogen peroxide.Hydrogen/molar equivalent is optimum to be 1～30: 1, and extra excessive hydrogen can increase the weight of to reclaim the burden of cyclic process, possibly produce unnecessary phenyl ring excessive hydrogenation reaction simultaneously; Optimum reaction pressure is 1～3Mpa, so that better control catalytic reaction, and the concentration that adapts to high as far as possible hydroperoxides, the operating cost of minimizing equipment.
Compare with the metallic catalyst of one-component; The stability of support type multicomponent precious metal alloys catalyst provided by the invention is better; Using it for aromatic radical hydrogen peroxide hydrogenating reduction prepares in the reaction of benzylalcohol; The conversion ratio of reaction can reach 100%, and selectivity is greater than 99%, move 14 days continuously after conversion ratio still can maintain 100%.In addition; Adopt catalyst of the present invention also can realize utilizing isopropylbenzene air oxidation liquid or the direct hydrogenation preparing of diisopropylbenzene (DIPB) air oxidation liquid in the production process pure accordingly; And hydrogenation products directly is used for subsequent reactions prepares target product; Pilot process does not use other solvents, has avoided product to separate unnecessary processes such as purification and contaminating impurity.
Description of drawings
Fig. 1 is Preparation of catalysts process chart described in the present invention.
The specific embodiment
Carried noble metal multicomponent catalyst described in the present invention adopts following method preparation:
In the salting liquid of multiple noble metal, add an amount of other auxiliary agent; Using acid for adjusting pH value is 3.5～4.5, and not generate active component degree of being precipitated as, described solution can be the aqueous solution or ethanolic solution; The adjusting of pH value requires solubilization of active ingredient even with 10% hydrochloric acid or nitric acid.In solution, add active carrier again, the carrier active component solution of generation is placed and is soaked after 4.5～5.5 hours 100～120 ℃ of evaporations and remove to desolvate and obtain catalyst precarsor.Carrier component can be silica, activated alumina, gama-alumina or active carbon etc.The gained precursor 100～120 ℃ further dry 12 hours, in tube furnace, obtain noble metal multi-component alloys catalyst with the slow heating reduction to 450 of speed of 1～3 ℃/min～500 ℃ under the hydrogen stream at last.Dried catalyst precarsor also can add thermal bake-out earlier under air gas atmosphere, again in hydrogen stream atmosphere progressively heating reduction generate noble metal multi-component alloys catalyst.The gained catalyst is transferred under the inert component environmental condition in isopropylbenzene or the diisopropylbenzene (DIPB) oxidation liquid and is carried out hydrogenation reaction.Catalyst precarsor in-situ reducing when carrying out catalytic reaction with fixed-bed process after the selection roasting is handled and is generated the multi-component alloys catalyst.
Embodiment 1 Preparation of catalysts
Use the palladium bichloride binary composition mixed solution of the chloroplatinic acid and 0.1～0.5% (wt) contain 0.2～0.8% (wt) simultaneously to soak the active aluminum oxide carrier of 20mesh under the metering condition, the pH value of wherein using hydrochloric acid conditioning solution is about 4.According to above method for preparing catalyst the alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.Get the dry catalyst precarsor of 0.3 gram roasting then, in the hydrogen stream of 25ml/min, be warmed up to 450 ℃ of reduction 12 hours gradually.Gained platinum-nickel alloys catalyst drops to after the room temperature under the nitrogen atmosphere protection condition or transfers in the glass reaction still under the flow hydrogen gas protective condition and accomplish hydrogenation reaction.
Embodiment 2 catalytic reactions
0.31% platinum-0.22% (wt) palladium bianry alloy catalyst, 0.30 gram with embodiment 1 obtains carries out catalytic hydrogenation reaction in the glass reaction still.The content of hydrogen phosphide cumene is 40% (wt) in the wherein used cumene oxidation liquid, and oxidation liquid consumption is 30ml, the flow velocity 100ml/min of hydrogen, 60 ℃ of the temperature of water-bath.Post-reacted conversion ratio was 100% in 5 hours, selectivity＞99.0%.
Embodiment 3 Preparation of Catalyst:
Use the gold chloride binary composition mixed solution of the chloroplatinic acid and 0.1～0.5% (wt) contain 0.2～0.8% (wt) simultaneously to soak the absorbent charcoal carrier of 20mesh under the metering condition, all the other steps are identical with embodiment 1.Transfer under the gained platinum alloy catalyst room temperature flow hydrogen gas protective condition and carry out hydrogenation reaction in the glass reaction still.
The contrast of embodiment 4 catalytic reactions:
The golden binary precious metal alloys of 0.46% (wt) platinum-0.15% (wt) catalyst 0.30 gram with embodiment 3 obtains carries out catalytic hydrogenation reaction in the glass reaction still.The content of hydrogen phosphide cumene is 53% (wt) in the wherein used cumene oxidation liquid, consumption 30ml, hydrogen flow rate 100ml/min.Metal Palladium/gama-alumina, 15% (wt) load cobalt-aluminium oxide catalyst of the Raney's nickel, 0.5% (wt) under the same treatment conditions of contrast use etc. carries out catalytic reaction.The conversion ratio of experiment condition and reaction is as shown in table 1:
The reactivity worth contrast of table 1. binary precious metal alloys catalyst and other catalyst
Can find out that from the data of table 1 platinum bianry alloy catalyst has been accomplished catalytic reaction in 60 ℃ and 5 hours, and other catalyst all there is lower catalytic reaction activity.Owing to used higher reaction temperature, the selectivity of non-precious metal catalyst is all less than 95%.
Embodiment 5 Preparation of Catalyst:
Use the gamma-aluminium oxide carrier of 20mesh under the ruthenic chloride binary composition mixed solution immersion metering condition of the palladium bichloride contain 0.2-0.8% (wt) simultaneously and 0.1-0.5% (wt), all the other steps are identical with embodiment 1.
The contrast of embodiment 6 catalytic reactions:
Carry out hydrogenation reaction in the agitated reactor with transferring under gained 0.6% (wt) palladium-0.2% (wt) ruthenium alloy among the embodiment 5/gamma-alumina catalyst room temperature flow hydrogen gas condition.Catalyst amount 0.3 gram; Course of reaction is carried out under normal pressure and 60 ℃ of conditions; 30ml raw material oxidation liquid, the content of hydrogen phosphide cumene are 40% (wt); Be reflected in 4.5 hours and accomplish; Catalyst circulation is used seven times, and hydrogenation reaction terminal point conversion ratio all reaches 100%, detects less than hydrogen phosphide cumene with chemical method.The conversion ratio of different reuse batch gained hydrogenation reactions, selectivity and and the experimental result contrast that gets of industrial sodium sulfide reducing process as shown in table 2:
Table 2 vulcanized sodium hydrogenation and catalytic hydrogenation product analysis contrast (gas chromatographic analysis, area normalization %)
*Hydrogenation reaction time lengthening to 5.5 hour. the hydrogenation reaction product of all batches all detects less than hydrogen phosphide cumene.
From result's raw material of above chromatography, contain 1.494% AMS and 5.96% acetophenone.This impurity is the product of peroxide thermal decomposition gained in the chromatography temperature-rise period.Thermal decomposition is the basic reason that generates these two kinds of accessory substances, also is the main side reaction in hydrogenation and the reduction process simultaneously.
From the major impurity AMS of a catalytic hydrogenation is 0.504%, and acetophenone is 0.907%, little amount 0.38% and 0.78% that is higher than corresponding impurity in the vulcanized sodium reduction.These impurity are results of acidic site catalytic reaction on the catalyst.When the secondary to seven from catalyst behind the acidic site inactivation uses the result to see that the content of these two kinds of impurity all is lower than the amount of corresponding impurity the vulcanized sodium reduzate; And the composition of secondary to seven time product reaches unanimity basically; Its selectivity is better than the accordingly result of industrial sodium sulfide reducing process slightly; Show that the selection hydrogenation that noble metal multi-component alloys catalyst is used for hydrogen phosphide cumene is preferably a kind of, the method that can compare with the vulcanized sodium reducing process fully.
If with catalytic reaction time lengthening one hour (seeing that six hydrogenation products are formed in the table 2); The amount that can see AMS wherein is 0.091% to be starkly lower than the amount of this component in other product; The method that is to say catalytic hydrogenation can become solvent with the part accessory substance hydrogenation of olefins that generates in the reaction simultaneously, and this also is the recommendable advantage of this method.
Embodiment 7 catalytic reactions:
Be used for fixing according to 0.45% (wt) platinum-0.15% (wt) palladium bianry alloy catalyst, 1.2 grams of embodiment 1 preparation and carry out hydrogenation reaction in the bed; Wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa; 60 ℃ of reaction temperatures, the content of hydrogen phosphide cumene is 53% in the oxidation liquid, raw material cumene oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 240 hours continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 98%.
Embodiment 8
Use the gamma-aluminium oxide carrier of 20mesh under the rhodium chloride binary composition mixed ethanol solution soaking metering condition of the chloroplatinic acid and 0.04% (wt) contain 0.16% (wt) simultaneously, the pH value of wherein using hydrochloric acid conditioning solution is about 4.According to above method for preparing catalyst the alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.In the hydrogen stream of 25ml/min, be warmed up to 450 ℃ of reduction 12 hours then gradually, obtain 0.36% (wt) platinum-0.09% (wt) rhodium alloy/gamma-alumina catalyst.
Gained alloy catalyst 1.2 gram is used for fixing carries out hydrogenation reaction in the bed; Wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa; 60 ℃ of reaction temperatures, the content of hydrogen phosphide cumene is 31.5% (wt) in the cumene oxidation liquid, raw material cumene oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 14 days continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 99%.
Embodiment 9
Use the gamma-aluminium oxide carrier of 20mesh under the iridium chloride binary composition mixed ethanol solution soaking metering condition of the palladium bichloride and 0.12% (wt) contain 0.36% (wt) simultaneously, the pH value of wherein using hydrochloric acid conditioning solution is about 4.According to above method for preparing catalyst the alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.In the hydrogen stream of 25ml/min, be warmed up to 450 ℃ of reduction 12 hours then gradually, obtain 1.5% (wt) palladium-0.5% (wt) iridium alloy/gamma-alumina catalyst.
Gained alloy catalyst 1.1 gram is used for fixing carries out hydrogenation reaction in the bed; Wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa; 60 ℃ of reaction temperatures, the content of hydrogen phosphide cumene is 38% (wt) in the cumene oxidation liquid, raw material cumene oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 14 days continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 99%.
Embodiment 10
Use the gamma-aluminium oxide carrier of 20mesh under the osmium chloride binary composition mixed ethanol solution soaking metering condition of the palladium bichloride and 0.27% (wt) contain 0.81% (wt) simultaneously, the pH value of wherein using hydrochloric acid conditioning solution is about 4.According to above method for preparing catalyst the alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.In the hydrogen stream of 25ml/min, be warmed up to 450 ℃ of reduction 12 hours then gradually, obtain 1.2% (wt) palladium-0.41% (wt) osmium alloy/gamma-alumina catalyst.
Gained alloy catalyst 1.2 gram is used for fixing carries out hydrogenation reaction in the bed; Wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa; 60 ℃ of reaction temperatures, the content of hydrogen phosphide cumene is 52% (wt) in the cumene oxidation liquid, raw material cumene oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 14 days continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 99%.
Embodiment 11
0.31% platinum-0.22% (wt) palladium bianry alloy catalyst, 0.30 gram with embodiment 1 obtains carries out catalytic hydrogenation reaction in the glass reaction still.In the middle of the wherein used diisopropylbenzene (DIPB) oxidation liquid (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 33% (wt); Between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content is 8.5% (wt); Oxidation liquid consumption is 30ml, the flow velocity 100ml/min of hydrogen, 65 ℃ of the temperature of water-bath.Post-reacted conversion ratio reached 100% in 5 hours, selectivity＞99.0%.
Embodiment 12
Embodiment 9 gained alloy catalysts 1.2 gram is used for fixing carries out hydrogenation reaction in the bed, wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume.The flow 0.1ml/min of diisopropylbenzene (DIPB) oxidation liquid; Hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in the middle of the diisopropylbenzene (DIPB) oxidation liquid (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 27.6% (wt); Between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content is 6.2% (wt), raw material diisopropylbenzene (DIPB) oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 14 days continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 99%.
Embodiment 13
Embodiment 10 gained alloy catalysts 1.2 gram is used for fixing carries out hydrogenation reaction in the bed, wherein using volume is 18 times quartz sand dilute catalyst of said catalyst volume.The flow 0.1ml/min of diisopropylbenzene (DIPB) oxidation liquid; Hydrogen flowing quantity 100ml/min; Reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in the middle of the diisopropylbenzene (DIPB) oxidation liquid (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 27.6% (wt); Between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content is 6.2% (wt), raw material diisopropylbenzene (DIPB) oxidation liquid and hydrogen and stream flow to the bottom from the top of reactor.Through 14 days continuous catalytic reaction, the conversion ratio that records hydrogenation reaction was 100%, and selectivity is greater than 99%.
Gained hydrogenation products in the foregoing description is carried out heavy metal ion content detect, the result shows that the heavy metal ion content in all products all is ppb levels.This explains that noble metal multi-component alloys catalyst provided by the present invention is highly stable, is difficult for oxidized and loss, can avoid the heavy metal pollution that takes place in the hydrogenation process.
Claims (10)
1. one kind is used for aromatic radical hydrogen peroxide hydrogenating reduction and prepares the correspondent alcohol catalyst for reaction; Be carried noble metal multi-component alloys catalyst; Comprise active component and carrier; Said active component comprises two or more metals among Pt, Pd, Ru, Rh, Ir, Au or the Os, and said active component accounts for 0.1～5.0% of total catalyst weight.
2. catalyst as claimed in claim 1 is characterized in that, said active component comprises two kinds of metals among Pt, Pd, Ru, Rh, Ir, Au or the Os, and the weight ratio of said two kinds of metals is (1～15): 1.
3. according to claim 1 or claim 2 catalyst is characterized in that said carrier is selected from silica, sieve and silica-sesquioxide, activated alumina, gama-alumina or active carbon.
4. one kind like arbitrary said Preparation of catalysts method among the claim 1-3, may further comprise the steps:
(1) salt with two or more metals among Pt, Pd, Ru, Rh, Ir, Au or the Os is dissolved in the solvent, and regulating the pH value is 3.5～4.5;
(2) by said proportioning, in step 1 gained solution, add carrier, places that evaporation obtains catalyst precarsor except that desolvating after 4.5～5.5 hours;
(3) with gained precursor in the step 2 after 100～120 ℃ of dryings, under hydrogen atmosphere, be warming up to 450～500 ℃ of roastings, obtain noble metal multi-component alloys catalyst.
5. be used for the reaction that catalytic hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol like arbitrary said catalyst among the claim 1-3.
6. purposes as claimed in claim 5; It is characterized in that the reaction that described hydrogenating reduction aromatic radical hydrogen peroxide prepares correspondent alcohol is for the hydrogenating reduction hydrogen phosphide cumene prepares α; The reaction of alpha-alpha-dimethyl benzylalcohol; Perhaps be between hydrogenating reduction (or to)-preparation of diisopropylbenzene (DIPB) list hydroperoxides between (or to)-isopropyl-α, the reaction of alpha-alpha-dimethyl benzylalcohol, or the reaction of (or to)-two-(2-hydroxyl-2-propyl group) benzene between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase preparation.
7. purposes as claimed in claim 6 is characterized in that, described hydrogenating reduction hydrogen phosphide cumene prepares α, and the reaction of alpha-alpha-dimethyl benzylalcohol is a raw material with cumene oxidation liquid; Between described hydrogenating reduction between the preparation of (or to)-diisopropylbenzene (DIPB) list hydroperoxides (or to)-isopropyl-α; The reaction of alpha-alpha-dimethyl benzylalcohol, or the reaction of (or to)-two-(2-hydroxyl-2-propyl group) benzene is a raw material with diisopropylbenzene (DIPB) oxidation liquid between the preparation of (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase.
8. purposes as claimed in claim 7 is characterized in that, said cumene oxidation liquid comprises following components in weight percentage: hydrogen phosphide cumene 10～53%, cumene 44～89%, oxidation reaction by-products 1～3%; Said diisopropylbenzene (DIPB) oxidation liquid comprises following components in weight percentage: (or to)-diisopropylbenzene (DIPB) list hydroperoxides 25～35%, (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase 5～10%, diisopropylbenzene (DIPB) 54～70%, oxidation reaction by-products 0～2%.
9. purposes as claimed in claim 7 is characterized in that, uses isopropylbenzene or α, and alpha-alpha-dimethyl benzylalcohol is regulated Determination of Cumene Hydroperoxide Concentration in the said cumene oxidation liquid; Use diisopropylbenzene (DIPB) to regulate the hydroperoxide concentration in the said diisopropylbenzene (DIPB) oxidation liquid.
10. like arbitrary described purposes among the claim 5-9, it is characterized in that said reacting in agitated reactor or the fixed bed reactors carried out.
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| CN201110040074.4A CN102641734B (en) | 2011-02-18 | 2011-02-18 | Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof |
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| CN102641734A true CN102641734A (en) | 2012-08-22 |
| CN102641734B CN102641734B (en) | 2014-08-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114192162A (en) * | 2021-12-13 | 2022-03-18 | 万华化学集团股份有限公司 | Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
| CN114746386A (en) * | 2019-11-26 | 2022-07-12 | 住友化学株式会社 | Method for producing aromatic alcohols |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1596239A (en) * | 2001-10-30 | 2005-03-16 | 罗狄亚聚酰胺中间体公司 | Method for catalytic decomposition of organic hydroperoxides |
| CN1724494A (en) * | 2004-07-22 | 2006-01-25 | 中国科学院大连化学物理研究所 | A kind of catalytic decomposition cyclohexane over hydrogenation H-H reaction system |
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- 2011-02-18 CN CN201110040074.4A patent/CN102641734B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1596239A (en) * | 2001-10-30 | 2005-03-16 | 罗狄亚聚酰胺中间体公司 | Method for catalytic decomposition of organic hydroperoxides |
| CN1724494A (en) * | 2004-07-22 | 2006-01-25 | 中国科学院大连化学物理研究所 | A kind of catalytic decomposition cyclohexane over hydrogenation H-H reaction system |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114746386A (en) * | 2019-11-26 | 2022-07-12 | 住友化学株式会社 | Method for producing aromatic alcohols |
| CN114192162A (en) * | 2021-12-13 | 2022-03-18 | 万华化学集团股份有限公司 | Dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
| CN114192162B (en) * | 2021-12-13 | 2023-06-16 | 万华化学集团股份有限公司 | Dimethylbenzyl alcohol hydrogenolysis catalyst and preparation method and application thereof |
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| CN102641734B (en) | 2014-08-20 |
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