CN102641734B - 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 ofly for reducing hydroperoxides, prepare Catalysts and its preparation method and the application of alcohol, especially relate to a kind of catalyst and application thereof for cumene oxidation liquid or diisopropylbenzene (DIPB) oxidation solution preparing alcohol by hydrogenating relative.
Background technology
Therefore organic peroxide has extremely strong oxidability, and many organic alcohol compound can be prepared by reducing the method for corresponding hydroperoxides.As reduce hydrogen phosphide cumene (CHP) and can prepare corresponding α, alpha-alpha-dimethyl benzylalcohol (CA), this alcohol is again by condensation obtains cumyl peroxide (DCP) with hydrogen phosphide cumene.Cumyl peroxide is a kind of crystalline solid, the cross-linking reaction process of producing for polyethylene, haloflex, polystyrene, ethane-acetic acid ethyenyl etc. in a large number.The reducing agent that hydroperoxides can be reduced to correspondent alcohol is varied, as vulcanized sodium, and sodium sulfite, ferrous sulfate, hydrogen iodide etc.The advantage of this class reduction reaction is that principle is simple, and handling safety reliably, is easily controlled.Reducing agent especially vulcanized sodium can be reduced to α by hydrogen phosphide cumene easily, alpha-alpha-dimethyl benzylalcohol, and its conversion ratio and selectively all in 98% left and right, reaction equation is as follows:
Use vulcanized sodium reducing agent to prepare α, the technique of alpha-alpha-dimethyl benzylalcohol just has report as far back as 20 beginnings of the century, and current 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 alcohol product for; Must drop into the fund of a great deal of and carry out the bulky equipment of using in configure and maintenance technique; Also have to drop into corresponding human resources and move the production technology that this falls behind; Its fatal shortcoming is also to generate in production the sulfate wastewater of equivalent simultaneously.Along with the deterioration of expanding economy, natural environment and the concern of each bound pair environmental problem of government and society, the backward technique 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 catalytic hydrogenation, as follows:
More than reaction is used hydrogen as reducing agent, and the subsidiary product of generation is water, is economic, practical, an eco-friendly reduction reaction process.
The reaction that organic hydroperoxide catalytic hydrogenation is prepared Organic Alcohol just has report the forties in last century, and catalyst activity component wherein comprises: Ni, Co, Pd, Pt etc.Transition metal Ni, the components such as Co need to be reacted because activity is lower under relatively high temperature and Hydrogen Vapor Pressure, low conversion rate, poor selectivity.As the hydrogen phosphide cumene that uses 50 milliliter 53% of 1g raney ni catalysis under the reaction temperature of 75 ℃ and 0.1MPa Hydrogen Vapor Pressure, react 5 hours after the conversion ratio of hydrogen phosphide cumene less than 20%, α, alpha-alpha-dimethyl benzylalcohol be selectively less than 90%.Wherein main accessory substance is acetophenone and AMS, and these products are mainly that the concurrent decomposition of hydrogen phosphide cumene produces.The activity of visible hydrogenation catalyst and target product be selectively complementary.
In order to improve the selective of reaction, it is effective that utilization adds the way that can generate organic amine impurity after a small amount of organic amine or hydrogenation in catalystic converter system, the strong absorption of considering organic amine from the angle of mechanism can replace from catalyst surface the Organic Alcohol generating reaction get off, and the minimizing of catalyst surface target product holdup time can effectively suppress the generation reducing 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.Using solvent is feasible as methyl alcohol, benzene etc. carry out catalytic reaction under the condition of dilution, but the distillation of solvent and a minute defection bring extra financial burden to industrial production, and solvent may be larger to the negative effect of catalytic reaction, such as analyzing the about 2mg/L of content of thiophene in purified petroleum benzin, the about 5mg/L of the content of sulphur in chemical pure toluene, this impurity makes metallic catalyst poisoning in the mode of equivalent chemical reaction, and poisoning process is irreversible.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, a kind of catalyst of preparing correspondent alcohol for aromatic radical hydrogen peroxide hydrogenating reduction is provided.
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 solution preparing alcohol by hydrogenating relative.
Technical scheme of the present invention is as follows:
A kind of catalyst of preparing correspondent alcohol for aromatic radical hydrogen peroxide hydrogenating reduction, for carried noble metal multi-component alloys catalyst, comprise active component and carrier, described active component comprises two or more metals in Pt, Pd, Ru, Rh, Ir, Au or Os, and described active component accounts for 0.1～5.0% of total catalyst weight.
Preferably, described active component accounts for 0.1～2.0% of total catalyst weight; Better, described 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.
Preferably, described active component comprises two kinds of metals in Pt, Pd, Ru, Rh, Ir, Au or Os, and the weight ratio of described two kinds of metals is (1～15): 1; Be preferably (1.3～5.4): 1.
Described carrier is selected from silica, sieve and silica-sesquioxide, activated alumina, gama-alumina or active carbon.
Preferably, described carrier is activated alumina or active carbon.Wherein, active carbon has good resistance to water.
The present invention also provides a kind of preparation method of above-mentioned catalyst, comprises the following steps:
(1) salt of two or more metals in Pt, Pd, Ru, Rh, Ir, Au or Os is dissolved in solvent, regulating pH value is 3.5～4.5;
(2) by described proportioning, in step 1 gained solution, add described carrier, places after 4.5～5.5 hours evaporation and remove desolventizing and obtain catalyst precarsor;
(3) by gained precursor in step 2 in 100～120 ℃ dry after, under hydrogen atmosphere, be warming up to 450～500 ℃ of roastings, obtain noble metal multi-component alloys catalyst.
In step (1): described solvent is water or ethanol, the adjusting of the pH value of described 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 step (2): the consumption of described carrier and solution can be determined by equi-volume impregnating conventional in this area.
In step (3): the speed of described intensification is unsuitable too fast, is advisable with 1～3 ℃/min.
The above-mentioned carried noble metal multicomponent catalyst providing in the present invention can be used for the reaction that catalytic hydrogenating reduction aromatic radical hydrogen peroxide is prepared correspondent alcohol.
Further, described hydrogenating reduction aromatic radical hydrogen peroxide is prepared the reaction of correspondent alcohol, for hydrogenating reduction hydrogen phosphide cumene is prepared α, the reaction of alpha-alpha-dimethyl benzylalcohol, or be between hydrogenating reduction between (or to)-diisopropylbenzene (DIPB) list hydroperoxides preparation (or to)-isopropyl-α, the reaction of alpha-alpha-dimethyl benzylalcohol, or the reaction of (or to)-bis--(2-hydroxyl-2-propyl group) benzene between being between the preparation of (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase.
Further, described hydrogenating reduction aromatic radical hydrogen peroxide is prepared the reaction of correspondent alcohol, and adopting the solution of aromatic radical hydrogen peroxide is raw material, need not be separated in hydrogenation process, directly use.
Described hydrogenating reduction hydrogen phosphide cumene is prepared α, and the reaction of alpha-alpha-dimethyl benzylalcohol be take hydrogen phosphide cumene solution as raw material; Described hydrogen phosphide cumene solution is the mixture that isopropylbenzene forms after air oxidation, comprises the component of following percentage by weight:
Hydrogen phosphide cumene 10～53%;
Isopropylbenzene 44～89%;
Oxidation reaction by-products 1～3%.
In above-mentioned oxidation solution, described oxidation reaction by-products comprises acetophenone and/or AMS; Comprise acetophenone and AMS simultaneously, or comprise a kind of in acetophenone and AMS.
In above-mentioned catalytic reaction, can use Organic Alcohol, aromatic hydrocarbons, alkane equal solvent to regulate the concentration of reaction mass.But the control for convenience and the reaction temperature of production process, in the present invention, preferably use isopropylbenzene or α, alpha-alpha-dimethyl benzylalcohol regulates the concentration of hydrogen phosphide cumene in described cumene oxidation liquid, and the concentration that makes hydrogen phosphide cumene in reaction mass is 10～25%.Same, in the present invention, preferably use diisopropylbenzene (DIPB) to regulate in the middle of the oxidation solution of described diisopropylbenzene (DIPB) the concentration of (or to)-diisopropylbenzene (DIPB) list hydroperoxides and (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase, making hydroperoxide concentration in reactant liquor is 10～25%.
Between described hydrogenating reduction, the reaction of (or to)-diisopropylbenzene (DIPB) list hydroperoxides and (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase, is to take diisopropylbenzene (DIPB) oxidation solution as raw material; Described diisopropylbenzene (DIPB) oxidation solution solution is the mixture that diisopropylbenzene (DIPB) forms after air oxidation, comprises the component of following percentage by weight:
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%.
Described hydrogenating reduction aromatic radical hydrogen peroxide is prepared the reaction of correspondent alcohol, comprises step: described benzene aromatic radical hydrogen peroxide is reacted with hydrogen under the existence of catalyst, described in react in fixed bed reactors or reactor and carry out, process conditions are as follows:
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 above-mentioned technique: the mol ratio of the consumption that described hydrogen/molar equivalent is hydrogen in reaction and described aromatic radical hydrogen peroxide.Hydrogen/molar equivalent is optimum is 1～30: 1, and extra excessive hydrogen can increase the weight of to reclaim the burden of cyclic process, may produce unnecessary phenyl ring excessive hydrogenation reaction simultaneously; Optimum reaction pressure is 1～3Mpa, to 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%, selectively be greater than 99%, move continuously 14 days after conversion ratio still can maintain 100%.In addition, the isopropylbenzene air oxidation liquid or the diisopropylbenzene (DIPB) air oxidation liquid direct hydrogenation that adopt catalyst of the present invention also can realize to utilize in production process are prepared corresponding alcohol, and hydrogenation products is directly used in to subsequent reactions prepares target product, pilot process is not used other solvents, has avoided the unnecessary processes such as product separation purification and contaminating impurity.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of catalyst described in the present invention.
The specific embodiment
Carried noble metal multicomponent catalyst described in the present invention adopts following methods preparation:
In the salting liquid of multiple noble metal, add appropriate 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, 10% hydrochloric acid or nitric acid for the adjusting of pH value, require solubilization of active ingredient even.In solution, add active carrier, the carrier active component solution of generation is placed and is soaked after 4.5～5.5 hours 100～120 ℃ of evaporations and obtain catalyst precarsor except desolventizing again.Carrier component can be silica, activated alumina, gama-alumina or active carbon etc.Gained precursor is further dried 12 hours at 100～120 ℃, and finally in tube furnace, under hydrogen stream, slow heating reduction to 450～500 of speed ℃ with 1～3 ℃/min obtain noble metal multi-component alloys catalyst.Dried catalyst precarsor also can first add thermal bake-out under air stream atmosphere, then in hydrogen stream atmosphere progressively heating reduction generate noble metal multi-component alloys catalyst.Gained catalyst is transferred in isopropylbenzene or diisopropylbenzene (DIPB) oxidation solution and is carried out hydrogenation reaction under inert component environmental condition.When carrying out catalytic reaction with fixed-bed process, select the catalyst precarsor in-situ reducing after roasting to process generation multi-component alloys catalyst.
The preparation of embodiment 1 catalyst
Using the palladium bichloride binary composition mixed solution of the chloroplatinic acid and 0.1～0.5% (wt) simultaneously contain 0.2～0.8% (wt) to soak the active aluminum oxide carrier of 20mesh under metering condition, is wherein 4 left and right by the pH value of hydrochloric acid conditioning solution.According to above method for preparing catalyst, alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.Then get 0.3 gram of catalyst precarsor that roasting is dry, in the hydrogen stream of 25ml/min, be warmed up to gradually 450 ℃ of reduction 12 hours.Gained platinum-nickel alloys catalyst drops to after room temperature under nitrogen atmosphere protection condition or transfers in glass reaction still under flow hydrogen gas protective condition and completes hydrogenation reaction.
Embodiment 2 catalytic reactions
0.30 gram of 0.31% platinum-0.22% (wt) the palladium bianry alloy catalyst obtaining with embodiment 1 carries out catalytic hydrogenation reaction in glass reaction still.Wherein in cumene oxidation liquid used, the content of hydrogen phosphide cumene is 40% (wt), and oxidation solution consumption is 30ml, the flow velocity 100ml/min of hydrogen, the temperature 60 C of water-bath.Within 5 hours, post-reacted conversion ratio is 100%, selective > 99.0%.
Embodiment 3 catalyst preparations:
Use the gold chloride binary composition mixed solution of the chloroplatinic acid and 0.1～0.5% (wt) simultaneously contain 0.2～0.8% (wt) to soak the absorbent charcoal carrier of 20mesh under metering condition, all the other steps are identical with embodiment 1.Under gained platinum alloy catalyst room temperature flow hydrogen gas protective condition, transfer to and in glass reaction still, carry out hydrogenation reaction.
Embodiment 4 catalytic reaction contrasts:
0.30 gram of the golden binary precious metal alloys of 0.46% (wt) platinum-0.15% (wt) catalyst obtaining with embodiment 3 carries out catalytic hydrogenation reaction in glass reaction still.Wherein in cumene oxidation liquid used, the content of hydrogen phosphide cumene is 53% (wt), consumption 30ml, hydrogen flow rate 100ml/min.Contrast is used Metal Palladium/gama-alumina, 15% (wt) Supported Co-aluminium oxide catalyst etc. of the Raney's nickel, 0.5% (wt) under same treatment conditions to carry 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
From the data of table 1, can find out, platinum bianry alloy catalyst has completed catalytic reaction in 60 ℃ and 5 hours, and other catalyst all has lower catalytic reaction activity.Owing to having used higher reaction temperature, non-precious metal catalyst be selectively all less than 95%.
Embodiment 5 catalyst preparations:
Use the gamma-aluminium oxide carrier that simultaneously contains 20mesh under the palladium bichloride of 0.2-0.8% (wt) and the ruthenic chloride binary composition mixed solution of 0.1-0.5% (wt) immersion metering condition, all the other steps are identical with embodiment 1.
Embodiment 6 catalytic reaction contrasts:
By transferring under gained 0.6% (wt) palladium-0.2% (wt) ruthenium alloy/gamma-alumina catalyst room temperature flow hydrogen gas condition in embodiment 5, in reactor, carry out hydrogenation reaction.0.3 gram of catalyst amount; Course of reaction is carried out under normal pressure and 60 ℃ of conditions; 30ml raw material oxidation solution, the content of hydrogen phosphide cumene is 40% (wt); Reaction completed in 4.5 hours; Catalyst circulation is used seven times, and hydrogenation reaction terminal conversion ratio all reaches 100%, with chemical method, can't detect hydrogen phosphide cumene.The conversion ratio of different reuse batch gained hydrogenation reactions, selective and and the experimental result contrast that obtains 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 can't detect hydrogen phosphide cumene.
From the result raw material of above chromatography, contain 1.494% AMS and 5.96% acetophenone.This impurity is the product of peroxide thermal decomposition gained in chromatography temperature-rise period.Thermal decomposition is the basic reason that generates these two kinds of accessory substances, is also the main side reaction in hydrogenation and reduction process simultaneously.
From the major impurity AMS of a catalytic hydrogenation, be 0.504%, acetophenone is 0.907%, micro-amount 0.38% and 0.78% higher than corresponding impurity in vulcanized sodium reduction.These impurity are results of acidic site catalytic reaction on catalyst.After acidic site inactivation, from the secondary to seven of catalyst, use content that result sees these two kinds of impurity all lower than the amount of corresponding impurity vulcanized sodium reduzate, and the composition of secondary to seven time product reaches unanimity substantially, it is selectively slightly better than the accordingly result of industrial sodium sulfide reducing process, show that noble metal multi-component alloys catalyst is a kind of good for the selection hydrogenation of hydrogen phosphide cumene, the method that can compare with vulcanized sodium reducing process completely.
If by catalytic reaction time lengthening one hour (seeing that in table 2, six hydrogenation products form), the amount that can see AMS is wherein 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 by the part accessory substance hydrogenation of olefins generating in reaction simultaneously, and this is also the recommendable advantage of the method.
Embodiment 7 catalytic reactions:
According to 1.2 grams of 0.45% (wt) platinum-0.15% (wt) the palladium bianry alloy catalyst of embodiment 1 preparation, for fixed bed, carry out hydrogenation reaction, wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in oxidation solution, the content of hydrogen phosphide cumene is 53%, and raw material cumene oxidation liquid and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 240 hours, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 98%.
Embodiment 8
Using the rhodium chloride binary composition mixed ethanol solution of the chloroplatinic acid and 0.04% (wt) simultaneously contain 0.16% (wt) to soak the gamma-aluminium oxide carrier of 20mesh under metering condition, is wherein 4 left and right by the pH value of hydrochloric acid conditioning solution.According to above method for preparing catalyst, alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.Then in the hydrogen stream of 25ml/min, be warmed up to gradually 450 ℃ of reduction 12 hours, obtain 0.36% (wt) platinum-0.09% (wt) rhodium alloy/gamma-alumina catalyst.
1.2 grams of gained alloy catalysts are carried out to hydrogenation reaction for fixed bed, wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in cumene oxidation liquid, the content of hydrogen phosphide cumene is 31.5% (wt), raw material cumene oxidation liquid and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 14 days, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 99%.
Embodiment 9
Using the iridium chloride binary composition mixed ethanol solution of the palladium bichloride and 0.12% (wt) simultaneously contain 0.36% (wt) to soak the gamma-aluminium oxide carrier of 20mesh under metering condition, is wherein 4 left and right by the pH value of hydrochloric acid conditioning solution.According to above method for preparing catalyst, alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.Then in the hydrogen stream of 25ml/min, be warmed up to gradually 450 ℃ of reduction 12 hours, obtain 1.5% (wt) palladium-0.5% (wt) iridium alloy/gamma-alumina catalyst.
1.1 grams of gained alloy catalysts are carried out to hydrogenation reaction for fixed bed, wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in cumene oxidation liquid, the content of hydrogen phosphide cumene is 38% (wt), raw material cumene oxidation liquid and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 14 days, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 99%.
Embodiment 10
Using the osmium chloride binary composition mixed ethanol solution of the palladium bichloride and 0.27% (wt) simultaneously contain 0.81% (wt) to soak the gamma-aluminium oxide carrier of 20mesh under metering condition, is wherein 4 left and right by the pH value of hydrochloric acid conditioning solution.According to above method for preparing catalyst, alumina support immersion was also further kept dry 12 hours at 110 ℃ of evaporates to dryness after 5 hours.Then in the hydrogen stream of 25ml/min, be warmed up to gradually 450 ℃ of reduction 12 hours, obtain 1.2% (wt) palladium-0.41% (wt) osmium alloy/gamma-alumina catalyst.
1.2 grams of gained alloy catalysts are carried out to hydrogenation reaction for fixed bed, wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume, the flow 0.1ml/min of cumene oxidation liquid, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, in cumene oxidation liquid, the content of hydrogen phosphide cumene is 52% (wt), raw material cumene oxidation liquid and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 14 days, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 99%.
Embodiment 11
0.30 gram of 0.31% platinum-0.22% (wt) the palladium bianry alloy catalyst obtaining with embodiment 1 carries out catalytic hydrogenation reaction in glass reaction still.Wherein in the middle of diisopropylbenzene (DIPB) oxidation solution used (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 33% (wt), between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content be 8.5% (wt), oxidation solution consumption is 30ml, the flow velocity 100ml/min of hydrogen, 65 ℃ of the temperature of water-bath.Within 5 hours, post-reacted conversion ratio reaches 100%, selective > 99.0%.
Embodiment 12
1.2 grams of embodiment 9 gained alloy catalysts are carried out to hydrogenation reaction for fixed bed, and wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume.The flow 0.1ml/min of diisopropylbenzene (DIPB) oxidation solution, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 27.6% (wt) in the middle of diisopropylbenzene (DIPB) oxidation solution, between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content be 6.2% (wt), raw material diisopropylbenzene (DIPB) oxidation solution and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 14 days, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 99%.
Embodiment 13
1.2 grams of embodiment 10 gained alloy catalysts are carried out to hydrogenation reaction for fixed bed, and wherein using volume is the quartz sand dilute catalyst of 18 times of described catalyst volume.The flow 0.1ml/min of diisopropylbenzene (DIPB) oxidation solution, hydrogen flowing quantity 100ml/min, reaction pressure 0.6MPa, 60 ℃ of reaction temperatures, (or to)-diisopropylbenzene (DIPB) list hydroperoxides content is 27.6% (wt) in the middle of diisopropylbenzene (DIPB) oxidation solution, between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase content be 6.2% (wt), raw material diisopropylbenzene (DIPB) oxidation solution and hydrogen stream flow to bottom from the top of reactor.Through the continuous catalytic reaction of 14 days, the conversion ratio that records hydrogenation reaction was 100%, is selectively greater than 99%.
Gained hydrogenation products in above-described embodiment is carried out to heavy metal ion content detection, and result shows that the heavy metal ion content in all products is all ppb levels.This illustrates that noble metal multi-component alloys catalyst provided by the present invention is highly stable, is difficult for oxidized and runs off, and can avoid the heavy metal pollution occurring in hydrogenation process.
Claims (9)
1. for aromatic radical hydrogen peroxide hydrogenating reduction, prepare the catalyst that correspondent alcohol reacts for one kind, for carried noble metal multi-component alloys catalyst, comprise active component and carrier, described active component comprises two or more metals in Pt, Pd, Rh, Ir, Au or Os, and described active component accounts for 0.1～5.0% of total catalyst weight;
Described hydrogenating reduction aromatic radical hydrogen peroxide is prepared the reaction of correspondent alcohol, for hydrogenating reduction hydrogen phosphide cumene is prepared α, the reaction of alpha-alpha-dimethyl benzylalcohol, or be between hydrogenating reduction between (or to)-diisopropylbenzene (DIPB) list hydroperoxides preparation (or to)-isopropyl-α, the reaction of alpha-alpha-dimethyl benzylalcohol, or the reaction of (or to)-bis--(2-hydroxyl-2-propyl group) benzene between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase preparation;
Described catalyst is made by the preparation method who comprises the following steps:
(1) salt of two or more metals in Pt, Pd, Rh, Ir, Au or Os is dissolved in solvent, hydrochloric acid or the nitre acid for adjusting pH value of employing 10% are 3.5～4.5;
(2) by described proportioning, in step 1 gained solution, add carrier, places after 4.5～5.5 hours evaporation and remove desolventizing and obtain catalyst precarsor;
(3) by gained precursor in step 2 in 100～120 ℃ dry after, under hydrogen atmosphere, with 1～3 ℃/min, be warming up to 450～500 ℃ of roastings, obtain noble metal multi-component alloys catalyst.
2. catalyst as claimed in claim 1, is characterized in that, described active component comprises two kinds of metals in Pt, Pd, Rh, Ir, Au or Os, and the weight ratio of described two kinds of metals is (1～15): 1.
3. catalyst as claimed in claim 1 or 2, is characterized in that, described carrier is selected from silica, sieve and silica-sesquioxide, activated alumina, gama-alumina or active carbon.
4. as a preparation method for catalyst as described in arbitrary in claim 1-3, comprise the following steps:
(1) salt of two or more metals in Pt, Pd, Rh, Ir, Au or Os is dissolved in solvent, regulating pH value is 3.5～4.5;
(2) by described proportioning, in step 1 gained solution, add carrier, places after 4.5～5.5 hours evaporation and remove desolventizing and obtain catalyst precarsor;
(3) by gained precursor in step 2 in 100～120 ℃ dry after, under hydrogen atmosphere, be warming up to 450～500 ℃ of roastings, obtain noble metal multi-component alloys catalyst.
5. as catalyst as described in arbitrary in claim 1-3 is prepared the reaction of correspondent alcohol for catalytic hydrogenating reduction aromatic radical hydrogen peroxide.
6. purposes as claimed in claim 5, is characterized in that, described hydrogenating reduction hydrogen phosphide cumene is prepared α, and the reaction of alpha-alpha-dimethyl benzylalcohol be take cumene oxidation liquid as raw material; 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 between (or to)-diisopropylbenzene (DIPB) dihydro-peroxidase preparation, the reaction of (or to)-bis--(2-hydroxyl-2-propyl group) benzene be take diisopropylbenzene (DIPB) oxidation solution as raw material.
7. purposes as claimed in claim 6, is characterized in that, described cumene oxidation liquid comprises the component of following percentage by weight: hydrogen phosphide cumene 10～53%, cumene 44～89%, oxidation reaction by-products 1～3%; Described diisopropylbenzene (DIPB) oxidation solution comprises the component of following percentage by weight: (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%.
8. purposes as claimed in claim 6, is characterized in that, uses isopropylbenzene or α, and alpha-alpha-dimethyl benzylalcohol regulates the concentration of hydrogen phosphide cumene in described cumene oxidation liquid; Use diisopropylbenzene (DIPB) to regulate the hydroperoxide concentration in described diisopropylbenzene (DIPB) oxidation solution.
9. as the purposes as described in arbitrary in claim 5-8, it is characterized in that, described in react in reactor or fixed bed reactors and carry out.
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| 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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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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