CN106964404A - A kind of new catalyst that production aldehyde ketone is aoxidized for alcohol and preparation method thereof - Google Patents

A kind of new catalyst that production aldehyde ketone is aoxidized for alcohol and preparation method thereof Download PDF

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CN106964404A
CN106964404A CN201710197089.9A CN201710197089A CN106964404A CN 106964404 A CN106964404 A CN 106964404A CN 201710197089 A CN201710197089 A CN 201710197089A CN 106964404 A CN106964404 A CN 106964404A
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alcohol
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aldehyde ketone
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CN106964404B (en
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吴功德
王晓丽
吕小笛
苏铖
郭明山
陶炳池
朱锐
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Nanjing Institute of Technology
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    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/56—Vanadium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract

The invention discloses a kind of new catalyst that production aldehyde ketone is aoxidized for alcohol and preparation method thereof, the catalyst is using houghite as carrier, using metal complex as catalytic oxidation activity center, metal complex is one or both of V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt, and the content of wherein institute's carried metal element accounts for the 0.03 ~ 5.00% of catalyst gross mass.The invention also discloses a kind of preparation method for the new catalyst that production aldehyde ketone is aoxidized for alcohol.The present invention is using alcohol and oxidizing agent as raw material, in the presence of prepared new catalyst, the conversion ratio of alcohol and the high income of aldehyde ketone, without any soda acid and organic additive in simultaneous reactions system, with yield is high, cost is low, pollution, many advantages, such as easily separated and Repeatability is good are not produced to environment；Simultaneously in the preparation process of catalyst, raw material sources enrich, many advantages, such as not producing pollution to environment.

Description

A kind of new catalyst that production aldehyde ketone is aoxidized for alcohol and preparation method thereof
Technical field
The invention belongs to new material and technical field, particularly relate to a kind of aoxidized for alcohol and produce the new of aldehyde ketone Catalyst and preparation method thereof.
Background technology
The increasingly depleted of petroleum resources, not only brings energy crisis, and also result in various industrial chemicals to the mankind Scarcity, therefore the substitute of sustainable regeneration must be sought for industrial chemicals.Aldehyde ketone is required original in many chemical process Material and intermediate, demand is growing day by day in recent years.Main aoxidized by alcohol of aldehyde ketone is made, and alcohol can derive from various biologies extensively In matter, therefore directly alcohol oxidative synthesis aldehyde ketone is expected to provide abundant raw material for Chemical Manufacture；But environmental protection, an efficient, practicality Alcohol oxidation reaction, do not require nothing more than that reactivity is high, good product selectivity, and require that catalyst can be recycled, react It is solvent-free（Or additive）Temperate condition under carry out；Therefore, alcohol selective oxidation synthesis aldehyde ketone turns into Green Chemistry/chemical industry In most one of technical process of challenge.
Traditionally the oxidation reaction of alcohol is mostly using oxidants, these oxidants such as chromate, permanganate, organic peracids Atom utilization is low, quantity of three wastes is big, pollution is heavy, therefore use environment friendly oxidant（Such as air, oxygen and hydrogen peroxide） The selective oxidation for making alcohol is had more into extensive industrial applications prospect instead of traditional oxidant.In addition, complex-catalyzed Agent is by designing different ligands（L）The anion different with structure（X）, can obtain activity high, the good, various structures of selectivity equal Phase catalyst.If complex is immobilized on carrier, the plurality of advantages of homogeneous composition catalyst, Er Qieke can not only be retained Reuse, reduce cost.
Summary is described, under conditions of using air, oxygen and hydrogen peroxide as oxidant, with supported metal complex For catalyst, the new way that aldehyde ketone explores green high-efficient will can be synthesized for alcohol selective catalytic oxidation, and further promote life Raw material of substance converts flourishing for industry to chemical products.
The content of the invention
In order to solve the above problems, the invention provides a kind of new catalyst and its system that production aldehyde ketone is aoxidized for alcohol Preparation Method.
In order to achieve the above object, the present invention is achieved by the following technical solutions：
The present invention is a kind of new catalyst that production aldehyde ketone is aoxidized for alcohol, and catalyst is with the class water with natural stabilisation structure Talcum is carrier, using the metal complex of high activity as catalytic oxidation activity center, the metal complex of the high activity is V, One or both of Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt, the content of wherein institute's carried metal element account for the total matter of catalyst The 0.03 ~ 5.00% of amount.
A kind of preparation method for the new catalyst that production aldehyde ketone is aoxidized for alcohol, the preparation comprises the following steps：
（1）The colloid mixture aqueous solution of magnesia, aluminum oxide and carbonate is prepared, magnesium, the mol ratio of aluminium content are 2.0~5.0, Magnesium, the total ion concentration of aluminium are 2.0~5.0 mol/L；Carbonate is identical with the mole dosage of aluminum oxide；It is stirred vigorously at room temperature After 1~6 hour, 60~120 DEG C of crystallization are placed in crystallizing kettle 6~24 hours, it is then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, and 60~100 DEG C of drying, the solid sample of gained is calcined 4~16 hours at 200~400 DEG C, is made Obtain corresponding Mg-Al composite oxide；
（2）Preparation steps（1）The colloid aqueous solution of the Mg-Al composite oxide of middle 40-600 mesh, controls its pH value to exist using alkali lye Between 9~11, temperature is 40~80 DEG C, is stirred vigorously aging 12-36 hours, then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, 60~100 DEG C of drying, prepares corresponding magnesia-alumina hydrotalcite compound；
（3）According toNature Communication, 2014, 5, 3470Described in prepare ligand L 1-L8, using dense H2SO4With oleum sulfonation L1-L8 parts, and using NaOH neutralize, contained-SO3A series of Na parts, then by institute Obtain the metal complex anions that sodium salt with metal salt be coordinated the sulfonation needed for obtaining in dichloroethane solvent system；
（4）By step（2）The magnesia-alumina hydrotalcite compound and step of preparation（3）The metal complex of the sulfonation of middle gained it is cloudy from Son reacts 12~48 hours in appropriate solution system, obtains the magnesia-alumina hydrotalcite of corresponding metal complex load.
It is preferred that：In the step（1）In, the carbonate is one kind in ammonium carbonate, sodium carbonate, potassium carbonate.
It is preferred that：In the step（2）In, the alkali lye is in sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea It is a kind of.
It is preferred that：In the step（3）In, the metal salt is acetate or chlorine for Fe, Co, Ni, Cu, V, Cr, Mn Compound, the metal salt is AuCl or Me for Au, Pd, Pt2SAuCl、PdCl2And PtCl2。
It is preferred that：In the step（4）In, the appropriate solution system be toluene, ethanol, dichloromethane, dichloroethanes, One or both of DMF.
The beneficial effects of the invention are as follows：（1）The catalyst of preparation shows very high activity in alcohol oxidation production aldehyde ketone, Using air, oxygen and hydrogen peroxide as oxidant, at 25 ~ 100 DEG C, 2 ~ 96 h are reacted, catalyst amount is the 0.6- of alcohol 2.0 wt%, the highest yield of aldehyde ketone is up to 98%；
（2）Catalyst preparation materials abundance, reusability is good, many advantages, such as not producing pollution to environment；
（3）Reaction condition is gentle, and without any soda acid and organic additive in reaction system, target product is easily separated.
Embodiment
In order to deepen the understanding of the present invention, the present invention is described in further detail below in conjunction with embodiment, the reality Apply example to be only used for explaining the present invention, protection scope of the present invention is not constituted and limited.
As shown in the Examples, the present invention be it is a kind of for alcohol aoxidize production aldehyde ketone new catalyst, catalyst with The houghite of natural stabilisation structure is carrier, using the metal complex of high activity as catalytic oxidation activity center, described high living Property metal complex one or both of for V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt, wherein institute's carried metal element Content account for the 0.03 ~ 5.00% of catalyst gross mass.
A kind of preparation method for the new catalyst that production aldehyde ketone is aoxidized for alcohol, the preparation comprises the following steps：
（1）The colloid mixture aqueous solution of magnesia, aluminum oxide and carbonate is prepared, magnesium, the mol ratio of aluminium content are 2.0~5.0, Magnesium, the total ion concentration of aluminium are 2.0~5.0 mol/L；Carbonate is identical with the mole dosage of aluminum oxide；It is stirred vigorously at room temperature After 1~6 hour, 60~120 DEG C of crystallization are placed in crystallizing kettle 6~24 hours, it is then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, and 60~100 DEG C of drying, the solid sample of gained is calcined 4~16 hours at 200~400 DEG C, is made Obtain corresponding Mg-Al composite oxide；The carbonate is one kind in ammonium carbonate, sodium carbonate, potassium carbonate；
（2）Preparation steps（1）The colloid aqueous solution of the Mg-Al composite oxide of middle 40-600 mesh, controls its pH value to exist using alkali lye Between 9~11, temperature is 40~80 DEG C, is stirred vigorously aging 12-36 hours, then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, 60~100 DEG C of drying, prepares corresponding magnesia-alumina hydrotalcite compound；The alkali lye is hydroxide One kind in sodium, potassium hydroxide, ammonium hydroxide and urea；
（3）According toNature Communication, 2014, 5, 3470Described in prepare ligand L 1-L8, using dense H2SO4With oleum sulfonation L1-L8 parts, and using NaOH neutralize, contained-SO3A series of Na parts, then by institute Obtain the metal complex anions that sodium salt with metal salt be coordinated the sulfonation needed for obtaining in dichloroethane solvent system；Institute It is acetate or chloride for Fe, Co, Ni, Cu, V, Cr, Mn to state metal salt, and the metal salt is AuCl for Au, Pd, Pt Or Me2SAuCl、PdCl2And PtCl2；
（4）By step（2）The magnesia-alumina hydrotalcite compound and step of preparation（3）The metal complex of the sulfonation of middle gained it is cloudy from Son reacts 12~48 hours in appropriate solution system, obtains the magnesia-alumina hydrotalcite of corresponding metal complex load；Institute It is one or both of toluene, ethanol, dichloromethane, dichloroethanes, DMF to state appropriate solution system.
Product analysis, liquid phase chromatogram condition is as follows：Centrifuged after sampling, 0.45 μm of membrane filtration utilizes efficient liquid phase Chromatograph analyzes product component（Agilent 1200）, Aminex-HPX-87H ion exclusion chromatography columns（U.S. Bio-Rad, 300 mm×7.8 μm）, the mol/L aqueous sulfuric acids of mobile phase 0.005, the mL/min of flow velocity 0.5, show difference and Uv-vwd detectors, ripple Long 210 nm, 333 K, the μ L of sample size 10, quantitative analysis is carried out by normalization method to each product.
Embodiment 1
By 2 mol MgO, 1 mol Al2O31.5 L colloids are made into deionized water with 1 mol sodium carbonate；It is violent at room temperature Stirring 1.0 hours, is placed in crystallizing kettle 60 DEG C of crystallization 6 hours, filters, is washed with water to neutrality, 60 DEG C of drying, the solid of gained Sample is calcined 4 hours at 200 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 40 mesh powder to be placed in water, used NH4OH regulation and control pH value is filtered and is washed with water to neutrality to be stirred vigorously aging 12 hours at 9.0,40 DEG C, 60 DEG C of drying, is obtained To carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 1 is taken to be dissolved in 100 mL dichloromethane, while 100 mL are added dropwise The nitration mixture of the concentrated sulfuric acid and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 mol/ It is 7.0 that L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, extract mixing vacuum distillation is obtained In solid, the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L1 of concentration.By gained sulfonate sodium In the dichloromethane solution for being dissolved in 500 mL, the AuCl for adding 0.1 mol reacts 2 hours, adds 1 mol carrier magnesia-aluminas Hydrotalcite compound, is reacted at room temperature 24 hours, filtering, and drying obtains the gold complex of houghite load at 40 DEG C.Take 1 Mol phenmethylol is added in 1000 mL reactors, is filled with 2 Mpa oxygen, adds the houghite of phenmethylol mass number 2% The gold complex of load, is warming up to after 60 DEG C, centrifuges catalyst and reaction solution after 6 h of reaction, reaction solution delivers to liquid phase Chromatogram identification and analysis, the yield of benzaldehyde is up to 87%.
Embodiment 2
By 6 mol MgO, 1.2 mol Al2O31.5 L colloids are made into deionized water with 1.2 mol sodium carbonate；At room temperature It is stirred vigorously 6.0 hours, is placed in crystallizing kettle 120 DEG C of crystallization 24 hours, filters, is washed with water to neutrality, 100 DEG C of drying, gained Solid sample calcined 16 hours at 400 DEG C, obtain corresponding Mg-Al composite oxide；It is ground to form into 600 mesh powder to be placed in In water, with sodium hydroxide regulation and control pH value to be stirred vigorously aging 36 hours at 11.0,80 DEG C, filter and be washed with water to neutrality, 100 DEG C of drying, obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 2 is taken to be dissolved in 100 mL dichloromethane, The nitration mixture of the 100 mL concentrated sulfuric acids and 300 mL oleums is added dropwise simultaneously, room temperature reaction adds 500 g frozen water after 24 hours is mixed Compound, and it is 7.0 to be neutralized to pH value with 6mol/L NaOH solution, is extracted 3 times with 500 mL dichloromethane respectively, extract Mixing vacuum distillation obtains solid, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L2 of concentration. By gained sulfonate sodium in the dichloromethane solution for being dissolved in 500 mL, 0.1 mol PtCl is added2Reaction 24 hours, then add Enter 1 mol carrier magnesia-alumina hydrotalcite compounds, react at room temperature 24 hours, filter, drying obtains houghite load at 40 DEG C Gold complex.Take 1 mol phenmethylol to add in 1000 mL reactors, be filled with 2 Mpa oxygen, add phenmethylol quality The platinum complex of the houghite load of number 2%, is warming up to after 100 DEG C, by catalyst and reaction solution centrifugation point after 96 h of reaction From reaction solution delivers to liquid chromatogram identification and analysis, and the yield of benzaldehyde is up to 98%.
Embodiment 3
By 3 mol MgO, 1 mol Al2O31.5 L colloids are made into deionized water with 1 mol sodium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 100 DEG C of crystallization 18 hours, filters, is washed with water to neutrality, 80 DEG C of drying, and gained is consolidated Body sample is calcined 12 hours at 350 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 200 mesh powder and is placed in water In, with potassium hydroxide regulation and control pH value to be stirred vigorously aging 24 hours at 10.0,60 DEG C, filter and be washed with water to neutrality, 80 DEG C drying, obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 3 is taken to be dissolved in 100 mL dichloromethane, simultaneously The nitration mixture of the 100 mL concentrated sulfuric acids and 300 mL oleums is added dropwise, room temperature reaction adds 500 g mixture of ice and water after 24 hours, And it is 7.0 that pH value is neutralized to 6mol/L NaOH solution, is extracted 3 times with 500 mL dichloromethane respectively, extract mixing Vacuum distillation obtains solid, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L3 of concentration.By institute Sulfonate sodium is obtained in the dichloromethane solution for being dissolved in 500 mL, 0.05 mol PtCl is added2With 0.05 mol PdCl2Instead Answer 24 hours, add 1 mol carrier magnesia-alumina hydrotalcite compounds, react at room temperature 24 hours, filter, dried at 40 DEG C The platinum palladium two-element match loaded to houghite.Take 1 mol methanol to add in 1000 mL reactors, be filled with 2 Mpa oxygen Gas, adds the platinum palladium two-element match of the houghite load of methanol quality number 0.6%, is warming up to after 25 DEG C, after 24 h of reaction Catalyst and reaction solution are centrifuged, reaction solution delivers to liquid chromatogram identification and analysis, and the yield of formaldehyde is up to 48%.
Embodiment 4
By 3 mol MgO, 2 mol Al2O31.5 L colloids are made into deionized water with 2 mol sodium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 100 DEG C of crystallization 12 hours, filter, be washed with water to neutral 100 DEG C of drying, and gained is consolidated Body sample is calcined 4 hours at 400 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 200 mesh powder to be placed in water, With urea regulation and control pH value to be stirred vigorously aging 24 hours at 9.0,60 DEG C, filter and be washed with water to neutrality, 80 DEG C of drying are obtained To carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 4 is taken to be dissolved in 100 mL dichloromethane, while 100 mL are added dropwise The nitration mixture of the concentrated sulfuric acid and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 mol/ It is 7.0 that L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, extract mixing vacuum distillation is obtained In solid, the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L4 of concentration.By gained sulfonate sodium In the dichloromethane solution for being dissolved in 500 mL, the copper acetate for adding 0.1 mol reacts 24 hours, adds 1 mol carrier magnesium Aluminium houghite compound, is reacted at room temperature 24 hours, filtering, and drying obtains the copper complex of houghite load at 40 DEG C.Take 1 mol ethanol is added in 1000 mL reactors, is filled with 4 Mpa air, and the houghite for adding ethanol mass number 2% is born The copper complex of load, is warming up to after 60 DEG C, centrifuges catalyst and reaction solution after 2 h of reaction, reaction solution delivers to liquid phase color Identification and analysis is composed, the yield of acetaldehyde is up to 43%.
Embodiment 5
By 3 mol MgO, 2 mol Al2O32.0 L colloids are made into deionized water with 2 mol ammonium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 100 DEG C of crystallization 8 hours, filters, is washed with water to neutral 80 DEG C of drying, the solid of gained Sample is calcined 4 hours at 300 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 60 mesh powder to be placed in water, used Sodium hydroxide regulation and control pH value is filtered and is washed with water to neutrality to be stirred vigorously aging 24 hours at 9.0,60 DEG C, 80 DEG C of drying, Obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 5 is taken to be dissolved in 100 mL dichloromethane, while being added dropwise 100 The nitration mixture of the mL concentrated sulfuric acids and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 It is 7.0 that mol/L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, and extract mixing decompression is steamed Solid is evaporated to obtain, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L5 of concentration.By gained sulfonic acid Sodium salt adds 0.05 mol FeCl in the dichloromethane and the mixed solution of ethanol for being dissolved in 500 mL2With 0.05 mol's CoCl3Reaction 24 hours, adds 2 mol carrier magnesia-alumina hydrotalcite compounds, reacts at room temperature 24 hours, filtering, at 40 DEG C Drying obtains the iron cobalt two-element match of houghite load.Take 1 mol 1- octanols to add in 1000 mL reactors, be filled with 4 Mpa air, adds the copper complex of the houghite load of 1- octanols mass number 2%, is warming up to after 60 DEG C, after 6 h of reaction Catalyst and reaction solution are centrifuged, reaction solution delivers to liquid chromatogram identification and analysis, and the yield of 1- octanals is up to 56%.
Embodiment 6
By 3 mol MgO, 2 mol Al2O32.0 L colloids are made into deionized water with 2 mol ammonium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 100 DEG C of crystallization 8 hours, filters, is washed with water to neutral 80 DEG C of drying, the solid of gained Sample is calcined 4 hours at 300 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 60 mesh powder to be placed in water, used Sodium hydroxide regulation and control pH value is filtered and is washed with water to neutrality to be stirred vigorously aging 24 hours at 9.0,60 DEG C, 80 DEG C of drying, Obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 6 is taken to be dissolved in 100 mL dichloromethane, while being added dropwise 100 The nitration mixture of the mL concentrated sulfuric acids and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 It is 7.0 that mol/L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, and extract mixing decompression is steamed Solid is evaporated to obtain, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L6 of concentration.By gained sulfonic acid Sodium salt adds 0.05 mol Me in the dichloroethane solution for being dissolved in 500 mL2SAuCl and 0.05 mol NiCl2Reaction 24 Hour, 1 mol carrier magnesia-alumina hydrotalcite compounds are added, are reacted at room temperature 24 hours, are filtered, drying obtains class at 40 DEG C The golden nickel two-element match of hydrotalcite load.Take 1 mol cinnamyl alcohol to add in 1000 mL reactors, add 4 mol H2O2, The copper complex of the houghite load of cinnamyl alcohol mass number 2% is added, is warming up to after 80 DEG C, by catalyst after 12 h of reaction Centrifuged with reaction solution, reaction solution delivers to liquid chromatogram identification and analysis, and the yield of cinnamic acid is up to 76%.
Embodiment 7
By 4 mol MgO, 2 mol Al2O31.0 L colloids are made into deionized water with 2 mol ammonium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 80 DEG C of crystallization 6 hours, filters, is washed with water to neutral 80 DEG C of drying, the solid of gained Sample is calcined 4 hours at 300 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 60 mesh powder to be placed in water, used Sodium hydroxide regulation and control pH value is filtered and is washed with water to neutrality to be stirred vigorously aging 24 hours at 9.0,80 DEG C, 80 DEG C of drying, Obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 7 is taken to be dissolved in 100 mL dichloromethane, while being added dropwise 100 The nitration mixture of the mL concentrated sulfuric acids and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 It is 7.0 that mol/L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, and extract mixing decompression is steamed Solid is evaporated to obtain, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L7 of concentration.By gained sulfonic acid Sodium salt adds 0.05 mol VCl in the toluene and DMF mixed solution for being dissolved in 500 mL2With 0.05 mol Mn (CH3COO)2Reaction 24 hours, adds 1 mol carrier magnesia-alumina hydrotalcite compounds, reacts at room temperature 48 hours, filtering, 40 Drying obtains the vanadium manganese two-element match of houghite load at DEG C.1 mol ethylene glycol is taken to add in 1000 mL reactors, Add 4 mol H2O2, the copper complex of the houghite load of quality of glycol number 2% is added, is warming up to after 80 DEG C, reacts Catalyst and reaction solution are centrifuged after 24 h, reaction solution delivers to liquid chromatogram identification and analysis, and the yield of glycolaldehyde is reachable 83%。
Embodiment 8
By 4 mol MgO, 2 mol Al2O31.0 L colloids are made into deionized water with 2 mol potassium carbonate；It is violent at room temperature Stirring 8.0 hours, is placed in crystallizing kettle 80 DEG C of crystallization 6 hours, filters, is washed with water to neutral 80 DEG C of drying, the solid of gained Sample is calcined 4 hours at 300 DEG C, obtains corresponding Mg-Al composite oxide；It is ground to form into 60 mesh powder to be placed in water, used Sodium hydroxide regulation and control pH value is filtered and is washed with water to neutrality to be stirred vigorously aging 24 hours at 9.0,80 DEG C, 80 DEG C of drying, Obtain carrier magnesia-alumina hydrotalcite compound.0.1 mol ligand L 8 is taken to be dissolved in 100 mL dichloromethane, while being added dropwise 100 The nitration mixture of the mL concentrated sulfuric acids and 300 mL oleums, room temperature reaction adds 500 g mixture of ice and water after 24 hours, and uses 6 It is 7.0 that mol/L NaOH solution, which is neutralized to pH value, is extracted 3 times with 500 mL dichloromethane respectively, and extract mixing decompression is steamed Solid is evaporated to obtain, in the cold methanol that the solid is dissolved in 200 mL, filtering, the sulfonate sodium for obtaining L8 of concentration.By gained sulfonic acid Sodium salt adds 0.1 mol acetic acid cadmium reaction 24 hours in the toluene and DMF mixed solution for being dissolved in 500 mL, adds 1 Mol carrier magnesia-alumina hydrotalcite compounds, are reacted at room temperature 12 hours, filtering, and drying obtains the cadmium of houghite load at 40 DEG C Complex.Take 1 mol glycerine to add in 1000 mL reactors, be filled with 2 Mpa oxygen, add glycerine mass number 2% Houghite load copper complex, be warming up to after 60 DEG C, centrifuge catalyst and reaction solution after 6 h of reaction, reaction Liquid delivers to liquid chromatogram identification and analysis, and the yield of 1,3-Dihydroxyacetone is up to 53%.

Claims (6)

1. a kind of new catalyst that production aldehyde ketone is aoxidized for alcohol, it is characterised in that：Catalyst is with natural stabilisation structure Houghite be carrier, using the metal complex of high activity as catalytic oxidation activity center, the metal combination of the high activity Thing is one or both of V, Cr, Mn, Fe, Co, Ni, Cu, Au, Pd, Pt, and the content of wherein institute's carried metal element accounts for catalysis The 0.03 ~ 5.00% of agent gross mass.
2. a kind of according to claim 1 be used for the preparation method that alcohol aoxidizes the new catalyst of production aldehyde ketone, its feature exists In：The preparation comprises the following steps：
（1）The colloid mixture aqueous solution of magnesia, aluminum oxide and carbonate is prepared, magnesium, the mol ratio of aluminium content are 2.0~5.0, Magnesium, the total ion concentration of aluminium are 2.0~5.0 mol/L；Carbonate is identical with the mole dosage of aluminum oxide；It is stirred vigorously at room temperature After 1~6 hour, 60~120 DEG C of crystallization are placed in crystallizing kettle 6~24 hours, it is then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, and 60~100 DEG C of drying, the solid sample of gained is calcined 4~16 hours at 200~400 DEG C, is made Obtain corresponding Mg-Al composite oxide；
（2）Preparation steps（1）The colloid aqueous solution of the Mg-Al composite oxide of middle 40-600 mesh, controls its pH value to exist using alkali lye Between 9~11, temperature is 40~80 DEG C, is stirred vigorously aging 12-36 hours, then that the gel filtration of gained or centrifugation is de- Water, is washed with water to neutrality, 60~100 DEG C of drying, prepares corresponding magnesia-alumina hydrotalcite compound；
（3）According toNature Communication, 2014, 5, 3470Described in prepare ligand L 1-L8, using dense H2SO4With oleum sulfonation L1-L8 parts, and using NaOH neutralize, contained-SO3A series of Na parts, then by institute Obtain the metal complex anions that sodium salt with metal salt be coordinated the sulfonation needed for obtaining in dichloroethane solvent system；
（4）By step（2）The magnesia-alumina hydrotalcite compound and step of preparation（3）The metal complex of the sulfonation of middle gained it is cloudy from Son reacts 12~48 hours in appropriate solution system, obtains the magnesia-alumina hydrotalcite of corresponding metal complex load.
3. a kind of according to claim 2 be used for the preparation method that alcohol aoxidizes the new catalyst of production aldehyde ketone, its feature exists In：In the step（1）In, the carbonate is one kind in ammonium carbonate, sodium carbonate, potassium carbonate.
4. a kind of according to claim 2 be used for the preparation method that alcohol aoxidizes the new catalyst of production aldehyde ketone, its feature exists In：In the step（2）In, the alkali lye is one kind in sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea.
5. a kind of according to claim 2 be used for the preparation method that alcohol aoxidizes the new catalyst of production aldehyde ketone, its feature exists In：In the step（3）In, the metal salt is acetate or chloride, the metal for Fe, Co, Ni, Cu, V, Cr, Mn Salt is AuCl or Me for Au, Pd, Pt2SAuCl、PdCl2And PtCl2。
6. a kind of according to claim 2 be used for the preparation method that alcohol aoxidizes the new catalyst of production aldehyde ketone, its feature exists In：In the step（4）In, the appropriate solution system is one kind in toluene, ethanol, dichloromethane, dichloroethanes, DMF Or two kinds.
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CN112371193A (en) * 2020-11-20 2021-02-19 江南大学 Hydrotalcite-loaded gold-nickel catalyst, and preparation method and application thereof
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