CN108554405A - A kind of noble-metal-supported zirconia-magnesia composites catalyst and the preparation method and application thereof of barium ions modification - Google Patents
A kind of noble-metal-supported zirconia-magnesia composites catalyst and the preparation method and application thereof of barium ions modification Download PDFInfo
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Abstract
The present invention provides a kind of noble-metal-supported zirconia-magnesia composites catalyst and the preparation method and application thereof of barium ions modification, the catalyst includes active component and carrier, active component is the combination of one or more of Pd, Ru, Pt, Rh, Au compound, it is prepared using sol-gal process, pass through the modification of barium ions, the saponification for greatly reducing catalytic reaction process maintains the high catalytic activity of catalyst.The catalyst prepares conjugated linoleic acid for heterogeneous catalysis linoleic acid, and obtained conjugated linoleic acid purity is more than 85%, and catalytic efficiency reaches 1.6g CLA g (CLA) L‑1(solvent)min‑1, catalysate is mainly three kinds of conjugated linoleic acid isomers with physiological activity.The catalyst of the present invention has high catalytic efficiency, and high bioactivity isomer products, catalyst are reusable, is not susceptible to the advantages that saponification, stability are good, and post-processing is simple, and production cost is low, production process does not generate secondary pollution.
Description
Technical field
The invention belongs to technical field of chemistry, and in particular to a kind of Ba2+The noble-metal-supported zirconium magnesium composite oxygen of ion modification
Compound catalyst and preparation method thereof is applied.
Background technology
Conjugated linoleic acid (CLA) is a kind of polyunsaturated fatty acid with physiological activity, is by essential fatty acid -- it is sub-
The general name of a variety of positions and geometric isomer of conjugated diene acid derived from oleic acid.It is main by natural and artificial synthesized CLAs
Ingredient is 9c, 11t-, 10t, 12c- and 10t, tetra- kinds of isomers of 12t- CLA, wherein 9c, 11t-, 10t, 12c-, 9t,
11t- isomers has been shown to have very strong biological activity.In the past 10 years the study found that conjugated linoleic acid have weight-reducing,
Anticancer, anti-diabetic resist athero- artery sclerosis, improve the different physiological roles such as metabolism of bone tissue, in medicine, food and feed neck
Domain has important researching value.
Current is both at home and abroad conjugated linoleic acid by linoleic acid（CLA）Research and production report be broadly divided into biology it is different
Structure method and chemical isomerization method, the high specificity of biological isomerate process, active CLA isomers content is high in product, and reaction condition is mild,
But low yield, manufacturing cost is high, and is difficult to apply to mass produce.Common chemical isomerization method is high-temperature alkali isomerization process,
Using linoleic acid or methyl linoleate as raw material, double bond conjugation is made under the action of highly basic, obtains the mixture of CLA isomerization,
The catalyst that high-temperature alkali isomerization process uses mainly has a highly basic such as KOH, NaOH, sodium methoxide, sodium ethoxide for highly basic, however highly basic
The fatty acid salt formed with fatty acid response, needs that a large amount of acid is added after the completion of reaction, to neutralize, not only to greatly increase in this way
The production cost of CLA, also results in environmental pollution.
Therefore, simple, the environmental-friendly heterogeneous catalyst of exploitation separating-purifying is the key that CLA productions.The public affairs such as Bernas
A series of catalyst of table are developed, Ru is carried on Al respectively2O3, SiO2, SiO2-Al2O3, TiO2, MCM-22, H-MCM-
Heterogeneous catalyst is made on the carriers such as 41 and C, catalytic result shows the chemisorption hydrogen ability of catalyst to linoleic turn
Rate has a major impact, and metal Ru and Ni show best conjugation catalytic performance.But these catalyst exist apparent
Defect, first, for noble-metal-supported on carrier, being easy to happen noble metal obscission, catalyst is easy inactivation, i.e. catalyst
Repeat performance reduces, simultaneously as noble metal remains on after falling off in CLA, CLA is made to be contaminated, affects making for CLA
With safety.Secondly, in these isomerization reactions, using a large amount of solvent, as 0.2g linoleic acid in be added the octanol of 70mL/
All there is certain toxicity, the difficulty for causing CLA to be detached with solvent to have seriously affected the use of CLA for decane, these solvents.Most
Afterwards, the catalytic efficiency of these catalyst is relatively low, and linoleic concentration substantially in 0.01mol/L, cannot achieve industrialized production.
Philippaerts etc. is by RuO2It is highly dispersed in the zeolite surface of Cs doping, under conditions of improving catalyst surface alkalinity,
Without hydrogen pretreatment, isomerization reaction is carried out to linoleic acid, it is found that the catalyst has a very high activity and selectivity, hydrogen in product
It is extremely low to change product, and cis-isomer content is very high in reaction product.But the catalyst preparation process is complicated, isomerization reaction
It needs to carry out under 3.5 atmospheric pressure, severe reaction conditions.The Chen Jiebo of one of inventor loads neatly using Ru
The solid base catalysts such as the zirconia-magnesia composites that stone composite oxides, Ru are loaded, catalysis linoleic acid prepare conjugated linoleic acid, obtain
To catalytic efficiency, the higher catalyst of linoleic acid rate, but the content of magnesium of these catalyst is all higher, and alkalinity is stronger, holds
Saponification is easily generated in catalytic reaction process, causes the inactivation of catalyst and is catalyzed the difficulty of post-reaction treatment.Therefore, it opens
Hair high activity, high stability, low saponification catalyst become key.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of high catalytic efficiency, high bioactivity isomers
Product, reusable Ba2+Noble-metal-supported zirconia-magnesia composites catalyst of ion modification and preparation method thereof, simultaneously
Low based on a kind of production cost of catalyst offer, post-processing is simple, high conversion rate, the preparation of environmental-friendly conjugated linoleic acid
Method.
To achieve the above object, the present invention uses following technical scheme：
A kind of Ba2+The noble-metal-supported zirconia-magnesia composites catalyst of ion modification, the catalyst include active component and
The preparation method of carrier, the catalyst is as follows：
1）By Zr4+ : Mg2+:The amount ratio of lemon acid substance=（1-4）:（1-4）:10, Ba2+Amount be zirconium magnesium gross mass
The mixture of 0.1-5% is dissolved in a small amount of distilled water, stirs to clarify viscous fluid, and 5-12 is heated under 85-90 DEG C of constant temperature
H evaporates excessive moisture and promotes the gelation of mixture, obtains yellow gel；
2）By the gel in 110-130 DEG C of dry 10- 14h, 3.5-4.5h is roasted at 480-500 DEG C, obtains Ba-MgO-
ZrO2Carrier is denoted as BZM-SG.
3）By equi-volume impregnating by above-mentioned carrier impregnation in the noble metal active component solution of metering, by super
The zirconia-magnesia composites catalyst of Ba modifications, i.e. the linoleic acid isomerization catalysis of precious metal doping are obtained after sound, drying, roasting
Agent.
The active component is one or more of Pd, Ru, Pt, Rh, Au compound, active component weight percentage
For 0.01-5%.
Further, the active component solution is nitrate, chloride, acetate or the acetyl in Pd, Ru, Pt, Rh, Au
One or more of acetone object.
Zr in raw material4+, Mg2+, Ba2+For Zr4+, Mg2+, Ba2+The forms such as nitrate, chloride or sulfate.
The catalyst prepares conjugated linoleic acid for being catalyzed linoleic acid, and method is as follows：
It takes 2g catalyst to be added in the three-neck flask of the linoleic n-undecane solution of 0.5 mol/L of 50mL, is passed through N2
10min removes the oxygen in reaction vessel, and 180 DEG C of heating 4h are centrifuged after cooling under 10000r/min supercentrifuges,
Upper layer oily liquids is taken, in case further gas chromatographic detection.
Catalytic reaction products analysis method
（1）Esterification：Reaction product is taken, 3mL13% boron trifluoride methanol solution is added, leads to nitrogen 5 minutes, heating is boiled
10min stops heating, and 3mL isooctane, which is added, after cooling from condenser pipe top transfers the solution into 60mL pear shape separatory funnels,
The saturated nacl aqueous solution of 20mL is added, fierce shaking 15 seconds after standing, takes upper organic layer, and anhydrous magnesium sulfate drying is added,
GC analyses are directly carried out after 0.32 μm of membrane filtration.
（2）Analysis detection：HP-88 capillary columns（100m×0.25mm×0.25μm）, 1 μ L of sample size, split ratio 30:1,
260 DEG C of injector temperature, helium gas flow：0.9mL/min, column temperature：150 DEG C of holding 0.5min, 230 DEG C are risen to 7 DEG C/min
, 290 DEG C then are risen to 10 DEG C/min, 290 DEG C of holding 10min.
The present invention, using zirconia-magnesia composites as carrier, is passed through using above technical scheme using noble metal as active component
Add Ba2+Ion modification agent improves the dispersion degree and strong metal-support interaction of noble metal, different to improve catalyst
Structure linoleic acid prepares the catalytic efficiency of conjugated linoleic acid, and then a kind of production cost of offer is low, and post-processing is simple, conversion ratio
Height, the method for environmental-friendly preparation conjugated linoleic acid.
Linoleic acid is directly utilized catalyst isomerization, filtration catalytic agent, obtained conjugated linoleic acid pure by the present invention
Degree is more than 85%, and catalytic efficiency is more than 1.6g CLA g (CLA) L-1(solvent) min-1, catalysate is mainly three kinds of tools
There are the conjugated linoleic acid isomers of physiological activity.The catalyst of the present invention has high catalytic efficiency, the production of high bioactivity isomers
Object, catalyst are reusable, and it is good to be not susceptible to saponification, stability, and post-processing is simple, and production cost is low, production
Process does not generate the advantages that secondary pollution.
Description of the drawings
Fig. 1 is the gas chromatogram of catalysate of the present invention.
Specific implementation mode
Embodiment 1
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=1 of lemon acid substance:1:10, Ba2+Amount be zirconium magnesium total material amount 0.5% mixture
It is dissolved in a small amount of distilled water, stirs to clarify viscous fluid, 5h is heated under 90 DEG C of constant temperatures, evaporate excessive moisture and promote
The gelation of mixture.Obtained yellow gel is placed in 120 DEG C of 12 h of drying, is obtained in 500 DEG C of 10 DEG C/min roastings 4h
To Ba-MgO-ZrO2Carrier.By equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of ruthenium trichloride+Precious metal ion
In solution, the linoleic acid isomerization catalyst of precious metal doping is obtained after ultrasound, drying, roasting.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min stops heating, and 30mL isooctane is added from condenser pipe top, separatory funnel is moved into after cooling, 50mL is added and is saturated NaCl
Solution is layered, and takes upper organic layer to sample cell, anhydrous magnesium sulfate water suction is added, gas chromatographic detection shows that product conjugation is sub-
Oleic acid content reaches 92%, wherein c10, t12-CLA, t9, c11-CLA, t9, and t11-CLA three's content reaches total conjugated linoleic acid
90%.
Embodiment 2
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=1 of lemon acid substance:1:10, Ba2+Amount be zirconium magnesium total material amount 2% mixture it is molten
In a small amount of distilled water, viscous fluid is stirred to clarify, 5h is heated under 90 DEG C of constant temperatures, evaporate excessive moisture and is promoted mixed
Close the gelation of object.Obtained yellow gel is placed in 120 DEG C of 12 h of drying, is obtained in 500 DEG C of 10 DEG C/min roastings 4h
Ba-MgO-ZrO2Carrier, by equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of palladium chloride solution, by super
The linoleic acid isomerization catalyst of precious metal doping is obtained after sound, drying, roasting.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min stops heating, and 30mL isooctane is added from condenser pipe top, separatory funnel is moved into after cooling, 50mL is added and is saturated NaCl
Solution is layered, and takes upper organic layer to sample cell, anhydrous magnesium sulfate water suction is added, gas chromatographic detection shows that product conjugation is sub-
Oleic acid content reaches 80%, wherein c10, t12-CLA, t9, c11-CLA, t9, and t11-CLA three's content reaches total conjugated linoleic acid
86%.
Embodiment 3
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=1 of lemon acid substance:4:10, Ba2+Amount be zirconium magnesium total material amount 0.5% mixture
It is dissolved in a small amount of distilled water, stirs to clarify viscous fluid, 5h is heated under 90 DEG C of constant temperatures, evaporate excessive moisture and promote
The gelation of mixture.Obtained yellow gel is placed in 120 DEG C of 12 h of drying, is obtained in 500 DEG C of 10 DEG C/min roastings 4h
To Ba-MgO-ZrO2Carrier.By equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of platinum acid chloride solution, by super
The linoleic acid isomerization catalyst of precious metal doping is obtained after sound, drying, roasting.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min, stops heating, and the saponification of part has occurred in reaction system.30mL isooctane is added at the top of from condenser pipe, after cooling
Separatory funnel is moved into, 50mL saturation NaCl solution layerings are added, takes upper organic layer to sample cell, anhydrous magnesium sulfate is added and inhales
Water, gas chromatographic detection show that product cla levels reach 36%.
Embodiment 4
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=4 of lemon acid substance:1:10, Ba2+Amount be zirconium magnesium total material amount 0.1% mixture
It is dissolved in a small amount of distilled water, stirs to clarify viscous fluid, 8h is heated under 85 DEG C of constant temperatures, evaporate excessive moisture and promote
The gelation of mixture.Obtained yellow gel is placed in 110 DEG C of dry 14h, 4.5h is roasted at 480 DEG C and obtains Ba-MgO-
ZrO2Carrier.By equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of chlorine rhodium acid ammonium solution, by ultrasound, dry
The linoleic acid isomerization catalyst of precious metal doping is obtained after dry, roasting.
Zr in raw material4+, Mg2+, Ba2+For Zr4+, Mg2+, Ba2+Nitrate.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min stops heating, and 30mL isooctane is added from condenser pipe top, separatory funnel is moved into after cooling, 50mL is added and is saturated NaCl
Solution is layered, and takes upper organic layer to sample cell, anhydrous magnesium sulfate water suction is added, gas chromatographic detection shows that product conjugation is sub-
Oleic acid content reaches 90%, wherein c10, t12-CLA, t9, c11-CLA, t9, and t11-CLA three's content reaches total conjugated linoleic acid
85%.
Embodiment 5
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=2 of lemon acid substance:3:10, Ba2+Amount be zirconium magnesium total material amount 2% mixture it is molten
In a small amount of distilled water, viscous fluid is stirred to clarify, 12h is heated under 90 DEG C of constant temperatures, evaporate excessive moisture and is promoted mixed
Close the gelation of object.Obtained yellow gel is placed in 123 DEG C of 10 h of drying, 3.5h is roasted at 500 DEG C and obtains Ba-MgO-
ZrO2Carrier.By equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of tetrachloro gold ammonium salt solution, by ultrasound, dry
The linoleic acid isomerization catalyst of precious metal doping is obtained after dry, roasting.
Zr in raw material4+, Mg2+, Ba2+For Zr4+, Mg2+, Ba2+Sulfate.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min stops heating, and 30mL isooctane is added from condenser pipe top, separatory funnel is moved into after cooling, 50mL is added and is saturated NaCl
Solution is layered, and takes upper organic layer to sample cell, anhydrous magnesium sulfate water suction is added, gas chromatographic detection shows that product conjugation is sub-
Oleic acid content reaches 89%, wherein c10, t12-CLA, t9, c11-CLA, t9, and t11-CLA three's content reaches total conjugated linoleic acid
84%.
Embodiment 6
1、Ba2+The preparation of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
By Zr4+：Mg2+：Amount ratio=3 of lemon acid substance:2:10, Ba2+Amount be zirconium magnesium total material amount 5% mixture it is molten
In a small amount of distilled water, viscous fluid is stirred to clarify, 5h is heated under 90 DEG C of constant temperatures, evaporate excessive moisture and is promoted mixed
Close the gelation of object.Obtained yellow gel is placed in 120 DEG C of 12 h of drying, 4h is roasted at 500 DEG C and obtains Ba-MgO-
ZrO2Carrier.By equi-volume impregnating by above-mentioned carrier impregnation in a certain amount of solution of ruthenium trichloride, by ultrasound, dry
The linoleic acid isomerization catalyst of precious metal doping is obtained after dry, roasting.
Zr in raw material4+, Mg2+, Ba2+For Zr4+, Mg2+, Ba2+Chloride.
2, catalysis linoleic acid prepares conjugated linoleic acid
It takes the above-mentioned catalyst of 2g to be added in the linoleic three-neck flask of 0.5 mol/L of 50mL, is passed through N2 10min is removed
Oxygen in reaction vessel, 180 DEG C of heating 4h, is added the boron trifluoride methanol solution of 50mL 12%, heating is boiled after cooling
5min stops heating, and 30mL isooctane is added from condenser pipe top, separatory funnel is moved into after cooling, 50mL is added and is saturated NaCl
Solution is layered, and takes upper organic layer to sample cell, anhydrous magnesium sulfate water suction is added, gas chromatographic detection shows that product conjugation is sub-
Oleic acid content reaches 91%, wherein c10, t12-CLA, t9, c11-CLA, t9, and t11-CLA three's content reaches total conjugated linoleic acid
85%.
Claims (7)
1. a kind of Ba2+The preparation method of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification, the catalyst packet
Include active component and carrier, it is characterised in that：The preparation method of the catalyst is as follows：
1）By Zr4+ : Mg2+:The amount ratio of lemon acid substance=（1-4）:（1-4）:10, Ba2+Amount be zirconium magnesium gross mass
The mixture of 0.1-5% is soluble in water, and 5-12 h are heated in stirring to viscous fluid under 85-90 DEG C of constant temperature, evaporate superfluous water
The gelation for dividing and promoting mixture, obtains gel；
2）By the gel in 110-130 DEG C of dry 10- 14h, 3.5-4.5h is roasted at 480-500 DEG C, obtains Ba-MgO-
ZrO2Carrier；
3）By above-mentioned carrier impregnation in the noble metal active component solution of metering, obtains Ba after ultrasound, drying, roasting and repair
The zirconia-magnesia composites catalyst of decorations.
2. according to a kind of Ba described in claim 12+The system of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
Preparation Method, it is characterised in that：The active component is one or more of Pd, Ru, Pt, Rh, Au compound, active component weight
Amount percentage composition is 0.01-5%.
3. according to a kind of Ba described in claim 22+The system of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
Preparation Method, it is characterised in that：The active component solution be Pd, Ru, Pt, Rh, Au in nitrate, chloride, acetate or
One or more of acetylacetone,2,4-pentanedione object.
4. according to a kind of Ba described in claim 12+The system of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
Preparation Method, it is characterised in that：Zr in raw material4+, Mg2+, Ba2+For Zr4+, Mg2+, Ba2+Nitrate, chloride or sulfate shape
Formula.
5. according to a kind of Ba described in claim 12+The system of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification
Preparation Method, it is characterised in that：The dipping uses equi-volume impregnating.
6. the Ba obtained according to any preparation methods of claim 1-52+The noble-metal-supported zirconia-magnesia composites of ion modification
Catalyst.
7. Ba as claimed in claim 62+The application of the noble-metal-supported zirconia-magnesia composites catalyst of ion modification, it is special
Sign is：The catalyst is used to prepare conjugated linoleic acid.
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| CN112495451A (en) * | 2020-11-24 | 2021-03-16 | 大连理工大学 | Method for manufacturing solid catalyst by using laser processing technology |
Citations (6)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112495451A (en) * | 2020-11-24 | 2021-03-16 | 大连理工大学 | Method for manufacturing solid catalyst by using laser processing technology |
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