CN103084209A - Application of nickel base micropore material in esterification reaction catalysis - Google Patents
Application of nickel base micropore material in esterification reaction catalysis Download PDFInfo
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Abstract
The present invention relates to a nickel base catalysis material and an application of the nickel base catalysis material in an esterification reaction. The nickel base catalyst preparation method comprises: respectively dispersing a nickel base compound and an organic monoacid or an organic polybasic acid into an organic solvent to prepare mother liquors with a certain concentration, mixing the mother liquors at a synthesis temperature of 0-150 DEG C under a stirring condition according to a Ni<2+>/-COOH (organic acid radical) molar ratio of 20:1-1:10, carrying out a reaction for 0.1-72 h, transferring the obtained material to a reaction kettle, standing for 1-360 h at a temperature of 0-200 DEG C, and carrying out separation, washing and drying on the obtained precipitate to obtain the catalyst. The esterification reaction process comprises: adding the prepared nickel base catalyst to a mixing system formed by mixing an organic acid and an alcohol according to a certain ratio, carrying out a reaction for a certain time under a stirring and heating condition, and stopping the reaction.
Description
Technical field
The invention belongs to catalysis material preparation and catalytic esterification technical field, be specifically related to a kind of Ni-based catalysis material and the application in esterification thereof.
Background technology
Ester is the important Organic Ingredients of a class, is widely used in the aspects such as solvent, plasticizer, resin, coating, essence and flavoring agent, cosmetics, medicine, surfactant and reaction intermediate, and esterification is the important channel of preparation Ester.Because its being widely used property and importance make Chinese scholars particularly pay attention to the research of esterification.Esterification needs to complete under catalyst action usually, traditional synthetic method is take corresponding Carboxylic acid and alcohol as raw material, adopting the concentrated sulfuric acid is that catalyst is produced, and this method side reaction is many, aftertreatment technology is complicated, equipment corrosion is serious, spent acid exhaust emission environment.In recent years, catalytic esterification method such as chemical catalysis (inorganic acid, solid acid, ionic liquid-catalyzed etc.), physical catalyze (microwave catalysis, magnetic field catalysis etc.), living things catalysis (biological enzyme) and reaction process is first-class all obtains very large progress, esterification yied is increased substantially, and the quality of esterification products is also obviously improved.
CN101049573A has prepared a kind of ionic liquid and has been applied to esterification, has higher reactivity.CN1323655 prepares oxide carried solid acid catalyst by coprecipitation, and in the esterification of catalysis acetic acid and n-butanol, the yield of n-butyl acetate reaches 90%.CN101108360A has announced the preparation method of a kind of silicon tungsten, phosphorus heteropoly tungstic acid loaded catalyst, shows good activity and selectivity in esterification.CN101485998A adopts organic phospho acid as the catalyst of esterification, and esterification yield reaches more than 90%.
At present, solid acid catalyst replaces sulfuric acid and carries out catalytic esterification, although overcome some shortcomings of sulfuric acid catalysis, as seriously corroded, the shortcoming such as seriously polluted but Shortcomings still, as: reaction temperature is higher, complicated process of preparation, cost is expensive, the easy inactivation of catalyst, and regeneration difficulty and reactivity are poor etc.As catalyst, prepare its uses of drawbacks limit such as complexity, severe reaction conditions for ionic liquid.Although the biological enzyme environmental protection, reaction condition is gentle, and the reaction time is longer, and productive rate is lower.
Therefore, develop a kind of the preparation simply, have greater activity and selective, the catalysis material that product yield is high and of reduced contamination causes researcher's extensive concern.
Summary of the invention
Meaning of the present invention has been to overcome the shortcoming that present catalyst for esterification reaction exists, as: preparation is complicated, poor activity, severe reaction conditions, it is catalyst based that contaminated environment etc. have prepared microporous nickel, and preparation is simple, and stability is high, and show very high activity in esterification, and environmental friendliness.
The catalyst of the present invention's design prepares by following scheme.The preparation process of described Ni-based catalysis material is as follows: with Ni-based compound and monobasic or multicomponent organic acid, make certain density mother liquor after being scattered in respectively organic solvent; In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.01～2.5mol/L, in monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.01～2.5mol/L;
Under 0 ℃～150 ℃ synthesis temperatures, under stirring condition, press Ni
2+/-COOH (organic acid) molar ratio of 20: 1～1: 10 mixes above-mentioned mother liquor, after reaction 0.1h～72h, is transferred to reactor, at 0 ℃～200 ℃ temperature, and standing 1h～360h; This nickel-base material will be made after sediment separation, washing, drying.
Be preferably: described Ni-based compound is one or more in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, nickel oxalate, acetylacetonate nickel, nickel sulfamic acid, nickel stearate; Described monobasic or multicomponent organic acid are: formic acid, acetic acid, propionic acid, 2-furancarboxylic acid, 2-pyridine carboxylic acid, benzoic acid, p-methylbenzoic acid, ethanedioic acid, malonic acid, succinic acid, suberic acid, 2,5-furandicarboxylic acid, 2, one or more in 5-pyridinedicarboxylic acid, terephthalic acid (TPA), phthalic acid.Described organic solvent is: formamide, N-METHYLFORMAMIDE, N-ethyl-formamide, DMF, N, one or more in the N-DEF; Synthesis temperature is 10 ℃～130 ℃, and the reaction time is: 0.5h～30h; Dwell temperature is: 20 ℃～150 ℃, time of repose is: 10h～240h;
In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.1～1.0mol/L;
In monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.1～1.0mol/L; Described Ni
2+The molar ratio of/-COOH is: 10: 1～1: 5.
Be more preferred from: described Ni-based compound is: one or more in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, acetylacetonate nickel; Described monobasic or multicomponent organic acid are: one or more in acetic acid, 2-pyridine carboxylic acid, benzoic acid, ethanedioic acid, FDCA, terephthalic acid (TPA); Described organic solvent is: N-METHYLFORMAMIDE, DMF, N, one or more in the N-DEF; Synthesis temperature is 20 ℃～50 ℃, and the reaction time is: 1h～5h; Dwell temperature is: 80 ℃～150 ℃, time of repose is: 24h～72h; In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.1～0.5mol/L; In monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.1～0.5mol/L; Described Ni
2+The molar ratio of/-COOH is: 5: 1～1: 2.
The best is; Described Ni-based compound is: one or more in nickel chloride, nickel acetate, acetylacetonate nickel; Described monobasic or multicomponent organic acid are: one or more in acetic acid, benzoic acid, FDCA; Described organic solvent is DMF.
The preparation principle of this Ni-based poromerics be the amide-type organic solvent under the organic acid effect, hydrolysis occurs, slowly discharge formate ion; Formate ion and nickel ion generation complex reaction are the microporous nickel sill with regular pore canal structure along certain axial growth.
Adopt the micropore nickel formate catalyst of said method preparation as the catalyst of esterification, and a certain amount of catalyst and a certain amount of organic acid and alcohol mixed, put into reaction bulb, stir and the condition of heating under, react certain hour.Having acidic-group in the duct of this micropore nickel formate catalyst, as surface hydroxyl, carboxylic acid group etc., is the activated centre of catalytic esterification.And due to such group be evenly distributed and density higher, therefore show activity and selectivity preferably.Another characteristics of this formates material are that stability is high.Common nickel formate sample is easy to be dissociated into homogeneous phase under acid condition, make the reaction homogeneous phase, without the duct catalytic effect.By comparison, the nickel formate of micropore forms 3-D solid structure in building-up process, be connected by the metal oxygen key, Stability Analysis of Structures and have pore passage structure abundant, after reaction by recycling after simple separation.The organic acid that can be suitable for is one or more in formic acid, acetic acid, propionic acid, stearic acid, palmitic acid, lactic acid, n-butyric acie, isobutyric acid, malonic acid, succinic acid, adipic acid, pimelic acid, benzoic acid, salicylic acid, cinnamic acid, syringic acid, P-hydroxybenzoic acid, ortho-toluic acid, meta-toluic acid, vanillic acid, terephthalic acid (TPA), FDCA.The Organic Alcohol that can be suitable for is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, butanols, n-hexyl alcohol, enanthol, octanol, phenmethylol, ethylene glycol, glycerine, isopropyl alcohol, the tert-butyl alcohol, sec-butyl alcohol, isoamyl alcohol, secondary octanol, 2-methyl-1-pentene alcohol, one or more in 2-methoxybenzene methyl alcohol.
The concrete implementation step of catalytic esterification is as follows:
In liquid system, employing concentration is that (Ni-based catalysis material COOH) is during as catalyst for 50g～500g/mol, and (OH) (mol ratio COOH) is 1～60 to alcohol with acid, stir, add thermal response 2h～40h at 50 ℃～200 ℃ temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 92%～100%, is selectively 95%～100%.Can continue to recycle through oven dry after the centrifugal recovery of catalyst, cycle-index is more than 3 times.
The present invention compares with traditional esterification reaction tech, has following several advantage:
1, the catalyst preparation is simple, has larger specific surface, and heat endurance is high.
2, the catalytic esterification system is simple, does not need additionally to add any solvent.
3, the catalyst centrifugation gets final product, and catalyst is recyclable to be recycled.
4, catalyzed conversion presents high conversion, high selectivity.
5, have good universality, all can generate corresponding ester class by catalyzed conversion for most of organic acid and alcohol.
The specific embodiment
For the present invention is further elaborated, the below provides several concrete case study on implementation, but the invention is not restricted to these embodiment.
Embodiment 1
14.5g six hydration nickel sulfate and 18g terephthalic acid (TPA) are added to respectively 400mL N, N-DEF and 5L N, in the organic solvent of N-DEF, dissolving; After dissolving, under 100 ℃, mix above-mentioned two kinds of solution, stir 8.5h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 140 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst based catalyst as esterification of microporous nickel.Put into reaction bulb together with the acetic acid of the above-mentioned catalyst of 57g and 1.8mol and 80.4mol n-hexyl alcohol and 500mL cyclohexane, stir, add thermal response 5h at 70 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 92%, is selectively 100%.
Embodiment 2
28.6g Nickel dichloride hexahydrate and 9.96g M-phthalic acid are added to respectively in the organic solvent of 240mL N-ethyl-formamide and 60mL N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 8h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 150 ℃ in reaction temperature, take out after reaction 48h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 60g and 3mol and 60mol n-hexyl alcohol and 1L, stir, add thermal response 7h at 90 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 94%, is selectively 99%.
Embodiment 3
With 62.6g nickel stearate and 4.5g 2,5-furans diacid is added to respectively 10L N, N-DEF and 400mL N, and in the organic solvent of N-DEF, dissolving; After dissolving, under 55 ℃, mix above-mentioned two kinds of solution, stir 3h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 120 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 110g and 10mol and 17mol n-hexyl alcohol and 700mL, stir, add thermal response 8h at 80 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 95%, is selectively 95%.
Embodiment 4
41.2g two oxalic acid hydrate nickel and 48.0g benzoic acid are added to respectively in the organic solvent of 1L N-ethyl-formamide and 2L N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 4h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 130 ℃ in reaction temperature, take out after reaction 60h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 60g and 2mol and 80mol n-hexyl alcohol and 1L, stir, add thermal response 8h at 90 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 94%, is selectively 96%.
Embodiment 5
With 96g nickel acetate tetrahydrate and 23.9g 2,5-furans diacid disperses respectively 2.5L and 2LN, makes mother liquor after dinethylformamide.Under 25 ℃, under the condition that stirs, above-mentioned mother liquor is mixed, after reaction 2.5h, be transferred to pressure vessel, at 140 ℃ of temperature, standing 48h.This nickel-base catalyst will be made after sediment separation, washing, drying.With the catalyst of microporous nickel sill as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 100g and 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 99%, is selectively 96%.
Embodiment 6
14.5g six hydration nickel sulfate and 18g terephthalic acid (TPA) are added to respectively 400mL N, N-DEF and 5L N, in the organic solvent of N-DEF, dissolving; After dissolving, under 100 ℃, mix above-mentioned two kinds of solution, stir 8.5h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 140 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 60g and 2mol and 70mol n-butanol and 10mL, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 99%, is selectively 99%.
Embodiment 7
28.6g Nickel dichloride hexahydrate and 9.96g M-phthalic acid are added to respectively in the organic solvent of 240mL N-ethyl-formamide and 60mL N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 8h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 150 ℃ in reaction temperature, take out after reaction 48h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 160g and 5mol and 50mol n-butanol and 500mL, stir, add thermal response 9h at 70 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 99%, is selectively 99%.
Embodiment 8
With 62.6g nickel stearate and 4.5g 2,5-furans diacid is added to respectively 10L N, N-DEF and 400mL N, and in the organic solvent of N-DEF, dissolving; After dissolving, under 55 ℃, mix above-mentioned two kinds of solution, stir 3h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 120 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the propionic acid of the above-mentioned catalyst of 60g and 5mol and 10mol ethanol and 600mL, stir, add thermal response 15h at 65 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 100%, is selectively 97%.
Embodiment 9
41.2g two oxalic acid hydrate nickel and 48.0g benzoic acid are added to respectively in the organic solvent of 1L N-ethyl-formamide and 2L N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 4h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 130 ℃ in reaction temperature, take out after reaction 60h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the stearic acid of the above-mentioned catalyst of 70g and 5mol and 50mol n-butanol and 1L, stir, add thermal response 20h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 100%, is selectively 96%.
Embodiment 10
With 96g nickel acetate tetrahydrate and 23.9g 2,5-furans diacid disperses respectively 2.5L and 2LN, makes mother liquor after dinethylformamide.Under 25 ℃, under the condition that stirs, above-mentioned mother liquor is mixed, after reaction 2.5h, be transferred to pressure vessel, at 140 ℃ of temperature, standing 48h.This nickel-base catalyst will be made after sediment separation, washing, drying.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the lactic acid of the above-mentioned catalyst of 100g and 1.8mol and 80.4mol n-octyl alcohol and 1L, stir, add thermal response 24h at 110 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 96%, is selectively 95%.
Embodiment 11
14.5g six hydration nickel sulfate and 18g terephthalic acid (TPA) are added to respectively 400mL N, N-DEF and 5L N, in the organic solvent of N-DEF, dissolving; After dissolving, under 100 ℃, mix above-mentioned two kinds of solution, stir 8.5h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 140 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the benzoic acid of the above-mentioned catalyst of 100g and 2mol and 10mol propyl alcohol and 500mL, stir, add thermal response 10h at 100 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 98%, is selectively 99%.
Embodiment 12
28.6g Nickel dichloride hexahydrate and 9.96g M-phthalic acid are added to respectively in the organic solvent of 240mL N-ethyl-formamide and 60mL N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 8h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 150 ℃ in reaction temperature, take out after reaction 48h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the propionic acid of the above-mentioned catalyst of 50g and 5mol and 50mol ethanol and 500mL, stir, add thermal response 11h at 50 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 99%, is selectively 100%.
Embodiment 13
With 62.6g nickel stearate and 4.5g 2,5-furans diacid is added to respectively 10L N, N-DEF and 400mL N, and in the organic solvent of N-DEF, dissolving; After dissolving, under 55 ℃, mix above-mentioned two kinds of solution, stir 3h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 120 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the stearic acid of the above-mentioned catalyst of 60g and 4mol and 80mol n-butanol and 1L, stir, add thermal response 13h at 80 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 95%, is selectively 100%.
Embodiment 14
41.2g two oxalic acid hydrate nickel and 48.0g benzoic acid are added to respectively in the organic solvent of 1L N-ethyl-formamide and 2L N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 4h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 130 ℃ in reaction temperature, take out after reaction 60h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the propionic acid of the above-mentioned catalyst of 100g and 7mol and 10mol ethanol and 500mL, stir, add thermal response 12h at 160 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 93%, is selectively 98%.
Embodiment 15
With 96g nickel acetate tetrahydrate and 23.9g 2,5-furans diacid disperses respectively 2.5L and 2LN, makes mother liquor after dinethylformamide.Under 25 ℃, under the condition that stirs, above-mentioned mother liquor is mixed, after reaction 2.5h, be transferred to pressure vessel, at 140 ℃ of temperature, standing 48h.This nickel-base catalyst will be made after sediment separation, washing, drying.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the stearic acid of the above-mentioned catalyst of 30g and 1.8mmol and 80.4mmol n-butanol and 10mL, stir, add thermal response 6h at 110 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 95%, is selectively 99%.
Embodiment 16
14.5g six hydration nickel sulfate and 18g terephthalic acid (TPA) are added to respectively 400mL N, N-DEF and 5L N, in the organic solvent of N-DEF, dissolving; After dissolving, under 100 ℃, mix above-mentioned two kinds of solution, stir 8.5h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 140 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the lactic acid of the above-mentioned catalyst of 40g and 2mol and 80mol n-octyl alcohol and 800mL, stir, add thermal response 10h at 100 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 96%, is selectively 100%.
Embodiment 17
28.6g Nickel dichloride hexahydrate and 9.96g M-phthalic acid are added to respectively in the organic solvent of 240mL N-ethyl-formamide and 60mL N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 8h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 150 ℃ in reaction temperature, take out after reaction 48h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the benzoic acid of the above-mentioned catalyst of 60g and 1.8mol and 80.4mol propyl alcohol and 1L, stir, add thermal response 15h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 92%, is selectively 99%.
Embodiment 18
With 62.6g nickel stearate and 4.5g 2,5-furans diacid is added to respectively 10L N, N-DEF and 400mL N, and in the organic solvent of N-DEF, dissolving; After dissolving, under 55 ℃, mix above-mentioned two kinds of solution, stir 3h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 120 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the propionic acid of the above-mentioned catalyst of 30g and 2mol and 70mol ethanol and 1L, stir, add thermal response 10h at 100 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 98%, is selectively 100%.
Embodiment 19
41.2g two oxalic acid hydrate nickel and 48.0g benzoic acid are added to respectively in the organic solvent of 1L N-ethyl-formamide and 2L N-ethyl-formamide dissolving; After dissolving, under 40 ℃, mix above-mentioned two kinds of solution, stir 4h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 130 ℃ in reaction temperature, take out after reaction 60h, centrifugal, washing, drying makes nickel-base material.With catalyst based catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 150g and 10mol and 100mol n-hexyl alcohol and 1.5L, stir, add thermal response 10h at 80 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 94%, is selectively 100%.
Embodiment 20
With 96g nickel acetate tetrahydrate and 23.9g 2,5-furans diacid disperses respectively 2.5L and 2LN, makes mother liquor after dinethylformamide.Under 25 ℃, under the condition that stirs, above-mentioned mother liquor is mixed, after reaction 2.5h, be transferred to pressure vessel, at 140 ℃ of temperature, standing 48h.This nickel-base catalyst will be made after sediment separation, washing, drying.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the acetic acid of the above-mentioned catalyst of 60g and 4mol and 80mol n-hexyl alcohol and 800mL, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 96%, is selectively 97%.
Embodiment 21
With 62.6g nickel stearate and 4.5g 2,5-furans diacid is added to respectively 10L N, N-DEF and 400mL N, and in the organic solvent of N-DEF, dissolving; After dissolving, under 55 ℃, mix above-mentioned two kinds of solution, stir 3h, make mother liquor.Above-mentioned mother liquor will be housed insert in reaction bulb, airtight, be under the condition of 120 ℃ in reaction temperature, take out after reaction 72h, centrifugal, washing, drying makes nickel-base material.With the catalyst of nickel-base catalyst as esterification.Put into reaction bulb together with the cyclohexane of the oxalic acid of the above-mentioned catalyst of 70g and 10mol and 10mol ethanol and 700mL, stir, add thermal response 10h at 80 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 98%, is selectively 99%.
The comparative example 1: with the concentrated sulfuric acid as catalyst for esterification reaction
Put into reaction bulb together with the cyclohexane of the acetic acid of the 100g concentrated sulfuric acid and 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 99%, is selectively 99%.
The comparative example 2: with Amberlyst-15 as catalyst for esterification reaction
Put into reaction bulb together with the cyclohexane of the acetic acid of 100g Amberlyst-15 and 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 95%, is selectively 100%.
The comparative example 3: with phosphorus heteropoly tungstic acid as catalyst for esterification reaction
Put into reaction bulb together with the cyclohexane of the acetic acid of 100g phosphorus heteropoly tungstic acid and 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 96%, is selectively 99%.
The comparative example 4: with load SO
4 2-TiO
2As catalyst for esterification reaction
With 100g load SO
4 2-TiO
2Put into reaction bulb together with the cyclohexane of the acetic acid of 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 98%, is selectively 98%.
The comparative example 5: with the nickel formate inorganic salts as catalyst for esterification reaction
Put into reaction bulb together with the cyclohexane of the acetic acid of 100g nickel formate inorganic salts and 1.8mol and 80.4mol n-hexyl alcohol and 1L, stir, add thermal response 10h at 85 ℃ of temperature, centrifugation, chromatogram detects.Chromatogram detects conversion ratio and reaches 90%, is selectively 82%.
Claims (9)
1. the application of Ni-based catalysis material in esterification is characterized in that:
The preparation process of described Ni-based catalysis material is as follows: with Ni-based compound and monobasic or multicomponent organic acid, make certain density mother liquor after being scattered in respectively organic solvent; In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.01～2.5mol/L, in monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.01～2.5mol/L;
Under 0 ℃～150 ℃ synthesis temperatures, under stirring condition, press Ni
2+/-COOH is the molar ratio of 20: 1～1: 10, and above-mentioned mother liquor is mixed, and after reaction 0.1h～72h, is transferred to reactor, at 0 ℃～200 ℃ temperature, and standing 1h～360h; This nickel-base material will be made after sediment separation, washing, drying.
2. according to application claimed in claim 1, it is characterized in that:
Described Ni-based compound is one or more in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, nickel oxalate, acetylacetonate nickel, nickel sulfamic acid, nickel stearate;
Described monobasic or multicomponent organic acid are: formic acid, acetic acid, propionic acid, 2-furancarboxylic acid, 2-pyridine carboxylic acid, benzoic acid, p-methylbenzoic acid, ethanedioic acid, malonic acid, succinic acid, suberic acid, 2,5-furandicarboxylic acid, 2, one or more in 5-pyridinedicarboxylic acid, terephthalic acid (TPA), phthalic acid;
Described organic solvent is: formamide, N-METHYLFORMAMIDE, N-ethyl-formamide, DMF, N, one or more in the N-DEF;
Synthesis temperature is 10 ℃～130 ℃, and the reaction time is: 0.5h～30h;
Dwell temperature is: 20 ℃～150 ℃, time of repose is: 10h～240h;
In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.1～1.0mol/L;
In monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.1～1.0mol/L; Described Ni
2+The molar ratio of/-COOH is: 10: 1～1: 5.
3. according to application claimed in claim 2, it is characterized in that:
Described Ni-based compound is: one or more in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, acetylacetonate nickel;
Described monobasic or multicomponent organic acid are: one or more in acetic acid, 2-pyridine carboxylic acid, benzoic acid, ethanedioic acid, FDCA, terephthalic acid (TPA);
Described organic solvent is: N-METHYLFORMAMIDE, DMF, N, one or more in the N-DEF;
Synthesis temperature is 20 ℃～50 ℃, and the reaction time is: 1h～5h; Dwell temperature is: 80 ℃～150 ℃, time of repose is: 24h～72h;
In Ni-based compound mother liquor, the Ni ion concentration is: Ni
2+: 0.1～0.5mol/L;
In monobasic or multicomponent organic acid mother liquor, the concentration of organic acid ion is :-COOH is 0.1～0.5mol/L; Described Ni
2+The molar ratio of/-COOH is: 5: 1～1: 2.
4. according to the described application of claim 2 or 3, it is characterized in that:
Described Ni-based compound is: one or more in nickel chloride, nickel acetate, acetylacetonate nickel;
Described monobasic or multicomponent organic acid are: one or more in acetic acid, benzoic acid, FDCA;
Described organic solvent is DMF.
5. according to application claimed in claim 1, it is characterized in that:
Adopt the described Ni-based catalysis material of claim 1 as the catalyst of esterification, the process of esterification is: the nickel-base material catalyst for preparing is added to the mixed system of organic acid and alcohol, reaction generates corresponding ester under stirring condition.
6. according to application claimed in claim 5, it is characterized in that:
Described organic acid is one or more in formic acid, acetic acid, propionic acid, stearic acid, palmitic acid, lactic acid, n-butyric acie, isobutyric acid, malonic acid, succinic acid, adipic acid, pimelic acid, salicylic acid, cinnamic acid, syringic acid, vanillic acid, benzoic acid, P-hydroxybenzoic acid, ortho-toluic acid, meta-toluic acid, terephthalic acid (TPA), FDCA;
Described Organic Alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, butanols, n-hexyl alcohol, enanthol, octanol, phenmethylol, ethylene glycol, glycerine, isopropyl alcohol, the tert-butyl alcohol, sec-butyl alcohol, isoamyl alcohol, secondary octanol, 2-methyl-1-pentene alcohol, one or more in 2-methoxybenzene methyl alcohol.
7. according to application claimed in claim 5, it is characterized in that:
In liquid system, employing concentration be 50g～500g/mol (Ni-based catalysis material COOH) is during as catalyst, and alcohol (OH) (mol ratio COOH) is 1～60, stirring reaction with acid, centrifugation catalyst recovery recycling gets esterification products.
8. according to the described method of claim 5 or 7, it is characterized in that: described reaction temperature is 50 ℃～200 ℃, and the reaction time is 2h～40h;
Better reaction temperature is 60 ℃～180 ℃, and the better reaction time is 2h～20h;
Best reaction temperature is 75 ℃～150 ℃, and the best reaction time is 2h～12h.
9. according to application claimed in claim 7, it is characterized in that: the catalyst recovery recycling can be carried out more than 3 times repeatedly.
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| CN201110332171.0A CN103084209B (en) | 2011-10-27 | 2011-10-27 | Application of nickel base micropore material in esterification reaction catalysis |
| PCT/CN2012/079084 WO2013060173A1 (en) | 2011-10-27 | 2012-07-24 | Nickel-based microporous material and preparation and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556444A (en) * | 2017-08-23 | 2018-01-09 | 安徽富煌门窗幕墙有限公司 | One kind coats sol-gel modified building heat preservation sheet material and preparation method thereof |
| CN112893858A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Preparation method of nickel-carbon-based material |
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| US5053211A (en) * | 1981-06-30 | 1991-10-01 | Amoco Corporation | Manufacture of AMS-18 crystalline borosilicate molecular sieve |
| CN1184100A (en) * | 1997-12-10 | 1998-06-10 | 中国科学院广州化学研究所 | Reduction-esterification process synthesizing carboxylate |
| US20030004364A1 (en) * | 2001-04-30 | 2003-01-02 | Yaghi Omar M. | Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage |
| CN101125813A (en) * | 2007-09-14 | 2008-02-20 | 杭州格林香料化学有限公司 | Method for synthesizing allyl cyclohexoxyacetate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5053211A (en) * | 1981-06-30 | 1991-10-01 | Amoco Corporation | Manufacture of AMS-18 crystalline borosilicate molecular sieve |
| CN1184100A (en) * | 1997-12-10 | 1998-06-10 | 中国科学院广州化学研究所 | Reduction-esterification process synthesizing carboxylate |
| US20030004364A1 (en) * | 2001-04-30 | 2003-01-02 | Yaghi Omar M. | Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107556444A (en) * | 2017-08-23 | 2018-01-09 | 安徽富煌门窗幕墙有限公司 | One kind coats sol-gel modified building heat preservation sheet material and preparation method thereof |
| CN112893858A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Preparation method of nickel-carbon-based material |
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