CN110157545A - The method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative - Google Patents
The method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative Download PDFInfo
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- CN110157545A CN110157545A CN201910415934.4A CN201910415934A CN110157545A CN 110157545 A CN110157545 A CN 110157545A CN 201910415934 A CN201910415934 A CN 201910415934A CN 110157545 A CN110157545 A CN 110157545A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/006—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by oxidation
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract
The invention discloses tungsten-based catalyst catalysis natural oil oxicracking preparation Short-Chain Fatty Acids and its methods of derivative, and this method is using common natural oil as raw material, after hydrolysis or transesterification, obtains the free fatty acid and its derivative of long-chain.Using 30% hydrogen peroxide as oxidant, the tert-butyl alcohol is solvent, the oxicracking free unsaturated fatty acid and its derivative under the action of tungsten-based catalyst.Catalyst has good universality to natural oils such as cottonseed oil, soybean oil, rapeseed oil, castor oil.Simultaneously upon reaction completion, remaining hydrogen peroxide in several hours removing systems of appropriate ultrasound, can prevent the leaching of active component tungsten.Catalyst is recycled through operations such as centrifugation, washing, dryings, and for catalysis next time, the conversion ratio of substrate and the yield of target compound do not significantly decrease, show good reusability.
Description
Technical field
The present invention relates to the methods for preparing Short-Chain Fatty Acids and its derivative by natural oil, more specifically, of the invention
It is related to being catalyzed the unsaturated fatty acid of natural oil and its preparation of derivative oxicracking using a kind of heterogeneous tungsten-based catalyst
The method of Short-Chain Fatty Acids and its derivative.Belong to organic synthesis field.
Background technique
Short-Chain Fatty Acids and its derivative are widely used in plasticizer, profit as a kind of large industrial chemicals
In lubrication prescription, resin, fire proofing material, food additives and cosmetics.In traditional production the method for short chain saturated fatty acid mostly with
Fossil material is raw material or directly extracts from natural plants.Such as: caproic acid is usually by sec-octyl alcohol dehydration or n-hexyl alcohol oxidation system
?；N-nonanoic acid is usually raw material by octene and natural gas, and aldehyde C-9 is made through being carbonylated, then obtains n-nonanoic acid through air oxidation；Nonyl two
The dicarboxylic acids such as acid, decanedioic acid are then mostly made by cyclic compound oxidation open loop.Compared to fossil feedstock, natural oil, which has, to be come
Many advantages, such as source is extensive, cheap, environmentally protective and renewable.The basic structure of natural oil is triglycerides, institute
The fatty acid contained is mainly C16、C18、C20Saturation, unsaturated fatty acid.Wherein due to containing in long-chain unsaturated fatty acid structure
Have C=C, can be oxidized agent oxicracking be in short chain fatty acid and its derivative.
Oxidant used in the oxicracking process of unsaturated fatty acid is usually periodate, permanganate, hypochlorous acid
The strong oxidizers such as salt, sulfuric acid, nitric acid.However, these oxidants of most of they are not environmental protection, and reaction process is more difficult
Control, causes by-product more.
And Ozone induction unsaturated fatty acid oxicracking is industrially generallyd use, O3It is the allotrope of oxygen, it can
To add to rapidly in C=C double bond, carboxylic acid is converted by alkene without using metal as catalyst.The process
It is as follows:
But there is a series of safety problem in ozone, if ozone intermediate is extremely unstable, reaction needs tight in use
Lattice control under low normal temp, but a large amount of heat can be released in ozonation, thus, if temperature control is bad, may cause
Explosion；Ozone intermediate has corrosivity to equipment simultaneously, and just to consersion unit, more stringent requirements are proposed for this；In addition, using
The waste that ozone generates will also result in serious harm to environment.
To avoid excessive by-product from generating, people continuously attempt to a kind of efficient catalyst of exploitation, are reducing energy consumption
Meanwhile acquisition target product as much as possible.Current most commonly used catalyst is transition metal-type catalyst, wherein mostly with
Based on the soluble metallic salt and its complex compound of Os, Mo, Ru, W etc..Although these homogeneous soluble transition metal salt, due to
Good mass transfer effect can preferably be contacted with reaction substrate, be shown in the cracking process of catalysis unsaturated fatty acid good
Good conversion ratio and selectivity, but due to homogeneous catalyst more difficult isolated defect after the completion of reaction, cause catalyst to repeat
Usability is poor；Simultaneously because the most price of transition metal is costly, cause production process at high cost, it is large-scale to limit it
Using.
Therefore, a kind of efficient, environmental-friendly heterogeneous catalysis of exploitation, is catalyzed natural oil not to high universality
Saturated fatty acid and its derivative cracking are just particularly important.
Summary of the invention
The purpose of the present invention is designing a kind of efficient, environmental-friendly heterogeneous catalysis, it is catalyzed unsaturated fatty acid
And its derivative be converted into high selectivity in short chain fatty acid and its derivative.
In order to achieve the above objectives, present invention employs the following technical solutions:
A kind of unsaturated fatty acid and its derivative of tungsten-based catalyst catalytic pyrolysis natural oil, are obtained with higher yield
To Short-Chain Fatty Acids and its derivative.Wherein, tungsten base heterogeneous catalysis the preparation method is as follows:
It is to prepare SnO first2Carrier, with cetyl trimethylammonium bromide (CTAB) for template, SnCl4·5H2O is
Tin source, and with molar ratio CTAB:SnCl4·5H2O=1.1~1.2 is mixed, and suitable ammonium hydroxide is added and adjusts PH to 2~3, room temperature
Lower sol-gel process prepares SnO2Carrier.
Then by 0.5~2% zinc nitrate (relative to SnO2Carrier) dissolution after, be uniformly impregnated in SnO2On carrier, decompression
After extra moisture is distilled off, 300~400 DEG C of calcination 2h in Muffle furnace are placed in, Zn-SnO is obtained2Carrier.
Finally by after one or more tungstenic substance dissolutions such as a certain amount of phosphotungstic acid, ammonium metatungstate, wolframic acid, equably soak
Stain is to Zn-SnO2On carrier, dry and 2~3h of calcination at 350~400 DEG C finally obtains W/Zn-SnO2Catalyst.
The primary structure of natural oil is triglycerides, due to the limitation of steric hindrance, is cracked directly as raw material
It is more difficult, usually need to be after hydrolysis or transesterification be free fatty acid or derivatives thereof, then cracked.
Therefore, the natural oil of selection should refer to GB5009.229-2016 " measurement of acid value in food " to measure grease
The acid value of raw material.If measuring acid value hydrolyzes (transesterification) grease under the conditions of acid (alkalinity) greater than 2 (less than 2), and washes
Free fatty acid (derivative) is obtained after being centrifuged to neutrality.
The fatty acid mass content of common natural oil is as shown in the table:
It is separately added into a certain amount of tungsten-based catalyst, hydrogen peroxide and the tert-butyl alcohol into free fatty acid and its derivative,
Under 80 DEG C of oil baths, under 400~600r/min return stirring for 24 hours after, it is ultrasonic at 50 DEG C, and with the measurement of hydrogen peroxide test paper
Residual volume in system, until the H in system2O2When concentration is less than 3mg/L, stop ultrasound.Ethanol washing filter cake is filtered and used, is done
Repetitive cycling uses after dry.For Product filtrate after filtering after esterification, GC analyzes the conversion ratio of raw material and the yield of product.
Esterification process is as follows: taking substrate about 200mg after reaction in 25ml flask, and 2ml is added thereto
1%H2SO4-CH3OH solution is condensed back reaction 30min at 60 DEG C, the 50%BF of 1ml is then added into system3-CH3OH
Solution, 60 DEG C of back flow reaction 20min.After taking-up flask is cooled to room temperature, 5ml n-hexane extraction is added, adds dropwise after being layered
Enter the 5% sodium chloride solution washing upper organic phase of 3ml, stratification takes upper organic phase, and to lower layer's water phase using same
Method extract again once, will be extracted twice after resulting organic phase is diluted to certain multiple, internal standard method GC analyzes product group
At.
Specific embodiment
Taken technical solution is illustrated with specific embodiment below, but protection content of the invention is without being limited thereto.
Illustrate hereby, all reagents used in the present invention are commercially available.Wherein, natural oil is commercially available edible
Oil measures its acid value and is respectively less than 1, thus be both needed to before as raw material transesterification under alkaline condition be fatty acid methyl ester after, then into
Row cracking.
Embodiment 1
11.8795g CTAB (cetyl trimethylammonium bromide) is weighed in the eggplant type bottle of 500ml, and 100ml is added and goes
Ionized water stirs to clarify at 40 DEG C, 8ml (being diluted to 40ml with deionized water) ammonium hydroxide is then added dropwise thereto, connects
The 10.0005g SnCl for being dissolved in 100ml deionized water is added dropwise with separatory funnel4·5H2O solution, to all drip
Bi Hou stoppers glass stopper, after stirring 3h under 40 DEG C of oil bath, still aging 48h at room temperature.It, will be above-mentioned after the completion of to be aged
The gel being aged is transferred in the centrifugal bottle of 500ml, and supernatant is removed after centrifugation, and interval is washed with deionized water and ethyl alcohol
Wash lower sediment.Last time ethanol washing after, drying precipitating, after being ground to powder, be placed in calcination in Muffle furnace, with 5 DEG C/
Min is warming up to 350 DEG C, and keeps 350 DEG C of calcination 1h, obtains faint yellow SnO2Carrier.
Weigh the SnO of above-mentioned 3g20.1450gZn (NO is added in 100ml flask in carrier thereto3)2·6H2O's
The solution of 30ml after stirring 1h at 30 DEG C, depressurizes rotary evaporation, and drying, grinding are placed in 300 DEG C of calcination 2h in Muffle furnace, rise
Warm rate is 5 DEG C/min, and 1%Zn-SnO is made2Carrier (mass fraction, similarly hereinafter).Then 0.4398g ammonium metatungstate and molten is weighed
Solution is in the deionized water of 30ml, with above-mentioned Zn-SnO21h is mixed at 30 DEG C, decompression rotary evaporation removes moisture, dries,
Calcination 3h at 350 DEG C, heating rate are 5 DEG C/min, and 10%W/Zn-SnO is made2Solid catalyst.
10g oleic acid (wt > 85%) is weighed in 100ml round-bottomed flask, is separately added into 1gW/Zn- obtained thereto
SnO2, H that the 50ml tert-butyl alcohol and 17.2g concentration are 30%2O2.After 400r/min is condensed back stirring for 24 hours at 80 DEG C, through methyl esters
After change, and it is diluted to a certain concentration, using undecanoic acid methyl ester as internal standard compound, draws standard curve, GC analyzes target compound
Content measures caproic acid 0.1763g in system, n-nonanoic acid 2.7620g, azelaic acid 3.4556g.Oleic acid conversion 100%, n-nonanoic acid yield
58.03%, azelaic acid yield 51.83%.
After reaction, ultrasound 2 to 4 hours at 50 DEG C, and H is measured with hydrogen peroxide test paper2O2Concentration is less than 3mg/L
When, stop ultrasound.Centrifugation filters and washs filter cake with dehydrated alcohol, after air-drying solid catalyst at room temperature, gives over to next circulation
It uses.
Embodiment 2
Cottonseed oil of the 10g after transesterification is weighed in the round-bottomed flask of 100ml, and with 1gW/Zn- obtained in example 1
SnO2Mixing, then the tert-butyl alcohol of 50ml and the H of 20g is added dropwise respectively thereto2O2(wt=30%), 400r/min is condensed at 80 DEG C
Return stirring is for 24 hours.After esterification, it is diluted to a certain concentration, using undecanoic acid methyl ester as internal standard compound, draws standard curve, GC
The content for analyzing target compound, measures caproic acid 0.7885g in system, n-nonanoic acid 0.6063g, azelaic acid 2.5641g.Caproic acid yield
30.63%, n-nonanoic acid yield 65.30%, azelaic acid yield 47.11%.
After reaction, ultrasound 2 to 4 hours at 50 DEG C, and H is measured with hydrogen peroxide test paper2O2Concentration is less than 3mg/L
When, stop ultrasound.Centrifugation filters and washs filter cake with dehydrated alcohol, after air-drying solid catalyst at room temperature, gives over to next circulation
It uses.
Embodiment 3
Soybean oil of the 10g after transesterification is weighed in the round-bottomed flask of 100ml, and with 1gW/Zn- obtained in example 1
SnO2Mixing, then the tert-butyl alcohol of 50ml and the H of 25g is added dropwise respectively thereto2O2(wt=30%), 400r/min is condensed at 80 DEG C
Return stirring is for 24 hours.After esterification, it is diluted to a certain concentration, using undecanoic acid methyl ester as internal standard compound, draws standard curve, GC
The content for analyzing target compound, measures caproic acid 0.7432g in system, n-nonanoic acid 0.8259g, azelaic acid 2.5364g.Caproic acid yield
31.50%, n-nonanoic acid yield 64.65%, azelaic acid yield 45.93%.
After reaction, ultrasound 2 to 4 hours at 50 DEG C, and H is measured with hydrogen peroxide test paper2O2Concentration is less than 3mg/L
When, stop ultrasound.Centrifugation filters and washs filter cake with dehydrated alcohol, after air-drying solid catalyst at room temperature, gives over to next circulation
It uses.
Embodiment 4
Castor oil of the 10g after transesterification is weighed in the round-bottomed flask of 100ml, and with 1g W/ obtained in example 1
Zn-SnO2Mixing, then the 50ml tert-butyl alcohol and 20gH is added dropwise respectively thereto2O2(wt=30%), 400r/min is condensed back at 80 DEG C
Stream stirring is for 24 hours.After esterification, it is diluted to a certain concentration, using undecanoic acid methyl ester as internal standard compound, draws standard curve, GC divides
The content for analysing target compound, measures octanoic acid 1.9308g, decanedioic acid 2.3495g in system.Sad yield 53.64%, decanedioic acid
Yield 46.53%.
After reaction, ultrasound 2 to 4 hours at 50 DEG C, and H is measured with hydrogen peroxide test paper2O2Concentration is less than 3mg/L
When, stop ultrasound.Centrifugation filters and washs filter cake with dehydrated alcohol, after air-drying solid catalyst at room temperature, gives over to next circulation
It uses.
Embodiment 5
Rapeseed oil of the 10g after transesterification is weighed in the round-bottomed flask of 100ml, and with 1gW/Zn- obtained in example 1
SnO2Mixing, then the tert-butyl alcohol of 50ml and the H of 20g is added dropwise respectively thereto2O2(wt=30%), 400r/min is condensed at 80 DEG C
Return stirring is for 24 hours.After esterification, using undecanoic acid methyl ester as internal standard compound, standard curve is drawn, GC analyzes target compound
Content measures caproic acid 0.2954g in system, n-nonanoic acid 1.7466g, azelaic acid 2.6538g.Caproic acid yield 29.18%, n-nonanoic acid yield
50.95%, azelaic acid yield 44.12%.
After reaction, ultrasound 2 to 4 hours at 50 DEG C, and H is measured with hydrogen peroxide test paper2O2Concentration is less than 3mg/L
When, stop ultrasound.Centrifugation filters and washs filter cake with dehydrated alcohol, after air-drying solid catalyst at room temperature, gives over to next circulation
It uses.
Claims (6)
1. the method that tungsten-based catalyst is catalyzed natural oil oxicracking preparation Short-Chain Fatty Acids and its derivative, feature exist
In: the preparation method of tungsten base heterogeneous catalysis is as follows,
It is to prepare SnO first2Carrier, using cetyl trimethylammonium bromide as template, SnCl4·5H2O is tin source, and to rub
You compare CTAB:SnCl4·5H2O=1.1~1.2 is mixed, and suitable ammonium hydroxide is added and adjusts PH to 2~3, at room temperature sol-gel process
Prepare SnO2Carrier；
Then it by after the dissolution of 0.5~2% zinc nitrate, is uniformly impregnated in SnO2On carrier, vacuum distillation removes extra moisture
Afterwards, 300~400 DEG C of calcination 2h in Muffle furnace are placed in, Zn-SnO is obtained2Carrier；
Finally by after one or more tungstenic substance dissolutions such as a certain amount of phosphotungstic acid, ammonium metatungstate, wolframic acid, it is uniformly impregnated with
Zn-SnO2On carrier, dry and 2~3h of calcination at 350~400 DEG C finally obtains W/Zn-SnO2Catalyst.
2. tungsten-based catalyst catalysis natural oil oxicracking according to claim 1 prepares Short-Chain Fatty Acids and its spreads out
The method of biology, it is characterised in that: the structure of natural oil is triglycerides, due to the limitation of steric hindrance, directly as original
Material is cracked more difficulty, usually need to be after hydrolysis or transesterification are free fatty acid or derivatives thereof, then is cracked.
3. tungsten-based catalyst catalysis natural oil oxicracking according to claim 1 prepares Short-Chain Fatty Acids and its spreads out
The method of biology, it is characterised in that: natural oil measures grease referring to GB5009.229-2016 " measurement of acid value in food "
The acid value of raw material；If measuring acid value is more than or equal to 2, in acid condition hydrolysate oil, and is washed to neutrality, after being centrifuged,
Obtain free fatty acid.
4. tungsten-based catalyst catalysis natural oil oxicracking according to claim 1 prepares Short-Chain Fatty Acids and its spreads out
The method of biology, it is characterised in that: natural oil measures grease referring to GB5009.229-2016 " measurement of acid value in food "
The acid value of raw material；If measuring acid value less than 2, transesterification grease under alkaline condition, and it is washed to neutrality, after being centrifuged, obtain
To free derivative of fatty acid.
5. tungsten-based catalyst catalysis natural oil oxicracking according to claim 1 prepares Short-Chain Fatty Acids and its spreads out
The method of biology, it is characterised in that: a certain amount of tungsten-based catalyst, double is separately added into free fatty acid and its derivative
Oxygen water and the tert-butyl alcohol, under 80 DEG C of oil baths, under 400~600r/min return stirring for 24 hours after, it is ultrasonic at 50 DEG C, and use peroxide
Change the residual volume in hydrogen test paper measurement system, until the H in system2O2When concentration is less than 3mg/L, stop ultrasound；It filters and uses second
Alcohol washs filter cake, and repetitive cycling uses after drying；For Product filtrate after filtering after esterification, GC analyzes the conversion ratio of raw material
And the yield of product.
6. tungsten-based catalyst catalysis natural oil oxicracking according to claim 1 prepares Short-Chain Fatty Acids and its spreads out
The method of biology, it is characterised in that: esterification process is as follows: taking substrate about 200mg after reaction in 25ml flask, and
The 1%H of 2ml is added thereto2SO4-CH3OH solution is condensed back reaction 30min at 60 DEG C, 1ml is then added into system
50%BF3-CH3OH solution, 60 DEG C of back flow reaction 20min；After taking-up flask is cooled to room temperature, 5ml n-hexane extraction is added,
The 5% sodium chloride solution washing upper organic phase of 3ml is added dropwise after being layered, stratification takes upper organic phase, and under
Layer water phase is extracted once again using same method, will be extracted twice after resulting organic phase is diluted to certain multiple, internal standard
Method GC analyzes product composition.
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Cited By (1)
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| CN110483286A (en) * | 2019-08-30 | 2019-11-22 | 浙江工业大学 | A kind of method that tungsten based solid acid catalyst catalysis consaturated oil oxydrolysis prepares biopolyol |
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| CN110483286B (en) * | 2019-08-30 | 2021-09-21 | 浙江工业大学 | Method for preparing bio-based polyol by catalyzing unsaturated grease to be oxidized and hydrolyzed by tungsten-based solid acid catalyst |
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