CN106397191A - Catalytic preparation method for methyl oleate - Google Patents
Catalytic preparation method for methyl oleate Download PDFInfo
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- CN106397191A CN106397191A CN201610758011.5A CN201610758011A CN106397191A CN 106397191 A CN106397191 A CN 106397191A CN 201610758011 A CN201610758011 A CN 201610758011A CN 106397191 A CN106397191 A CN 106397191A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a catalytic preparation method for methyl oleate. The method comprises the steps of adding oleic acid, methanol and a solid catalyst into a reactor, carrying out an esterification reaction for 2 to 4 hours at the temperature of 70 DEG C to 90 DEG C, then, filtrating a reaction solution, applying the solid catalyst to repeated mechanical application, and subjecting the filtrate to silica-gel column chromatography purification, thereby obtaining the target product, i.e., methyl oleate. The solid catalyst is prepared through loading copper oxide to modified nano-kaolin, which serves as a carrier, by dipping, baking and roasting methods in a manner of taking copper nitrate as a precursor. A method for preparing the modified nano-kaolin comprises the steps of dispersing 30-40 parts of nano-kaolin into 45-55 parts of triethylene tetramine with the mass percent of 5% to 15%, carrying out stirring for 25 to 35 minutes at the temperature of 40 DEG C to 50 DEG C, then, adding 5-15 parts of Zn(NO3)2.6H2O, carrying out stirring for 20 to 30 minutes, carrying out cooling, then, carrying out filtration, and carrying out drying, thereby obtaining the modified nano-kaolin. According to the method provided by the invention, the operation is simple and easy, and the conversion ratio is high; and the solid catalyst can be repeatedly applied mechanically after the solid catalyst is separated.
Description
Technical field
The invention belongs to chemical field, it is related to the preparation of intermediate and in particular to a kind of catalysis preparation side of methyl oleate
Method.
Background technology
Methyl oleate is the oily liquids of pale yellow transparent, is widely used in the organic synthesiss such as chemical industry, weaving and medicine,
The intermediate being mainly used as surface detergent, emulsifying agent, stabilizer is it is also possible to make biodiesel or substituted fatty acid as many
The raw material of grease chemical article.Synthesis for methyl oleate has research very early, and most typical traditional preparation methods are with Oleic acid
It is raw material with methanol, be heated to reflux for catalyst using sulphuric acid, response time 10h, being neutralized to pH with Feldalat NM is 8-9,
It is washed with water to neutrality, be then dried with anhydrous calcium chloride, filter.
Content of the invention
It is an object of the invention to provide a kind of catalysis preparation method of methyl oleate.
The above-mentioned purpose of the present invention is achieved by techniques below scheme：
A kind of catalysis preparation method of methyl oleate：Oleic acid, methanol and solid catalyst are added in reactor, 70-90
DEG C esterification 2-4 hour, then by reacting liquid filtering, solid catalyst is used for repeatedly applying mechanically, and filtrate carries through silica gel column chromatography
Pure obtain target product methyl oleate；Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma,
By the method for dipping, drying, roasting, copper oxide is carried on modified Nano Kaolin；
Wherein, described modified Nano Kaolin preparation method is：Nano kaoline 30-40 part is taken to be scattered in 45-55 part matter
Amount fraction is in the triethylene tetramine of 5-15%, stirs 25-35min, add 5-15 part Zn under the conditions of 40-50 DEG C
(NO3)2·6H2O, stirs 20-30min, filters, be drying to obtain after cooling.
Preferably, described modified Nano Kaolin preparation method is：Take 35 parts of nano kaoline to be scattered in 50 parts of quality to divide
In the triethylene tetramine for 10% for the number, stir 30min under the conditions of 45 DEG C, add 10 parts of Zn (NO3)2·6H2O, stirring
25min, filters after cooling, is drying to obtain.
Preferably, the concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:10-1:20, ultrasonic disperse 30-60 minute, power 120-240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8-12h, wherein copper nitrate with modified
The mass ratio of nano kaoline is 1:10-1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80-120 DEG C of drying in baking oven, subsequently
Transfer in tube furnace, be warming up to 400-450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3-5h, fall at this temperature
Take out after temperature and obtain final product described solid catalyst.
Preferably, Oleic acid and methanol molar ratio are 1:1.5-4.5.
Preferably, described solid catalyst weight is the 10-20% of oleic acid weight.
Advantages of the present invention：
The method that the present invention provides is simply easily operated, high conversion rate；Solid catalyst can be applied mechanically after separating repeatedly, and
Repeatedly apply mechanically catalytic efficiency after repeatedly no substantially to reduce.
Specific embodiment
Further illustrate the essentiality content of the present invention with reference to embodiment, but present invention protection model is not limited with this
Enclose.Although being explained in detail to the present invention with reference to preferred embodiment, it will be understood by those within the art that, can be right
Technical scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention.
Embodiment 1：The catalysis preparation method of methyl oleate
Oleic acid, methanol and solid catalyst are added in reactor, 80 DEG C of esterifications 3 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:3.Described solid catalyst weight is the 15% of oleic acid weight.
Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano Kaolin the method for roasting, and concrete preparation method includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The kaolinic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 430 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 50 parts of mass fractions is 10%
Triethylene tetramine in, under the conditions of 45 DEG C stir 30min, add 10 parts of Zn (NO3)2·6H2O, stirs 25min, after cooling
Filter, be drying to obtain.
Embodiment 2：The catalysis preparation method of methyl oleate
Oleic acid, methanol and solid catalyst are added in reactor, 70 DEG C of esterifications 4 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:1.5.Described solid catalyst weight is the 10% of oleic acid weight.
Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano Kaolin the method for roasting, and concrete preparation method includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:10, ultrasonic disperse 30 minutes, power 120W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8h, wherein copper nitrate and modified Nano
Kaolinic mass ratio is 1:10；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80 DEG C of drying in baking oven, subsequently shifts
To in tube furnace, it is warming up to 400 DEG C under nitrogen atmosphere or argon gas atmosphere, and keeps 5h at this temperature, taking-up after cooling is
Obtain described solid catalyst.
Described modified Nano Kaolin preparation method is：Taking 30 parts of nano kaoline to be scattered in 45 parts of mass fractions is 5%
Triethylene tetramine in, under the conditions of 40 DEG C stir 35min, add 5 parts of Zn (NO3)2·6H2O, stirs 20min, after cooling
Filter, be drying to obtain.
Embodiment 3：The catalysis preparation method of methyl oleate
Oleic acid, methanol and solid catalyst are added in reactor, 90 DEG C of esterifications 2 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:4.5.Described solid catalyst weight is the 20% of oleic acid weight.
Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano Kaolin the method for roasting, and concrete preparation method includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:20, ultrasonic disperse 60 minutes, power 240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 12h, wherein copper nitrate and modification are received
The kaolinic mass ratio of rice is 1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 120 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Described modified Nano Kaolin preparation method is：Taking 40 parts of nano kaoline to be scattered in 55 parts of mass fractions is 15%
Triethylene tetramine in, under the conditions of 50 DEG C stir 25min, add 15 parts of Zn (NO3)2·6H2O, stirs 30min, after cooling
Filter, be drying to obtain.
Embodiment 4：The catalysis preparation method of methyl oleate
Oleic acid, methanol and solid catalyst are added in reactor, 80 DEG C of esterifications 3 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:3.Described solid catalyst weight is the 12% of oleic acid weight.
Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano Kaolin the method for roasting, and concrete preparation method includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The kaolinic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 430 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 50 parts of mass fractions is 10%
Triethylene tetramine in, under the conditions of 45 DEG C stir 30min, add 10 parts of Zn (NO3)2·6H2O, stirs 25min, after cooling
Filter, be drying to obtain.
Embodiment 5：The catalysis preparation method of methyl oleate
Oleic acid, methanol and solid catalyst are added in reactor, 80 DEG C of esterifications 3 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:3.Described solid catalyst weight is the 18% of oleic acid weight.
Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate as presoma, by dipping, dry,
Copper oxide is carried on modified Nano Kaolin the method for roasting, and concrete preparation method includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionization
Water quality is than for 1:15, ultrasonic disperse 45 minutes, power 180W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 10h, wherein copper nitrate and modification are received
The kaolinic mass ratio of rice is 1:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 430 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Described modified Nano Kaolin preparation method is：Taking 35 parts of nano kaoline to be scattered in 50 parts of mass fractions is 10%
Triethylene tetramine in, under the conditions of 45 DEG C stir 30min, add 10 parts of Zn (NO3)2·6H2O, stirs 25min, after cooling
Filter, be drying to obtain.
Embodiment 6：Comparative example, nano kaoline is not modified
Oleic acid, methanol and solid catalyst are added in reactor, 80 DEG C of esterifications 3 hours, then by reactant liquor mistake
Filter, solid catalyst is used for repeatedly applying mechanically, and filtrate obtains target product methyl oleate through silica gel column chromatography purification.Oleic acid and methanol
Mol ratio is 1:3.Described solid catalyst weight is the 15% of oleic acid weight.
Described solid catalyst with nano kaoline as carrier, with copper nitrate as presoma, by dipping, dry, roasting
Method copper oxide is carried on nano kaoline, concrete preparation method includes：
Step S1：A certain amount of nano kaoline is added in deionized water, nano kaoline and deionized water quality ratio
For 1:15, ultrasonic disperse 45 minutes, power 180W；Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation
10h, wherein copper nitrate are 1 with the mass ratio of nano kaoline:15；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 100 DEG C of drying in baking oven, subsequently turns
Move on in tube furnace, be warming up to 430 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 4h at this temperature, take out after cooling
Obtain final product described solid catalyst.
Embodiment 7：Effect example
Catalytic efficiency fall after respectively the conversion ratio (%) of testing example 1-6 reaction and catalyst apply mechanically 50 times repeatedly
Low percentage value (%), result is as follows.
| Conversion ratio (%) | Catalytic efficiency reduces percentage rate (%) | |
| Embodiment 1 | 99.9 | 5 |
| Embodiment 6 | 89.7 | 45 |
Embodiment 2-5 measurement result is basically identical with embodiment 1, no longer enumerates one by one.
Result shows, the method that the present invention provides is simply easily operated, high conversion rate；Solid catalyst can be anti-after separating
Apply mechanically again, and repeatedly apply mechanically catalytic efficiency after repeatedly and no substantially reduce.
The effect of above-described embodiment indicates that the essentiality content of the present invention, but does not limit the protection of the present invention with this
Scope.It will be understood by those within the art that, technical scheme can be modified or equivalent,
Essence without deviating from technical solution of the present invention and protection domain.
Claims (5)
1. a kind of methyl oleate catalysis preparation method it is characterised in that：Oleic acid, methanol and solid catalyst are added reactor
In, 70-90 DEG C of esterification 2-4 hour, then by reacting liquid filtering, solid catalyst is used for repeatedly applying mechanically, and filtrate is through silica gel
Column chromatography purification obtains target product methyl oleate；Described solid catalyst with modified Nano Kaolin as carrier, with copper nitrate
For presoma, by the method for dipping, drying, roasting, copper oxide is carried on modified Nano Kaolin；
Wherein, described modified Nano Kaolin preparation method is：Take nano kaoline 30-40 part to be scattered in 45-55 part quality to divide
In the triethylene tetramine for 5-15% for the number, stir 25-35min under the conditions of 40-50 DEG C, add 5-15 part Zn (NO3)2·
6H2O, stirs 20-30min, filters, be drying to obtain after cooling.
2. catalysis preparation method according to claim 1 is it is characterised in that described modified Nano Kaolin preparation method
For：Taking 35 parts of nano kaoline to be scattered in 50 parts of mass fractions is in 10% triethylene tetramine, stirs under the conditions of 45 DEG C
30min, adds 10 parts of Zn (NO3)2·6H2O, stirs 25min, filters, be drying to obtain after cooling.
3. catalysis preparation method according to claim 1 is it is characterised in that the concrete preparation method of solid catalyst includes：
Step S1：A certain amount of modified Nano Kaolin is added in deionized water, modified Nano Kaolin and deionized water
Amount ratio is 1:10-1:20, ultrasonic disperse 30-60 minute, power 120-240W；
Step S2：Copper nitrate is added in the material of step S1 gained, magnetic agitation 8-12h, wherein copper nitrate and modified Nano
Kaolinic mass ratio is 1:10-1:20；
Step S3：Step S2 gained material is evaporated in a water bath, is subsequently transferred to 80-120 DEG C of drying in baking oven, subsequently shifts
To in tube furnace, it is warming up to 400-450 DEG C under nitrogen atmosphere or argon gas atmosphere, and keep 3-5h at this temperature, after cooling
Taking-up obtains final product described solid catalyst.
4. according to claim 1 catalysis preparation method it is characterised in that：Oleic acid and methanol molar ratio are 1:1.5-4.5.
5. according to claim 1 catalysis preparation method it is characterised in that：Described solid catalyst weight is oleic acid weight
10-20%.
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| CN201610758011.5A CN106397191A (en) | 2016-08-29 | 2016-08-29 | Catalytic preparation method for methyl oleate |
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| CN201610758011.5A CN106397191A (en) | 2016-08-29 | 2016-08-29 | Catalytic preparation method for methyl oleate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658767A (en) * | 2018-07-12 | 2018-10-16 | 常州市金坛区维格生物科技有限公司 | A kind of preparation method of methyl oleate |
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|---|---|---|---|---|
| CN102125856A (en) * | 2011-01-31 | 2011-07-20 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
| CN102154065A (en) * | 2011-03-16 | 2011-08-17 | 天津工业大学 | Method for preparing methyl oleate from vegetable oil under catalysis of silicon dioxide-supported heteropolyacid |
| CN103319341A (en) * | 2013-06-28 | 2013-09-25 | 华东师范大学 | Method for synthesizing methyl oleate |
| CN104230708A (en) * | 2014-10-10 | 2014-12-24 | 徐震霖 | Preparation method of methyl formate |
-
2016
- 2016-08-29 CN CN201610758011.5A patent/CN106397191A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125856A (en) * | 2011-01-31 | 2011-07-20 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
| CN102154065A (en) * | 2011-03-16 | 2011-08-17 | 天津工业大学 | Method for preparing methyl oleate from vegetable oil under catalysis of silicon dioxide-supported heteropolyacid |
| CN103319341A (en) * | 2013-06-28 | 2013-09-25 | 华东师范大学 | Method for synthesizing methyl oleate |
| CN104230708A (en) * | 2014-10-10 | 2014-12-24 | 徐震霖 | Preparation method of methyl formate |
Non-Patent Citations (1)
| Title |
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| 陈志胜 等: ""SO42 － /SnO2 -高岭土催化合成食用香精丙酸正丁酯"", 《食品与发酵工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108658767A (en) * | 2018-07-12 | 2018-10-16 | 常州市金坛区维格生物科技有限公司 | A kind of preparation method of methyl oleate |
| CN108658767B (en) * | 2018-07-12 | 2021-01-01 | 常州市金坛区维格生物科技有限公司 | Preparation method of methyl oleate |
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