CN108947780A - A method of rectifying high-boiling components in processing Ethyl vanillin preparation - Google Patents
A method of rectifying high-boiling components in processing Ethyl vanillin preparation Download PDFInfo
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- CN108947780A CN108947780A CN201810814758.7A CN201810814758A CN108947780A CN 108947780 A CN108947780 A CN 108947780A CN 201810814758 A CN201810814758 A CN 201810814758A CN 108947780 A CN108947780 A CN 108947780A
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- ethyl vanillin
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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Abstract
The invention discloses a kind of methods of rectifying high-boiling components in processing Ethyl vanillin preparation, include the following steps: that A. dissolves high-boiling components heating, are placed in reaction kettle, and catalyst is added；B. -90Kpa~-40Kpa is set by reaction system, and is to slowly warm up to 80 DEG C~130 DEG C, keep 0.2~10h；C. 160 DEG C~210 DEG C are warming up to, after reacting 4h~10h, using nitrogen vacuum breaker, the reaction system is made to be in 10Kpa~50Kpa；D. 120 DEG C~150 DEG C are cooled to, o-ethoxyphenol is obtained by distillation；Wherein, the catalyst is the one or more of following each group catalyst: 1. Pt and A12O3, 2. Ag and Al2O3, 3. Pd and Al2O3, 4. Pt-Pd and Al2O3, 5. Pt-Rh and Al2O3, 6. Pt and SiO2, 7. Pd and SiO2, 8. Rh and SiO2.Process of the present invention control is simple, and production cost is low, easy to operate, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of methods for handling Ethyl vanillin rectifying high-boiling components.
Background technique
Ethyl vanillin, also known as ethyl vanillin are white to yellowish scale crystalline powder, are in sweet chocolate fragrance
And the distinctive aroma of vanillic aldehyde, substantially nonhazardous, it is widely used in the row such as fragrance, cosmetics, food additives, medicine
Industry.The first essence synthesized by the mankind is exactly vanillic aldehyde, he be breathed out by the M. of Germany Germania doctor and G. Thailand mambo scholar in
Synthesis in 1874 is successful.Now, there are many production process route, mainly using guaethol as raw material, that there are yields is low,
The problems such as seriously polluted, at high cost.Specifically using guaethol and glyoxylic acid as raw material, contract under alkaline condition
It closes, then Ethyl vanillin is made through aoxidizing, process is shown in formula 1:
The producer of domestic production at present mainly uses this synthesis route.The recyclable benefit of guaethol in this technique
With, but yield is not high, and the auxiliary facility needed is more so that production cost increased.
Ethyl vanillin is produced according to this technique, by-product can be generated in reaction process, these by-products can reduce ethyl
The yield and quality of vanillic aldehyde, such as crystal form, fragrance, color, especially as essence substance, micro by-product just be can be changed
Its fragrance odor type.One of by-product is 2,4- dialdehyde-based -6- thanatol, and structural formula is shown in formula 2.
If the Ethyl vanillin for containing this large amount of compound is modulated to essence as fragrance, essence or added may cause
The product of essence changes colour.
The boiling point of Ethyl vanillin is 295 DEG C (760mmHg), and the boiling point of 2,4- dialdehyde-based -6- thanatols is 320.6
DEG C (760mmHg), so the method by rectifying can separate them.When rectifying, after Ethyl vanillin acquires certain amount, open
Begin acquisition high-boiling components.High-boiling components are mainly Ethyl vanillin, wherein containing a certain amount of 2,4- dialdehyde-based -6- thanatol.
The high-boiling components of every batch materials are mixed and are tested and analyzed, Ethyl vanillin content (weight) is 65-75%, 2,4- dialdehyde-based -6-
Ethoxybenzene phenol content (weight) is 20-30%, also contains other impurity.This high-boiling components cannot be divided using conventional rectification mode
From alternatively separation costs are very high.This part high-boiling components cannot function as fragrance or other raw materials use, and can only be used as dangerous waste
Object processing, processing cost is expensive, increases the production cost of Ethyl vanillin.
Therefore those skilled in the art are dedicated to developing a kind of handles Ethyl vanillin during preparing Ethyl vanillin
The method of rectifying high-boiling components, can not only reduce the production cost of Ethyl vanillin, and the yield of Ethyl vanillin can be improved.
Summary of the invention
In view of the above drawbacks of the prior art, technical problem to be solved by the invention is to provide one kind to prepare ethyl
The method that Ethyl vanillin rectifying high-boiling components are handled during vanillic aldehyde, can not only reduce the production cost of Ethyl vanillin,
And the yield of Ethyl vanillin can be improved.
To achieve the above object, the present invention provides it is a kind of processing Ethyl vanillin preparation in rectifying high-boiling components method,
Include the following steps:
A. high-boiling components heating is dissolved, is placed in reaction kettle, and catalyst is added；
B. -90Kpa~-40Kpa is set by reaction system, and is to slowly warm up to 80 DEG C~130 DEG C, holding 0.2~
10h；
C. 160 DEG C~210 DEG C are warming up to, after reacting 4h~10h, using nitrogen vacuum breaker, is made at the reaction system
In 10Kpa~50Kpa；
In this step, 2,4- dialdehyde-based -6- thanatol and Ethyl vanillin reaction in the high-boiling components start anti-
It answers, reaction equation is shown in formula 3 and formula 4 respectively:
D. 120 DEG C~150 DEG C are cooled to, o-ethoxyphenol is obtained by distillation；
Wherein, the catalyst is the one or more of following each group catalyst:
1. Pt and A12O3, 2. Ag and Al2O3, 3. Pd and Al2O3, 4. Pt-Pd and Al2O, 5. Pt-Rh and Al2O3, 6. Pt and
SiO2, 7. Pd and SiO2, 8. Rh and SiO2。
Preferably, in the step B, reaction system temperature 0.5~4h between 80 DEG C~130 DEG C is kept.
Preferably, the catalyst amount is the 0.5%~5% of the high-boiling components weight.
Preferably, the catalyst is one of following composite catalyst:
I, 1. Pt and A12O3With 3. Pd and Al2O3It is compound, wherein 1. Pt and A12O3Account for 0~20wt%；
II, Pt and SiO is 6. organized2With 7. group Pd and SiO2It is compound, wherein 6. organizing Pt and SiO2Account for 0~20wt%；
Preferably, each Ingredient Wt ratio is as follows in each group catalyst:
1. Pt and A12O3Weight ratio is 1:0.2~10 2. Ag and Al2O3Weight ratio is 1:0.2~10 3. Pd and Al2O3Weight
Than for 1:0.2~10 4. Pt-Pd and Al2O3Weight ratio is 1:0.2~10P 5. Pt-Rh and Al2O3Weight ratio be 1:0.2~10 6.
Pt and SiO2Weight ratio is 1:0.2~10 7. Pd and SiO2Weight ratio is 1:0.2~10 8. Rh and SiO2Weight ratio be 1:0.2~
10。
Preferably, each Ingredient Wt ratio is 1:1 in each group catalyst.
Preferably, described group 9. Pt accounts for 20wt%~40wt% in Pt-Pd；Described group 10. in Pt-Rh Pt account for 20wt%~
40wt%.
Preferably, it in the step D, after being cooled to 120 DEG C~150 DEG C, first passes through vacuum distillation and obtains crude product, then use
Rectifying mode removes impurity.Wherein, after vacuum distillation, the kettle after distillation remains in equipment, adds the height of phase homogenous quantities
Object is boiled, the aforesaid vacuum distilation steps in step A, B, C and D is repeated, so applies 3~10 times, can reach best catalytic effect
And efficiency.
The beneficial effects of the present invention are: process of the present invention control is simple, production cost is low, easy to operate, is suitble to industry metaplasia
It produces；Reaction speed is fast, can comparatively fast handle rectifying high-boiling components in Ethyl vanillin preparation；Catalyst is easy to get, and consumes low, catalyst time
High income；High conversion rate, more than 95%, gained o-ethoxyphenol precision is high, and gained O-ethoxyl phenol content is greater than 99%；
High-boiling components are converted into raw material, turn waste into wealth, and save production cost.
Specific embodiment
With embodiment, the invention will be further described below, embodiment described herein only to explain the present invention,
Not to limit the present invention.
In following embodiment, it is condensed under alkaline condition using guaethol and glyoxylic acid as raw material, then through oxygen
Change and Ethyl vanillin is made, after the completion of preparation, being detected includes Ethyl vanillin content (weight in obtained rectifying high-boiling components
Amount) it is 72%, 2,4- dialdehyde-based -6- ethoxybenzene phenol content (weight) are 26%, are also 2% containing other impurity (weight).
Embodiment 1 to 12 handles above-mentioned high-boiling components according to the following steps, wherein specific preparation condition control, it is each to be catalyzed
See Table 1 for details for agent selection and dosage selection:
A method of rectifying high-boiling components in processing Ethyl vanillin preparation include the following steps:
A. high-boiling components 200g is taken, high-boiling components heating is dissolved, is placed in reaction kettle, and catalyst is added；
B. -90Kpa~-40Kpa is set by reaction system, and is to slowly warm up to 80 DEG C~130 DEG C, holding 0.2~
10h；
C. 160 DEG C~210 DEG C are warming up to, after reacting 4h~10h, using nitrogen vacuum breaker, is made at the reaction system
In 10Kpa~50Kpa；
D. 120 DEG C~150 DEG C are cooled to, vacuum distillation is first passed through and obtains crude product, then impurity is removed using rectifying mode.
Table 1:
O-ethoxyphenol analysis, the weighing that embodiment 1 to 12 is obtained, calculate Ethyl vanillin and 2,4- dialdehyde-based-
6- thanatol conversion ratio, and its purity is surveyed, residual catalyst weighing is collected, is obtained as follows as a result, being shown in Table 2:
Table 2:
O-ethoxyphenol is important industrial chemicals, is a kind of important fine-chemical intermediate, downstream chemical products
Mainly Ethyl vanillin is widely used in the industries such as medicine, fragrance, has great market value.Ethyl vanillin will prepared
What is generated in the process generally brings the high-boiling components waste material disposed and is prepared into o-ethoxyphenol, turns waste into wealth, has saved production
Cost, and high conversion rate, purity is high, there is Important Economic value.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (8)
1. a kind of method of rectifying high-boiling components in processing Ethyl vanillin preparation, it is characterized in that: including the following steps:
A. high-boiling components heating is dissolved, is placed in reaction kettle, and catalyst is added；
B. -90Kpa~-40Kpa is set by reaction system, and is to slowly warm up to 80 DEG C~130 DEG C, keep 0.2~10h；
C. 160 DEG C~210 DEG C are warming up to, after reacting 4h~10h, using nitrogen vacuum breaker, is in the reaction system
10Kpa~50Kpa；
D. 120 DEG C~150 DEG C are cooled to, o-ethoxyphenol is obtained by distillation；
Wherein, the catalyst is the one or more of following each group catalyst:
1. Pt and A12O3, 2. Ag and Al2O3, 3. Pd and Al2O3, 4. Pt-Pd and Al2O3, 5. Pt-Rh and Al2O3, 6. Pt and SiO2、
7. Pd and SiO2, 8. Rh and SiO2。
2. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: the step B
In, keep reaction system temperature 0.5~4h between 80 DEG C~130 DEG C.
3. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: the catalyst
Dosage is the 0.5%~5% of the high-boiling components weight.
4. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: the catalyst
For one of following composite catalyst:
I, 1. Pt and A12O3With 3. Pd and Al2O3It is compound, wherein 1. Pt and A12O3Account for 0~20wt%；
II, Pt and SiO is 6. organized2With 7. group Pd and SiO2It is compound, wherein 6. organizing Pt and SiO2Account for 0~20wt%.
5. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: each group is urged
Each Ingredient Wt ratio is as follows in agent:
1. Pt and A12O3Weight ratio is 1:0.2~10 2. Ag and Al2O3Weight ratio is 1:0.2~10 3. Pd and Al2O3Weight ratio is
1:0.2~10 4. Pt-Pd and Al2O3Weight ratio is 1:0.2~10P 5. Pt-Rh and Al2O3Weight ratio be 1:0.2~10 6. Pt and
SiO2Weight ratio is 1:0.2~10 7. Pd and SiO2Weight ratio is 1:0.2~10 8. Rh and SiO2Weight ratio is 1:0.2~10.
6. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: each group is urged
Each Ingredient Wt ratio is 1:1 in agent.
7. as described in claim 1 processing Ethyl vanillin preparation in rectifying high-boiling components method, it is characterized in that: described group 4.
Pt accounts for 20wt%~40wt% in Pt-Pd；Described group 5. Pt accounts for 20wt%~40wt% in Pt-Rh.
8. the method for handling rectifying high-boiling components in Ethyl vanillin preparation as described in claim 1, it is characterized in that: the step D
In, after being cooled to 120 DEG C~150 DEG C, first passes through vacuum distillation and obtain crude product, then impurity is removed using rectifying mode.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4897827A (en) * | 1972-03-30 | 1973-12-13 | ||
| JPS5365840A (en) * | 1976-11-22 | 1978-06-12 | Ube Ind Ltd | Preparation of 3-alkoxy-4-hydroxy-benzaldehyde and 5-alkoxy-4-hydroxyisophthalaldehyde |
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
| JPS57112346A (en) * | 1981-11-10 | 1982-07-13 | Ube Ind Ltd | Preparation of formylated phenolic compound |
| CN1179414A (en) * | 1996-08-30 | 1998-04-22 | 宇部兴产株式会社 | Catalyst for decarbonylation reaction |
| CN1229319C (en) * | 1996-11-22 | 2005-11-30 | 罗狄亚化学公司 | Method for preparing 4-hydroxybenzaldehyde and its derivatives |
| CN1238752C (en) * | 2001-06-08 | 2006-01-25 | 住友精密工业株式会社 | Substrate processing devices |
| CN104045537A (en) * | 2014-06-24 | 2014-09-17 | 上海应用技术学院 | Method for treating 5-aldehyde vanillin side product in vanillin production process |
| CN105693478A (en) * | 2016-03-16 | 2016-06-22 | 重庆欣欣向荣精细化工有限公司 | Preparation method for converting ortho-position ethyl vanillin into ethoxyphenol |
-
2018
- 2018-07-23 CN CN201810814758.7A patent/CN108947780A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4897827A (en) * | 1972-03-30 | 1973-12-13 | ||
| JPS5365840A (en) * | 1976-11-22 | 1978-06-12 | Ube Ind Ltd | Preparation of 3-alkoxy-4-hydroxy-benzaldehyde and 5-alkoxy-4-hydroxyisophthalaldehyde |
| US4165341A (en) * | 1977-02-04 | 1979-08-21 | Ube Industries, Ltd. | Process for preparing protocatechualdehyde and its derivatives |
| JPS57112346A (en) * | 1981-11-10 | 1982-07-13 | Ube Ind Ltd | Preparation of formylated phenolic compound |
| CN1179414A (en) * | 1996-08-30 | 1998-04-22 | 宇部兴产株式会社 | Catalyst for decarbonylation reaction |
| CN1229319C (en) * | 1996-11-22 | 2005-11-30 | 罗狄亚化学公司 | Method for preparing 4-hydroxybenzaldehyde and its derivatives |
| CN1238752C (en) * | 2001-06-08 | 2006-01-25 | 住友精密工业株式会社 | Substrate processing devices |
| CN104045537A (en) * | 2014-06-24 | 2014-09-17 | 上海应用技术学院 | Method for treating 5-aldehyde vanillin side product in vanillin production process |
| CN105693478A (en) * | 2016-03-16 | 2016-06-22 | 重庆欣欣向荣精细化工有限公司 | Preparation method for converting ortho-position ethyl vanillin into ethoxyphenol |
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