CN104926658A - Preparation technology for catalytically synthetizing L-(+)-diethyl tartrate by using strong acid cation exchange resin as catalyst - Google Patents
Preparation technology for catalytically synthetizing L-(+)-diethyl tartrate by using strong acid cation exchange resin as catalyst Download PDFInfo
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- CN104926658A CN104926658A CN201510215154.7A CN201510215154A CN104926658A CN 104926658 A CN104926658 A CN 104926658A CN 201510215154 A CN201510215154 A CN 201510215154A CN 104926658 A CN104926658 A CN 104926658A
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- exchange resin
- cation exchange
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of spices, and relates to a preparation technology for catalytically synthetizing L-(+)-diethyl tartrate by using strong acid cation exchange resin as a catalyst. The preparation technology comprises the following steps: adding L-(+)-tartaric acid, absolute ethyl alcohol and a catalyst to a reaction container, and performing a stirring and heating reaction; after the reaction is completed, cooling the reagent to room temperature, and then filtering the reagent to recycle the catalyst, wherein the catalyst is the strong acid cation exchange resin; and directly distilling a filter liquor to obtain the colorless clear liquid L-(+)-diethyl tartrate. According to the preparation technology, the yield of the L-(+)-diethyl tartrate can be improved, the technology is simple, the operation is convenient, the problems of catalysis and recycling by using a strong acid liquid and a solvent are avoided, the whole technological process is clean and environment-friendly, waste acid, waste water and waste gas cannot be generated, the environment is rarely polluted, and recycled ethyl alcohol and catalyst can be repeatedly used.
Description
Technical field
The present invention relates to spices technical field, relating to a kind of is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate.
Background technology
Essence and flavoring agent industrial expansion depends on the new high-quality perfume material of constant discovery and improves its preparation technology.L-(+)-diethyl tartrate is a kind of colourless or faint yellow oily thick liquid, in faint Wine Aroma.Be mainly used in chiral drug and asymmetric catalysis field, and be the flavouring agent that GB2760-1996 specifies to allow to use.The synthetic method of L-(+)-industrial routine of tartrate diethyl is by L-(+ under dense H2SO4 catalysis)-tartrate and ethanol utilizes CCl4 esterification to dewater and forms.Due to dense H2SO4 severe corrosive, easily cause side reaction, and organic solvent serious environment pollution.People's proposition boric acid in patent CN200710011923.7 such as kingdom's victory, peaceful CHIGO substitute dense H2SO4 catalysis and obtain product, but when washing catalyzer off after esterification terminates, still can form a large amount of spent acid, waste water when catalyzer is washed out together with water, and solvent recuperation pollutes the environment equally.
Summary of the invention
The object of the invention is for above-mentioned deficiency of the prior art, thering is provided a kind of is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, can L-(+ be improved) yield of-diethyl tartrate, technique is simple, easy to operate, do not relate to and use the problem such as strong acidic liquid catalysis and solvent recuperation, whole technological process clean environment firendly, spent acid, waste water, waste gas can not be produced, almost environment is not polluted, and reclaim ethanol and catalyzer all reusable.
Object of the present invention is achieved through the following technical solutions.
A kind of is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, comprise the following steps:
Step (1): by L-(+)-tartrate, dehydrated alcohol, catalyzer join in reaction vessel, and stirring heating is reacted;
Step (2): after having reacted, after reactant is cooled to room temperature, filters and obtain filtrate, reclaim catalyzer, described catalyzer is storng-acid cation exchange resin;
Step (3): filtrate straight run distillation obtains colourless transparent liquid L-(+)-diethyl tartrate.Underpressure distillation parameter is 118-120 DEG C/66.7Pa.
L-(+ of the present invention) preparation principle of-diethyl tartrate is as follows:
Below in conjunction with specific embodiment, the present invention is further illustrated:
In following examples, if no special instructions, material used is commercially available prod.Target product L-(+)-diethyl tartrate, its structural formula is:
。
Wherein, in described step (1), L-(+) mass ratio of-tartrate and described dehydrated alcohol is 1:1-10.
Wherein, in described step (1), L-(+) mass ratio of-tartrate and described catalyzer is 1:0.1-0.6.
Wherein, in described step (1), reacting by heating temperature is 55-100 DEG C.
Wherein, in described step (1), reacting by heating temperature is 70-80 DEG C.
Wherein, in described step (1), the reaction times is 8-24 hour.
Wherein, in described step (1), the reaction times is 12-16 hour.
Wherein, in described step (2), storng-acid cation exchange resin is DOWEX DR 2030 Zeo-karb or the trade mark is NKC-9 or D072 Zeo-karb.
Wherein, in step (2), described storng-acid cation exchange resin and the recyclable recycling of unreacted ethanol.
Wherein, the granularity of described storng-acid cation exchange resin is 0.4-1.25mm >=95%, total exchange amount * (a) >=4.7 (b) >=1.5, rate of small round spheres >=90% after mill.
Wherein, in described step (1), reaction vessel is the there-necked flask that agitator, prolong, thermometer are housed.
Wherein, in described step (1), the massfraction of dehydrated alcohol is >=99.7%, in the dehydrated alcohol that the present invention selects, water content is lower, ensures its catalyst activity to greatest extent, catalytic effect, obtained L-(+)-diethyl tartrate yield is high.
beneficial effect of the present invention:
(1) the present invention adopts L-(+)-tartrate and dehydrated alcohol direct reaction under storng-acid cation exchange resin catalysis, dehydrated alcohol can serve as solvent simultaneously and use, can by L-(+ after temperature of reaction increases to over 50 DEG C)-tartrate all dissolves, and this reaction yield is up to 98%.
(2) storng-acid cation exchange resin used in the present invention (outward appearance: hunchbacked brown spherical particle, granularity: 0.4-1.25mm >=95%, total exchange amount * (a) >=4.7 (b) >=1.5, rate of small round spheres (%) >=90 after mill) to have exchange capacity high, uniform particles, the advantages such as wear resisting property is good, use as ester class catalyzer, there is excellent reactive behavior and selectivity, simultaneously, catalyzer can be recycled, and the time of recycling is greater than 200 hours, economizes on resources and cost.
(3) present invention process is simple, and easy to operate, utilization rate of raw materials is high.
(4) present invention process environmental protection, does not produce " three wastes ", and without the need to carrying out spent acid, wastewater treatment the present invention excessive dehydrated alcohol used is reusable after Calcium Chloride Powder Anhydrous drying dewaters after reclaiming.
Embodiment
For ease of understanding the present invention better, be illustrated by following instance.These examples belong to protection scope of the present invention, but do not limit the scope of the invention.
embodiment 1
By 3.0Kg L-(+)-tartrate, 15.0Kg ethanol, 0.9Kg DOWEX DR 2030 type storng-acid cation exchange resin join in the there-necked flask with agitator, prolong and thermometer successively, start stirring, temperature of reaction is 78 DEG C, reaction times is 18 hours, react complete and reaction system is cooled to room temperature, filtering recovering catalyst, air distillation removes unreacted ethanol, and underpressure distillation (b.p.:118 DEG C/66.7Pa) obtains colourless transparent liquid L-(+)-diethyl tartrate product 2.95Kg.
embodiment 2
By 3.0Kg L-(+)-tartrate, 15.0Kg ethanol, 0.6Kg DOWEX DR 2030 type storng-acid cation exchange resin join in the there-necked flask with agitator, prolong and thermometer successively, start stirring, temperature of reaction is 78 DEG C, reaction times is 18 hours, react complete and reaction system is cooled to room temperature, filtering recovering catalyst, air distillation removes unreacted ethanol, and underpressure distillation (b.p.:119 DEG C/66.7Pa) obtains colourless transparent liquid L-(+)-diethyl tartrate product 2.68 Kg.
embodiment 3
By 3.0Kg L-(+)-tartrate, 15.0Kg ethanol, 0.9Kg DOWEX DR 2030 type storng-acid cation exchange resin join in the there-necked flask with agitator, prolong and thermometer successively, start stirring, temperature of reaction is 78 DEG C, reaction times is 12 hours, react complete and reaction system is cooled to room temperature, filtering recovering catalyst, air distillation removes unreacted ethanol, and underpressure distillation (b.p.:120 DEG C/66.7Pa) obtains colourless transparent liquid L-(+)-diethyl tartrate product 2.44 Kg.
embodiment 4
By 3.0Kg L-(+)-tartrate, 15.0Kg ethanol, 0.9Kg DOWEX DR 2030 type storng-acid cation exchange resin join in the there-necked flask with agitator, prolong and thermometer successively, start stirring, temperature of reaction is 60 DEG C, reaction times is 18 hours, react complete and reaction system is cooled to room temperature, filtering recovering catalyst, air distillation removes unreacted ethanol, and underpressure distillation (b.p.:118 DEG C/66.7Pa) obtains colourless transparent liquid L-(+)-diethyl tartrate product 2.15 Kg.
embodiment 5
By 3.0Kg L-(+)-tartrate, 9.0Kg ethanol, 0.9Kg DOWEX DR 2030 type storng-acid cation exchange resin join in the there-necked flask with agitator, prolong and thermometer successively, start stirring, temperature of reaction is 78 DEG C, reaction times is 18 hours, react complete and reaction system is cooled to room temperature, filtering recovering catalyst, air distillation removes unreacted ethanol, and underpressure distillation (b.p.:120 DEG C/66.7Pa) obtains colourless transparent liquid L-(+)-diethyl tartrate product 2.41 Kg.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. be that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: comprise the following steps:
Step (1): by L-(+)-tartrate, dehydrated alcohol, catalyzer join in reaction vessel, and stirring heating is reacted;
Step (2): after having reacted, after reactant is cooled to room temperature, filtering recovering catalyst, described catalyzer is storng-acid cation exchange resin;
Step (3): filtrate straight run distillation obtains colourless transparent liquid L-(+)-diethyl tartrate.
2. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), L-(+) mass ratio of-tartrate and described dehydrated alcohol is 1:1-10.
3. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), L-(+) mass ratio of-tartrate and described catalyzer is 1:0.1-0.6.
4. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), reacting by heating temperature is 55-100 DEG C.
5. one according to claim 4 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), reacting by heating temperature is 70-80 DEG C.
6. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), the reaction times is 8-24 hour.
7. one according to claim 6 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), the reaction times is 12-16 hour.
8. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (2), storng-acid cation exchange resin is DOWEX DR 2030 Zeo-karb or the trade mark is NKC-9 or D072 Zeo-karb.
9. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in step (2), the granularity of described storng-acid cation exchange resin is 0.4-1.25mm, total exchange amount * (a) >=4.7 (b) >=1.5, rate of small round spheres >=90% after mill.
10. one according to claim 1 is that catalyst synthesizes L-(+ with storng-acid cation exchange resin) preparation technology of-diethyl tartrate, it is characterized in that: in described step (1), reaction vessel is the there-necked flask that agitator, prolong, thermometer are housed.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807957A (en) * | 2020-07-02 | 2020-10-23 | 深圳飞扬兴业科技有限公司 | Synthetic method of geranyl acetate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100428A (en) * | 2007-06-29 | 2008-01-09 | 沈阳化工学院 | Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid |
-
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- 2015-04-30 CN CN201510215154.7A patent/CN104926658A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100428A (en) * | 2007-06-29 | 2008-01-09 | 沈阳化工学院 | Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid |
Non-Patent Citations (2)
| Title |
|---|
| DOW: "DOWEX DR-2030 and DOWEX MONOSPHERE DR-2030 Catalysts", 《DOWEX ION EXCHANGE RESINS》, 31 May 2002 (2002-05-31) * |
| 吴桐等: "离子交换树脂催化合成L-（+）-酒石酸二乙酯的研究", 《化学工程师》, vol. 168, no. 9, 31 December 2009 (2009-12-31), pages 1 - 3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807957A (en) * | 2020-07-02 | 2020-10-23 | 深圳飞扬兴业科技有限公司 | Synthetic method of geranyl acetate |
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