CN108440621A - A kind of process for refining and purifying of avermectin - Google Patents
A kind of process for refining and purifying of avermectin Download PDFInfo
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- CN108440621A CN108440621A CN201810355792.2A CN201810355792A CN108440621A CN 108440621 A CN108440621 A CN 108440621A CN 201810355792 A CN201810355792 A CN 201810355792A CN 108440621 A CN108440621 A CN 108440621A
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- avermectin
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- fine work
- methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/08—Hetero rings containing eight or more ring members, e.g. erythromycins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
Abstract
The present invention relates to a kind of process for refining and purifying of avermectin, this method eliminates mother liquor heating concentration in process of production, and it is changed to Recycling Mother Solution and applies mechanically, the saturation degree of crystallization can be met without the concentration that heats up using mother liquid recycle, a previous Refining times are shortened 5 hours or so, and save the steam consumption consumed when concentration.And without the content for reducing purified product.Shortening working hour, energy-saving purpose are reached.
Description
Technical field：
The present invention relates to a kind of process for refining and purifying of avermectin, belong to biological pesticide technical field of refinement.
Background technology：
Avermectin be it is a kind of low toxicity, efficiently, high selection, green, environmental protection, biological source insecticide, it completely solves biography
System pesticide there are problems that generating pollution to environment, be the emphasis tackling key problem of China's " the Seventh Five-Year Plan ", " eight or five ", " 95 " and Eleventh Five-Year Plan
Project.It with the universal of avermectin in recent years and downstream product and promotes, has not only driven China's agricultural, animal husbandry energetically
Development, and agriculture-stock production is promoted to green, innoxious direction transformation.As maximally efficient insecticide in the world at present
One of avermectin, domestic usage amount is about 2500 tons or so, becomes the main product in agricultural chemical insecticide.
In current avermectin process for refining, refining crystallization mainly is carried out using alcohols, production stage generally comprises：It rises
The processes such as warm dissolving, filtering, concentration, decrease temperature crystalline achieve the purpose that improve crystallization purity by recycling to refine.But this work
Skill there are problems that：1, primary purification purification process takes around expenditure of time about 11-13 hours, in condensing crystallizing process
In need to carry out lysate in crystallizing tank heating concentration and need 6-8 hours or so, account for 50% of total time or so.2, due to
Concentration time is long, and steam consumption is also bigger in concentration process, high energy consumption.
Invention content：
In view of the deficiencies of the prior art, the present invention provides a kind of process for refining and purifying of avermectin, and this method contracts significantly
The short purification time saves steam usage amount, saves energy consumption.
Technical scheme is as follows：
A kind of process for refining and purifying of avermectin, the refined purification of first batch avermectin by existing conventional method into
Row is carried out per a batch of refined purification in the form of applying mechanically mother liquor later, including steps are as follows：
(1) when the refined purification of second batch avermectin, first batch avermectin essence is added into avermectin crude product
Two times methanol mother liquors in system purification, are then heated up, are kept the temperature, and avermectin is filtered after all dissolving, filtered
Crystal solution carries out decrease temperature crystalline, and then press filtration progress first pass is refined, obtains first pass time fine work, the mother liquor conduct being obtained by filtration
First pass time methanol mother liquor is applied mechanically when giving over to lower batch crude product refining；
(2) three times methanol mother liquors into first pass time fine work in the refined purification of addition first batch avermectin are risen
Temperature, heat preservation carry out decrease temperature crystalline after first pass time fine work dissolving, then press filtration carry out second time it is refined, obtain second time essence
Product, the mother liquor after press filtration are applied mechanically when giving over to lower batch crude product refining as second time methanol mother liquor；
(3) new methanol is added into second time fine work to be heated up, kept the temperature, cool down after second time fine work dissolving
Crystallization, then press filtration carry out third all over refining, obtain third all over time fine work, avermectin fine work is obtained after drying；
(4) when the refined purification of third batch avermectin, the first pass time first of step (1) is added into avermectin crude product
Then alcohol mother liquor is heated up, is kept the temperature, avermectin is filtered after all dissolving, and filtered crystal solution carries out cooling knot
Crystalline substance, then press filtration progress first pass is refined, obtains first pass time fine work, the mother liquor being obtained by filtration is as first pass time methanol mother liquor
It is applied mechanically when giving over to lower batch crude product refining；
(5) second time methanol mother liquor into first pass time fine work in addition step (2) is heated up, is kept the temperature, first
Carry out decrease temperature crystalline after the dissolving of time fine work, then press filtration carry out second time it is refined, obtain second time fine work, the mother after press filtration
Liquid is applied mechanically when giving over to lower batch crude product refining as second time methanol mother liquor；Second time fine work adds new methanol and is risen
Temperature is kept the temperature, and decrease temperature crystalline is carried out after second time fine work dissolving, and then press filtration carries out third all over refining, and obtains third all over time essence
Product obtain avermectin fine work after drying；
(6) later each batch is carried out by the process for refining and purifying of second batch, and Recycling Mother Solution applies mechanically use.
According to currently preferred, in step (1), avermectin mass content is 60~75% in avermectin crude product.
Currently preferred, the dosage of avermectin crude product is react tank volume 0.76-0.8 times in step (1).
Currently preferred, in step (1), the additive amount of two times methanol mother liquors is the 6.9- of avermectin crude product weight
7.5 again.
Currently preferred, in step (1), heating and heat preservation temperature is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
Currently preferred, in step (1), time of filter pressing is 2-6 hours.
Currently preferred, in step (2), the additive amount of three times methanol mother liquors is the 8.1- of avermectin crude product weight
8.5 times, heating and heat preservation temperature is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
Currently preferred, in step (3), third is carried out all over refined using methanol, and the additive amount of methanol is avermectin
8.5-9.2 times of crude product weight.
It is currently preferred, in step (4), during the first pass of third batch is refined, the additive amount of first pass time methanol mother liquor
It it is 6.9-7.5 times of avermectin crude product weight, heating and heat preservation temperature is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
It is currently preferred, in step (5), during second time of third batch is refined, the additive amount of second time methanol mother liquor
It it is 8.1-8.5 times of avermectin crude product weight, heating and heat preservation temperature is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
The effect and advantage of the present invention：
The crude product and inventory of the present invention show that inventory can excessively cause dissolution time to extend by long-term experiment
And not readily dissolve, the amount of the methanol mother liquor used is also to accumulate to obtain by cycle production, disclosure satisfy that production cycle uses,
Mother liquor will not be caused overstocked or shortage.
Currently preferred heating and heat preservation temperature is 70-75 DEG C, time fine work can be made fully to dissolve in methyl alcohol, and not
It can make a big impact in subtractive process to secondary fine work impurity, while ensure that solution rate.
For currently preferred cooling temperature between 25-30 DEG C, excessively high temperature can cause potency in dissolving mother liquor higher,
Yield is reduced, low temperature is crossed and also results in impurity raising in crystallization, influence product quality.
For currently preferred time of filter pressing at 2 hours or more, sufficient press filtration can reduce residue of mother in time fine work,
Reduce the amount of impurity.
The present invention eliminates mother liquor heating concentration in process of production, and is changed to Recycling Mother Solution and applies mechanically, using mother liquid recycle
The saturation degree that crystallization can be met without the concentration that heats up, a previous Refining times are shortened 5 hours or so, and saves
The steam consumption consumed when concentration.And without the content for reducing purified product.Reach shortening working hour, it is energy-saving
Purpose.
Specific implementation mode：
Below by specific embodiment result, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of process for refining and purifying of avermectin, the refined purification of first batch avermectin by existing conventional method into
Row is carried out per a batch of refined purification in the form of applying mechanically mother liquor later, including steps are as follows：
(1) when the refined purification of second batch avermectin, first batch avermectin essence is added into avermectin crude product
Two times methanol mother liquors in system purification, the additive amount of two times methanol mother liquors are 6.9 times of avermectin crude product weight, are then carried out
It is warming up to 70 DEG C to be kept the temperature, avermectin is filtered after all dissolving, and filtered crystal solution is cooled to 25 DEG C and is tied
Crystalline substance, then press filtration 4h progress first pass is refined, obtains first pass time fine work, and the mother liquor being obtained by filtration is female as first pass time methanol
Liquid is applied mechanically when giving over to lower batch crude product refining；
(2) three times methanol mother liquors into first pass time fine work in the refined purification of addition first batch avermectin are risen
70 DEG C of heat preservations of Wen Zhibao, the additive amount of three times methanol mother liquors are 8.1 times of avermectin crude product weight, first pass time fine work dissolving
After carry out being cooled to 25 DEG C of crystallizations, then press filtration carry out second time it is refined, obtain second time fine work, the mother liquor conduct after press filtration
It is applied mechanically when time methanol mother liquor gives over to lower batch crude product refining for second time；
(3) it adds new methanol into second time fine work to be heated up, kept the temperature, the additive amount of methanol is avermectin crude product
8.5 times of weight carry out decrease temperature crystalline after second time fine work dissolving, and then press filtration carries out third all over refining, and obtains third time
Secondary fine work obtains avermectin fine work after drying；
(4) when the refined purification of third batch avermectin, the first pass time first of step (1) is added into avermectin crude product
Alcohol mother liquor, the additive amount of first pass time methanol mother liquor are 6.9 times of avermectin crude product weight, are then heated up, are kept the temperature, Ah
Dimension rhzomorph is filtered after all dissolving, and filtered crystal solution carries out decrease temperature crystalline, and then press filtration progress first pass is refined, obtains
To first pass time fine work, the mother liquor being obtained by filtration is applied mechanically when giving over to lower batch crude product refining as first pass time methanol mother liquor；
(5) second time methanol mother liquor into first pass time fine work in addition step (2) is heated up, is kept the temperature, second
Additive amount all over time methanol mother liquor is 8.1 times of avermectin crude product weight, and decrease temperature crystalline is carried out after first pass time fine work dissolving,
Then press filtration carry out second time it is refined, obtain second time fine work, the mother liquor after press filtration gives over to as second time methanol mother liquor
It is applied mechanically when lower batch crude product refining；Second time fine work adds new methanol and is heated up, kept the temperature, and second time fine work dissolving is laggard
Row decrease temperature crystalline, then press filtration carry out third all over refining, obtain third all over time fine work, avermectin fine work is obtained after drying；
(6) later each batch is carried out by the process for refining and purifying of second batch, and Recycling Mother Solution applies mechanically use.
Embodiment 2
A kind of process for refining and purifying of avermectin, with embodiment 1, the difference is that：
The additive amount of (1) two time methanol mother liquor of step is 7.1 times of avermectin crude product weight, then carries out being warming up to 72
It DEG C is kept the temperature, avermectin is all filtered after dissolving, and filtered crystal solution is cooled to 27 DEG C and is crystallized, and then presses
It is refined to filter 6h progress first passes,
Three time methanol mother liquors of the step (2) into first pass time fine work in the refined purification of addition first batch avermectin into
Row is warming up to 72 DEG C of heat preservations of guarantor, and the additive amount of three times methanol mother liquors is 8.3 times of avermectin crude product weight, first pass time fine work
It carries out being cooled to 27 DEG C of crystallizations after dissolving；
Step (3) adds new methanol into second time fine work and is heated up, kept the temperature, and the additive amount of methanol is avermectin
8.8 times of crude product weight；
When the refined purification of step (4) third batch avermectin, the first pass of step (1) is added into avermectin crude product
Secondary methanol mother liquor, the additive amount of first pass time methanol mother liquor are 7.1 times of avermectin crude product weight, are then heated up, are protected
Temperature,
Second time methanol mother liquor of the step (5) into first pass time fine work in addition step (2) is heated up, is kept the temperature,
The additive amount of second time methanol mother liquor is 8.3 times of avermectin crude product weight.
Embodiment 3
A kind of process for refining and purifying of avermectin, with embodiment 1, the difference is that：
The additive amount of (1) two time methanol mother liquor of step is 7.5 times of avermectin crude product weight, then carries out being warming up to 75
It DEG C is kept the temperature, avermectin is all filtered after dissolving, and filtered crystal solution is cooled to 30 DEG C and is crystallized, and then presses
It is refined to filter 4h progress first passes,
Three time methanol mother liquors of the step (2) into first pass time fine work in the refined purification of addition first batch avermectin into
Row is warming up to 75 DEG C of heat preservations of guarantor, and the additive amount of three times methanol mother liquors is 8.5 times of avermectin crude product weight, first pass time fine work
It carries out being cooled to 30 DEG C of crystallizations after dissolving；
Step (3) adds new methanol into second time fine work and is heated up, kept the temperature, and the additive amount of methanol is avermectin
9.0 times of crude product weight；
When the refined purification of step (4) third batch avermectin, the first pass of step (1) is added into avermectin crude product
Secondary methanol mother liquor, the additive amount of first pass time methanol mother liquor are 7.5 times of avermectin crude product weight, are then heated up, are protected
Temperature,
Second time methanol mother liquor of the step (5) into first pass time fine work in addition step (2) is heated up, is kept the temperature,
The additive amount of second time methanol mother liquor is 8.5 times of avermectin crude product weight.
Comparative example 1
A kind of process for refining and purifying of avermectin, with embodiment 1, the difference is that：Every time time the methanol used is new
Methanol, dosage is identical as embodiment, and condensing crystallizing process is all made of 60-65 DEG C of normal pressure and at the uniform velocity concentrates, concentration volume to 2m3, remove
Above outer, other technological parameters of comparative example are pressed embodiment same process parameter and are produced.
Comparative example 2
A kind of process for refining and purifying of avermectin, with embodiment 2, the difference is that：Every time time the methanol used is new
Methanol, dosage is identical as embodiment, and condensing crystallizing process is all made of 60-65 DEG C of normal pressure and at the uniform velocity concentrates, concentration volume to 2m3, remove
Above outer, other technological parameters of comparative example are pressed embodiment same process parameter and are produced.
Comparative example 3
A kind of process for refining and purifying of avermectin, with embodiment 2, the difference is that：Every time time the methanol used is new
Methanol, dosage is identical as embodiment, and condensing crystallizing process is all made of 60-65 DEG C of normal pressure and at the uniform velocity concentrates, concentration volume to 2m3, remove
Above outer, other technological parameters of comparative example are pressed embodiment same process parameter and are produced.
Experimental example：
The refined purification of Example 1-3 thirds batch avermectin obtains respectively avermectin fine work test b 1a contents,
B1 contents, B1a purity and B1b purity, while the B1a contents of the avermectin of test comparison example 1-3 acquisitions, B1 contents, B1a are pure
Degree and B1b purity, are as a result shown in Table 1, table 2, table 3, table 4 respectively；
The parameter for the avermectin fine work that the refined purification of 1 embodiment of table, 1 third batch avermectin obtains
The parameter for the avermectin fine work that the refined purification of 2 embodiment of table, 2 third batch avermectin obtains
The parameter for the avermectin fine work that the refined purification of 3 embodiment of table, 3 third batch avermectin obtains
The parameter for the avermectin fine work that the refined purification of 4 comparative example 1-4 avermectin of table obtains
Analysis comparing result is shown in Table 5,
Table 5 analyzes comparative example result
It is being produced by refining purifying technique using avermectin provided by the invention known to Experimental comparison's case in upper table
In average every batch of production hour reduce 16 hours or so, and the batch matter of product quality and normal use concentration and crystallization process
Without larger difference in amount, reduces concentration process and steam consumption is greatly saved, 1 ton hour of steam consumption, every batch of are pressed in concentration production
Secondary production can save 16 tons of steam usage amounts.
Claims (9)
1. a kind of process for refining and purifying of avermectin, the refined purification of first batch avermectin by existing conventional method into
Row is carried out per a batch of refined purification in the form of applying mechanically mother liquor later, including steps are as follows：
(1) when the refined purification of second batch avermectin, into avermectin crude product, addition first batch avermectin is refined carries
Two times methanol mother liquors in pure, are then heated up, are kept the temperature, and avermectin is filtered after all dissolving, filtered crystallization
Liquid carries out decrease temperature crystalline, and then press filtration progress first pass is refined, obtains first pass time fine work, the mother liquor being obtained by filtration is as first
It is applied mechanically when giving over to lower batch crude product refining all over time methanol mother liquor；
(2) three times methanol mother liquors into first pass time fine work in the refined purification of addition first batch avermectin heated up,
Heat preservation carries out decrease temperature crystalline after first pass time fine work dissolving, then press filtration carry out second time it is refined, obtain second time fine work,
Mother liquor after press filtration is applied mechanically when giving over to lower batch crude product refining as second time methanol mother liquor；
(3) new methanol is added into second time fine work to be heated up, kept the temperature, cooling knot is carried out after second time fine work dissolving
Crystalline substance, then press filtration carry out third all over refining, obtain third all over time fine work, avermectin fine work is obtained after drying；
(4) when the refined purification of second batch avermectin, the first pass time methanol that step (1) is added into avermectin crude product is female
Then liquid is heated up, is kept the temperature, avermectin is filtered after all dissolving, and filtered crystal solution carries out decrease temperature crystalline, so
Press filtration progress first pass is refined afterwards, obtains first pass time fine work, and the mother liquor being obtained by filtration gives over to as first pass time methanol mother liquor
It is applied mechanically when lower batch crude product refining；
(5) second time methanol mother liquor into first pass time fine work in addition step (2) is heated up, is kept the temperature, first pass
Carry out decrease temperature crystalline after fine work dissolving, then press filtration carry out second time it is refined, obtain second time fine work, the mother liquor after press filtration is made
It is applied mechanically when giving over to lower batch crude product refining for second time methanol mother liquor；Second time fine work adds new methanol and is heated up, protected
Temperature carries out decrease temperature crystalline after second time fine work dissolving, and then press filtration carries out third all over refining, and obtains third all over time fine work, dries
Avermectin fine work is obtained after dry；
(6) later each batch is carried out by the process for refining and purifying of second batch, and Recycling Mother Solution applies mechanically use.
2. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (1), avermectin
Avermectin mass content is 60~75% in crude product.
3. the process for refining and purifying of avermectin according to claim 1, which is characterized in that avermectin in step (1)
The dosage of crude product is react tank volume 0.76-0.8 times.
4. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (1), two times methanol
The additive amount of mother liquor is 6.9-7.5 times of avermectin crude product weight.
5. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (1), heating and heat preservation
Temperature is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C, and time of filter pressing is 2-6 hours.
6. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (2), two times methanol
The additive amount of mother liquor is 8.1-8.5 times of avermectin crude product weight, and heating and heat preservation temperature is 70-75 DEG C, decrease temperature crystalline temperature
It is 25-30 DEG C.
7. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (3), third is all over essence
System is carried out using methanol, and the additive amount of methanol is 8.5-9.2 times of avermectin crude product weight.
8. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (4), second batch
During first pass is refined, the additive amount of first pass time methanol mother liquor is 6.9-7.5 times of avermectin crude product weight, heating and heat preservation temperature
Degree is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
9. the process for refining and purifying of avermectin according to claim 1, which is characterized in that in step (5), second batch
During second time refined, the additive amount of second time methanol mother liquor is 8.1-8.5 times of avermectin crude product weight, heating and heat preservation temperature
Degree is 70-75 DEG C, and decrease temperature crystalline temperature is 25-30 DEG C.
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| US5077398A (en) * | 1986-11-18 | 1991-12-31 | Merck & Co., Inc. | Process for isolation of avermectin B1 components with improved purity and subsequent isolaton of B2 components |
| KR20010039119A (en) * | 1999-10-29 | 2001-05-15 | 김선진 | Process for the purification of Avermectin |
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Application publication date: 20180824 |