CN102233278B - Method for recovering rhodium catalyst from imipenem medicine production - Google Patents
Method for recovering rhodium catalyst from imipenem medicine production Download PDFInfo
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- CN102233278B CN102233278B CN 201010164835 CN201010164835A CN102233278B CN 102233278 B CN102233278 B CN 102233278B CN 201010164835 CN201010164835 CN 201010164835 CN 201010164835 A CN201010164835 A CN 201010164835A CN 102233278 B CN102233278 B CN 102233278B
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Abstract
The invention relates to a method for recovering a rhodium catalyst from imipenem medicine producing. The method is characterized by: adding a certain amount of an adsorbent to mother liquid of imipenem medicine bicyclic parent nucleus synthesis reaction catalyzed through a rhodium octanoate dimmer catalyst, followed by holding for a certain time, then absorbing the rhodium octanoate dimmer catalyst through active carbon; dissolving the absorbed rhodium octanoate dimmer through a first solvent; removing metal impurities through ion exchange resin; then carrying out a vacuum distillation to remove most the first solvent, followed by cooling, crystallizing and filtering; washing the resulting filter cake through a small quantity of a second solvent, followed by drying. The first solvent is a mixture which comprises, but is not limited to, octanoic acid and chlorobenzene, wherein a ratio of the octanoic acid to the chlorobenzene is 1:1. The second solvent is, but is not limited to the chlorobenzene. The method provided by the present invention has characteristics of economy and environmental protection, simple operation, good quality of the resulting rhodium catalyst and high yield of the rhodium catalyst.
Description
Technical field
The present invention relates to catalyst recovery and noble metal chemical technology field, aim to provide a kind of method of producing recovery rhodium catalyst reaction solution from penem-like pharmaceutical.
Background technology
Penem-like pharmaceutical is that U.S. medical research personnel are in the new antibiotic of a kind of brand-new chemical constitution of the exploitation seventies in last century.Belong to beta-lactam antibiotic together with PCs, cephalo-type; Clinical research shows, training southern class all has powerful antibacterial power to gram-positive bacteria and negative bacterium, also can be used for tackling the caused infection of various common methicillin-resistant antibody-resistant bacterium disease.According to studies show that of international antibiotic industrial quarters, in being put into 3 kinds of the fastest antibiotic new drugs of international medical market speedup in recent years, penem-like pharmaceutical ranks the umber one.
Synthesizing of penem-like pharmaceutical series key intermediate, all need use the Noble Metal Rhodium catalyst, its use amount is larger.And because the exploitation of rhodium is extracted all more difficult, the rhodium catalyst preparation process is very complicated, with high costs, therefore, along with the rhodium rise day by day of price in the international market, the recovery rhodium catalyst also improves its utilization rate, has become the inevitable choice of penem-like pharmaceutical manufacturing enterprise, so not only be more conducive to environmental protection, also be conducive to the reduction of enterprise's production cost.
At present, on market, the method for disclosed penem-like pharmaceutical production field, recovery rhodium mainly contains extraction, submerged combustion, ashing firing method etc.
Extraction uses strong acid and peroxide that reaction mother liquor is processed and makes it to generate water oil two-phase mixture, the destroyed laggard water that enters of the rhodium complex in organic phase, two-phase separately after rhodium separated.But because the chemical bond power of Noble Metal Rhodium is stronger, the complex compound of generation is more stable, therefore reclaims rhodium content low, and the rate of recovery is not high yet.
Submerged combustion is that the mother liquor with rhodium catalyst is entered the submerged combustion Indoor Combustion together with air, and the product water absorbs, and obtains rhodium after filtration.This method cost is high, and yield is low.
The ashing firing method at high temperature will be burned into ash content with the mother liquor of rhodium catalyst, then with molten condition under alkali compounds reaction, generate the rhodium salt of solubility, then adopt electrolysis tech that rhodium is separated.This method is high to equipment requirement, and is seriously polluted.
Summary of the invention
The purpose of this invention is to provide a kind of method from recovering rhodium catalyst from imipenem medicine producing.
The present invention processes is mother liquor (hereinafter to be referred as the dicyclo mother liquor) through the penem-like pharmaceutical bicyclic mother nucleus synthetic reaction of sad rhodium catalysis, after rhodium catalyst uses some cycles, its activity drops to a certain degree just must discharge carries out regeneration activating or recovery, repeatedly just become the spent rhodium catalyst raffinate after activation cycle, activity recovery, just must reclaim again.
Technical scheme of the present invention is achieved in that
A kind of method of recovering rhodium catalyst from imipenem medicine producing is provided, it is characterized in that:
Add the sad rhodium catalyst of a certain amount of adsorbent insulation certain hour absorption in the mother liquor of the penem-like pharmaceutical bicyclic mother nucleus synthetic reaction of sad rhodium catalyst catalysis, use again the hereinafter described sad rhodium of the first dissolution with solvents charcoal absorption, remove metal impurities through ion exchange resin, then most of the first solvent is removed in decompression distillation, crystallisation by cooling filters, and filter cake is with hereinafter described dry after the second solvent wash on a small quantity.
Described adsorbent refers to but is not limited to Powdered Activated Carbon, silica gel.The adsorbent addition is 1～2%, and adsorption temp is 60～70 ℃, and temperature retention time is half an hour.
The first solvent of the sad rhodium of described lytic activity charcoal absorption refer to but be not limited to sad, by the sad and chlorobenzene of 1: 1 proportioning.
The crystallisation by cooling temperature of the sad rhodium solution of described recovery is-5～0 ℃.
A small amount of the second solvent that described washing leaching cake is used refers to but is not limited to chlorobenzene.
Described filtration cakes torrefaction temperature is 50 ℃, and be 2 hours drying time.
Below, further describe technical scheme of the present invention:
The dicyclo mother liquor that will contain dead catalyst is warmed up to 60～70 ℃, adds inward the adsorbent of 1～2% (w%), is incubated half an hour, filters, and obtains containing the adsorbent filter cake of sad rhodium catalyst; Filter cake stirs and slowly is warming up to 150 ℃ after loose and removes solvent in filter cake and high boiling point by-products produced; With 4 times sad 60 ℃ of adsorbent filter cakes 2 hours that soak after heat treated, filter, with a small amount of sad washing leaching cake twice, merging filtrate; Filtrate is passed through cation exchange column with the speed of 5～8m/h, except metal heteroions such as de-iron, copper; Decompression distillation is concentrated into 1/4 with liquor capacity, is cooled to 0 ℃, filters, and after filter cake washed with a small amount of cold chlorobenzene, 50 ℃ of lower vacuum drying namely got the rhodium catalyst after recovery in 2 hours.
The present invention has economic environmental protection, the characteristics that easy and simple to handle, reaction gained rhodium catalyst quality is good, the rate of recovery is high.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but be not limited to the present embodiment:
Add the dicyclo mother liquor 100g (rhodium mass fraction 0.20%) that contains dead catalyst in the 250ml reaction bulb, stirring is warmed up to 65 ℃, add inward Powdered Activated Carbon 2g, be incubated half an hour, filter, filter cake is weighed as 30.8g, stirs to pour into after loose slowly to be warming up to 150 ℃ in the 100ml beaker and to remove solvent in filter cake and high boiling point by-products produced, is weighed as 21.8g.
Soak with the sad stirring of 100ml, slowly be warmed up to 60 ℃, be incubated 2 hours, filter, use respectively the sad washing leaching cake twice of 10ml, merging filtrate.
Filtrate is passed through cation exchange column with the speed of 5～8m/h, except metal heteroion decompression distillation such as de-iron, copper, liquor capacity is concentrated into 1/4, be cooled to 0 ℃, filter, after filter cake washed with a small amount of cold chlorobenzene, 50 ℃ of lower vacuum drying namely got the rhodium catalyst after recovery, the rhodium rate of recovery 95.83% in 2 hours.
Embodiment 2:
Add the dicyclo mother liquor 300g (rhodium mass fraction 0.20%) that contains dead catalyst in the 500ml reaction bulb, stirring is warmed up to 65 ℃, add inward silica gel of powder 6g, be incubated half an hour, filter, filter cake is weighed as 91.5g, stirs to pour into after loose slowly to be warming up to 150 ℃ in the 250ml beaker and to remove solvent in filter cake and high boiling point by-products produced, is weighed as 63.9g.
Successively add sad the stirring with the 150ml chlorobenzene of 150ml to soak, slowly be warmed up to 60 ℃, be incubated 2 hours, filter, use respectively the sad washing leaching cake twice of 10ml, merging filtrate.
Filtrate is passed through cation exchange column with the speed of 5～8m/h, except metal heteroion decompression distillation such as de-iron, copper, liquor capacity is concentrated into 1/4, be cooled to 0 ℃, filter, after filter cake washed with a small amount of cold chlorobenzene, 50 ℃ of lower vacuum drying namely got the rhodium catalyst after recovery, the rhodium rate of recovery 97.35% in 2 hours.
Although above shown detailed embodiment of the present invention, apparent, those skilled in the art is under prerequisite of the present invention, can carry out the part modifications and changes; The content that description is above mentioned is the illustration of property as an illustration only, is not as limitation of the present invention; Method with recovering rhodium catalyst from imipenem medicine producing of technical characterictic described herein all falls into this patent protection domain.
Claims (6)
1. the method for a recovering rhodium catalyst from imipenem medicine producing, it is characterized in that: add the sad rhodium catalyst of a certain amount of adsorbent insulation certain hour absorption in the mother liquor of the penem-like pharmaceutical bicyclic mother nucleus synthetic reaction of sad rhodium catalyst catalysis, use again the sad rhodium of the first dissolution with solvents charcoal absorption, remove metal impurities through ion exchange resin, then most of the first solvent is removed in decompression distillation, crystallisation by cooling filters, filter cake with a small amount of the second solvent wash after drying.
2. the method for recovering rhodium catalyst from imipenem medicine producing as claimed in claim 1, it is characterized in that: described adsorbent refers to Powdered Activated Carbon, and the adsorbent addition is 1～2%, and adsorption temp is 60～70 ℃, and temperature retention time is half an hour.
3. the method for recovering rhodium catalyst from imipenem medicine producing as claimed in claim 1 is characterized in that: described the first solvent refers to sad or by the sad and chlorobenzene of 1: 1 proportioning.
4. the method for recovering rhodium catalyst from imipenem medicine producing as claimed in claim 1 is characterized in that: the temperature that described crystallisation by cooling filters is-5～0 ℃.
5. the method for recovering rhodium catalyst from imipenem medicine producing as claimed in claim 1, it is characterized in that: described the second solvent refers to chlorobenzene.
6. the method for recovering rhodium catalyst from imipenem medicine producing as claimed in claim 1 is characterized in that: described filter cake with a small amount of the second solvent wash after dry temperature be 50 ℃, be 2 hours drying time.
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| CN 201010164835 CN102233278B (en) | 2010-04-29 | 2010-04-29 | Method for recovering rhodium catalyst from imipenem medicine production |
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| CN 201010164835 CN102233278B (en) | 2010-04-29 | 2010-04-29 | Method for recovering rhodium catalyst from imipenem medicine production |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101180051A (en) * | 2005-05-26 | 2008-05-14 | 盐野义制药株式会社 | Method for preparation of aqueous doripenem solution |
| CN101348486A (en) * | 2008-08-29 | 2009-01-21 | 深圳市海滨制药有限公司 | Preparation of meropenem |
| CN101560215A (en) * | 2009-05-27 | 2009-10-21 | 复旦大学 | Method for removing residual palladium of faropenem sodium |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101180051A (en) * | 2005-05-26 | 2008-05-14 | 盐野义制药株式会社 | Method for preparation of aqueous doripenem solution |
| CN101348486A (en) * | 2008-08-29 | 2009-01-21 | 深圳市海滨制药有限公司 | Preparation of meropenem |
| CN101560215A (en) * | 2009-05-27 | 2009-10-21 | 复旦大学 | Method for removing residual palladium of faropenem sodium |
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