CN109368594A - The recovery method of iodine in a kind of cephalosporins medicine waste liquid - Google Patents
The recovery method of iodine in a kind of cephalosporins medicine waste liquid Download PDFInfo
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- CN109368594A CN109368594A CN201811395548.5A CN201811395548A CN109368594A CN 109368594 A CN109368594 A CN 109368594A CN 201811395548 A CN201811395548 A CN 201811395548A CN 109368594 A CN109368594 A CN 109368594A
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- iodine
- waste liquid
- cephalosporins medicine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/13—Iodine; Hydrogen iodide
- C01B7/14—Iodine
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cephalosporin Compounds (AREA)
Abstract
The present invention settles sth. according to policy or law the recovery method of iodine in cephalosporins medicine waste liquid a kind of, include the following steps: to add alkali extraction and separation to go out methanol, acetone and lye cephalosporins medicine waste liquid, the hydrolysis of lye circulating-heating, acidification slot acidification is transferred to after filtering, stratification removes organic matter not soluble in water, and aqueous phase oxidation reaction tower is by I later‑It is oxidized to IO3 ‑, then be passed through IO in reduction kettle3 ‑It is reduced to I2, elemental iodine is precipitated, thick iodine is recovered by filtration to obtain, continues to heat, distil, elemental iodine of sublimating to obtain.This method recycles noble metal iodine in waste liquid, iodine is set to exist in solution with free state by alkaline hydrolysis, acidification, and decomposite organic matter not soluble in water, this method is not necessarily to strict control oxidizer, safety easy to operate, the rate of recovery of iodine is set to reach 98.5% or more, suitable process amplification production.
Description
Technical field
The present invention relates to a kind of recovery methods of cephalosporins medicine waste liquid iodine.
Background technique
The production of Cefepime, Cefpirome, cefotaxime these three bulk pharmaceutical chemicals, wherein 3 substitution reactions generate in 3
Mesosome needs trimethyl silicane iodine alkane to participate in reaction, this, which makes to produce in waste liquid, contains iodide ion, in order to avoid elemental iodine waste, needs
The recycling of elemental iodine is carried out to cephalosporins medicine waste liquid.
The cephalosporins medicine of most of China production at present does not recycle waste liquid to iodine, iodine in cephalosporins medicine waste liquid
It is female that ion source production cephalosporins medicine intermediate in trimethyl silicane iodine alkane, industry needs excessive Iodotrimethylsilane to participate in
The protection of core functional group and iodide reaction, with anion ion-exchange reactions occurs for iodide ion again in compound later, so that instead
The iodine in whole trimethyl silicane iodine alkane used is answered all to be present in the form of iodide ion in cephalosporins medicine waste liquid, but due to anti-
The hydroiodic acid that should be generated is deposited in the solution, and hydriodate is formed in conjunction with cephalosporin compound, and the recycling for causing iodine is tired
It is difficult.Since elemental iodine is precious metal, this phenomenon causes the waste of iodine, therefore the recycling of iodine is extremely urgent.
The iodine of devil liquor recovery containing iodine mainly uses oxidizing process, reduction method, ion-exchange, air blowout method, floatation, work
The methods of property carbon adsorption, extractive distillation method and liquid-film method are recycled the iodine in waste liquid containing iodine in the form of thick iodine.However
No matter mentioning iodine with which type of raw material, basic principle is all identical: iodine must be transferred to liquid phase first, obtained containing iodine
Iodine component in material liquid is become iodine then by the method for oxidation or reduction by material liquid.Generate the process of iodine
It is one of the committed step in technique of extracting iodine.
Summary of the invention
The present invention provides a kind of recovery method of iodine in cephalosporins medicine waste liquid, this method is gone back using hydrolysis-oxidation-
Original-filtering-distils-recovery method sublimated, waste liquid make iodide ion exist in solution with free state through basification, pass through
Some column processing rate of recovery are high, purity is good, and have process route simple, and large-scale production is suitble to utilize.
The recovery method of iodine in a kind of cephalosporins medicine waste liquid comprising the steps of:
A, cephalosporins medicine waste liquid is passed through in reaction kettle, alkali extraction and separation is added to go out methanol, acetone and water phase, water phase circulation
It flows back in reaction kettle and heats again, be filtered to remove insoluble impurity after treatment；
B, after water phase enters the acidification of acidification slot, stir process, stratification removes organic matter not soluble in water.
C, water phase is passed through oxidizing tower to react, liquid enters in tower from tower top sprinkling by water phase I-It is oxidized to IO3 -；
D, water phase is passed through reduction kettle later and reducing agent is added by IO3 -It is reduced to I2Purple red precipitate is generated, by filtering,
Heat, distil, sublimating and to obtain elemental iodine.
In preferred steps a, alkali is 20%~30% sodium hydroxide or potassium hydroxide solution, adjusts pH value 12~13, heating
90~120 DEG C of hydrolysis temperature.
In preferred steps b, acidification pH value is 1~5, is stirred to react 1~3h.
In preferred steps c, oxidant is potassium chlorate or sodium chlorate, and oxidant is with cephalosporins medicine waste liquid mass volume ratio
20~30g:1L.
In preferred steps d, reducing agent is sulfur dioxide or sodium hydrogensulfite, sodium hydrogensulfite and cephalosporins medicine waste liquid matter
Amount volume ratio is 50~100g:1L, and sulfur dioxide and cephalosporins medicine waste liquid mass volume ratio are 25~50g:1L, and filtering adds
Heat distils, sublimates and complete in same device, obtains thick iodine after filtering removal waste liquid, continues to heat iodine distillation later to be iodine vapor, then
It is cooling to be passed through condensed water, so that iodine vapor is sublimated to obtain elemental iodine, heating temperature is 50~100 DEG C.
In step a, 20%~30% sodium hydroxide or potassium hydroxide solution is added in cephalosporins medicine waste liquid, by destroying medicine
Object component separates methanol and acetone from waste liquid, and remaining lye heating hydrolysis separates the organic matter generated from lye,
Residue is not dissolved in by being filtered to remove.
In step b, acidification, stratification water phase are separated with organic phase again after above-mentioned alkalization hydrolysis, in this way in reaction
The iodine of generation, which is all enriched in the form of iodine anion, to be in water phase.
Step c, in d, iodide ion can save the stringent control of oxidizer by being oxidized to iodate ion in this way
System, iodate ion is reduced to elemental iodine under reducing agent effect by iodate ion later, by filtering to obtain thick iodine, is continued
Heating iodine distillation is iodine vapor, through supercooling, sublimates to obtain elemental iodine, wherein filtering, heating, distilling, sublimating all fills at one
Middle completion is set, device sealing avoids iodine vapor from volatilizing, it is ensured that obtain high-purity elemental iodine.
The present invention has the beneficial effect that:
The technical issues of the invention patent is solved recycles iodide ion in cephalosporins medicine waste liquid, passes through combination
Alkalization hydrolysis and acidification hydrolization processing separate iodide ion with organic matter, and iodide ion is enriched in water phase, facilitates the separation of elemental iodine
Recycling.Oxidant is directly by I-It is oxidized to IO3 -, then by IO3 -Restore I2, it thus is avoided that in prior art because of peroxidating phenomenon pair
The strict control of oxidizer, facilitates operation, and the processing method restored in this way through peroxidating improves the rate of recovery of iodine.
This process is easy to operate, and the rate of recovery of iodine is high, purity is good, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is process equipment flow chart of the invention；
In figure: 1- reaction kettle；2- alkali liquid tank；3- solvent tank；4- water phase fluid reservoir；Transfering material pump；6- filter；7- acid
Flow container 8- is acidified slot；10- oxidizing tower；11- reducing agent holding vessel；12- reduction kettle；13- filtering and heating tank；14- iodine recycles storage tank；
15- waste liquid holding vessel；16- waste residue recycling can；17- organic phase recycling can.
Specific embodiment
In order to deepen the understanding of the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not
Constitute limiting the scope of the present invention.
Fig. 1 is process equipment flow chart of the invention, as described in Figure 1, in a kind of cephalosporins medicine waste liquid of the present invention
The recovery method of iodine, after cephalosporins medicine waste liquid initially enters 1- reaction kettle addition lye, adjusting pH value is 12~13, stirring,
Stratification isolates solvent methanol, acetone and lye, recycles lye later, and lye circulation flows back to 1- reaction kettle again, and heating is stirred
Mix back hydrolysis, by being filtered to remove insoluble impurity, remaining liq again acidification hydrolization destroy drug component isolate it is not soluble in water
Organic phase, water phase is passed through 10- oxidizing tower, iodide ion in water phase made to be oxidized to iodate ion, and liquid flows into 12- reduction later
Elemental iodine is reduced in kettle, by thick iodine is obtained by filtration, in order to purify iodine, remaining solid heating sublimation becomes iodine vapor, later
It is cooling to be passed through condensed water, sublimates to obtain pure iodine, recycles elemental iodine.
Embodiment 1
1L cephalosporins medicine waste liquid is added in reaction kettle, 20% sodium hydroxide is added and adjusts pH=12, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 90 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=5, and water phase is passed through oxidizing tower oxidation, and sodium chlorate 20g is added in the inside, carries out oxidation reaction
20min enters reduction kettle later, and sulfur dioxide 25g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
50 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 98.7% of iodine after measured, the content 99.1% of iodine.
Embodiment 2
2L cephalosporins medicine waste liquid is added in reaction kettle, 30% sodium hydroxide is added and adjusts pH=13, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 120 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=1, and water phase is passed through oxidizing tower oxidation, sodium chlorate 60g is added, and carries out oxidation reaction
30min enters reduction kettle later, and sulfur dioxide 100g is added, and reacts 20min, has dark precipitate generation to filter to obtain thick iodine,
100 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 99% of iodine after measured, the content 99.2% of iodine.
Embodiment 3
1.5L cephalosporins medicine waste liquid is added in reaction kettle, 20% potassium hydroxide is added and adjusts pH=12, is stirred to react
Half an hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, and lye follows
Circulation enters heating kettle, and 100 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot is passed through after filtering and is stirred
Acidification is mixed, 36% hydrochloric acid is added and adjusts pH=2, water phase is passed through oxidizing tower oxidation, and potassium chlorate 30g is added in the inside, aoxidize anti-
30min is answered, enters reduction kettle later, sodium sulfite 75g is added, reacts 30min, has dark precipitate generation to filter slightly
Iodine heats up 80 DEG C of heating temperature, cooling later, pure iodine of sublimating to obtain.The rate of recovery 98.8% of iodine after measured, the content of iodine
99.1%.
Embodiment 4
1L cephalosporins medicine waste liquid is added in reaction kettle, 30% potassium hydroxide is added and adjusts pH=13, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 120 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=3, and water phase is passed through oxidizing tower oxidation, and potassium chlorate 30g is added in the inside, carries out oxidation reaction
20min enters reduction kettle later, and sodium sulfite 100g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
70 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 98.5% of iodine after measured, the content 99.2% of iodine.
Comparative example 1
1L cephalosporins medicine waste liquid is added in reaction kettle, 30% potassium hydroxide is added and adjusts pH=10, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 120 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=3, and water phase is passed through oxidizing tower oxidation, and potassium chlorate 30g is added in the inside, carries out oxidation reaction
20min enters reduction kettle later, and sodium sulfite 100g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
70 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 82.3% of iodine after measured, the content 98.1% of iodine.
Comparative example 2
2L cephalosporins medicine waste liquid is added in reaction kettle, 30% sodium hydroxide is added and adjusts pH=14, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 120 DEG C of heating temperature, after being stirred to react a hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=1, and water phase is passed through oxidizing tower oxidation, sodium chlorate 50g is added, and carries out oxidation reaction
30min enters reduction kettle later, and sulfur dioxide 80g is added, and reacts 20min, has dark precipitate generation to filter to obtain thick iodine,
100 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 83.3% of iodine after measured, the content 98.9% of iodine.
Comparative example 3
1L cephalosporins medicine waste liquid is added in reaction kettle, 20% sodium hydroxide is added and adjusts pH=12, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 90 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=5, and water phase is passed through oxidizing tower oxidation, and sodium chlorate 15g is added in the inside, carries out oxidation reaction
20min enters reduction kettle later, and sulfur dioxide 25g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
50 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 85.1% of iodine after measured, the content 98.3% of iodine.
Comparative example 4
1L cephalosporins medicine waste liquid is added in reaction kettle, 20% potassium hydroxide is added and adjusts pH=12, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 100 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=2, and water phase is passed through oxidizing tower oxidation, and potassium chlorate 50g is added in the inside, carries out oxidation reaction
30min enters reduction kettle later, and sodium sulfite 50g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
80 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 78.8% of iodine after measured, the content 97.9% of iodine.
Comparative example 5
2L cephalosporins medicine waste liquid is added in reaction kettle, 20% potassium hydroxide is added and adjusts pH=12, is stirred to react half
A hour, stratification separate lye and methanol, acetone, and methanol, acetone are recycled by solvent separating technology, lye circulation
Heating kettle is flowed into, 100 DEG C of heating temperature, after being stirred to react half an hour, standing separates water phase, and acidification slot stirring is passed through after filtering
Acidification is added 36% hydrochloric acid and adjusts pH=7, and water phase is passed through oxidizing tower oxidation, and potassium chlorate 40g is added in the inside, carries out oxidation reaction
30min enters reduction kettle later, and sodium sulfite 100g is added, and reacts 30min, has dark precipitate generation to filter to obtain thick iodine,
80 DEG C of heating temperature of heating, cooling later, pure iodine of sublimating to obtain.The rate of recovery 78.2% of iodine after measured, the content 98.1% of iodine.
Claims (6)
1. the recovery method of iodine in a kind of cephalosporins medicine waste liquid, it is characterised in that comprise the steps of:
A, cephalosporins medicine waste liquid is passed through in reaction kettle, alkali extraction and separation is added to go out methanol, acetone and water phase, water phase circulation flows again
It returns in reaction kettle and heats, be filtered to remove insoluble impurity after treatment；
B, after water phase enters the acidification of acidification slot, stir process, stratification removes organic matter not soluble in water.
C, water phase is passed through oxidizing tower to react, liquid enters in tower from tower top sprinkling by water phase I-It is oxidized to IO3 -；
D, water phase is passed through reduction kettle later and reducing agent is added by IO3 -It is reduced to I2Purple red precipitate is generated, by filtering, is added
Heat distils, elemental iodine of sublimating to obtain.
2. the recovery method of iodine in cephalosporins medicine waste liquid according to claim 1, it is characterised in that in step a, alkali is
20%~30% sodium hydroxide or potassium hydroxide solution adjust pH value 12~13, heat 90~120 DEG C of hydrolysis temperature.
3. the recovery method of iodine in cephalosporins medicine waste liquid according to claim 1, it is characterised in that in step b, acidification
PH value is 1~5, is stirred to react 1~3h.
4. the recovery method of iodine in cephalosporins medicine waste liquid according to claim 1, it is characterised in that in step c, oxidation
Agent is potassium chlorate or sodium chlorate, and oxidant and cephalosporins medicine waste liquid mass volume ratio are 20~30g:1L.
5. the recovery method of iodine in cephalosporins medicine waste liquid according to claim 1, it is characterised in that in step d, reduction
Agent is sulfur dioxide or sodium hydrogensulfite, and sodium hydrogensulfite and cephalosporins medicine waste liquid mass volume ratio are 50~100g:1L, two
Sulfur oxide and cephalosporins medicine waste liquid mass volume ratio are 25~50g:1L.
6. the recovery method of iodine in cephalosporins medicine waste liquid according to claim 1, it is characterised in that in step d, filtering,
It heats, distil, sublimating and completed in same device, obtaining thick iodine after filtering removal waste liquid, continuing to heat iodine distillation later to be iodine vapor,
It is cooling that it is passed through condensed water again, so that iodine vapor is sublimated to obtain elemental iodine, heating temperature is 50~100 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551760A (en) * | 2020-12-22 | 2021-03-26 | 上海鲲谷环保科技有限公司 | Method for removing iodine in wastewater |
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|---|---|---|---|---|
| EP0106934A1 (en) * | 1982-08-09 | 1984-05-02 | BRACCO INDUSTRIA CHIMICA Società per Azioni | Process for recovering iodine from mother liquor and waste water containing organic iodides |
| DE19745106C1 (en) * | 1997-10-11 | 1999-03-25 | Degussa | Iodine recovery from aqueous solutions or waste water containing other salts |
| CN102992541A (en) * | 2012-11-23 | 2013-03-27 | 中国水产科学研究院黄海水产研究所 | Method for simultaneously extracting iodine and fucoidin from salted kelp blanching wastewater |
| CN104803503A (en) * | 2015-01-15 | 2015-07-29 | 珠海保税区丽珠合成制药有限公司 | Treatment device of ceftriaxone synthesis pharmaceutical production waste water |
| CN105439089A (en) * | 2016-01-11 | 2016-03-30 | 浙江海洲制药有限公司 | Method for recovering iodine from wastewater in medicine production |
-
2018
- 2018-11-22 CN CN201811395548.5A patent/CN109368594B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0106934A1 (en) * | 1982-08-09 | 1984-05-02 | BRACCO INDUSTRIA CHIMICA Società per Azioni | Process for recovering iodine from mother liquor and waste water containing organic iodides |
| DE19745106C1 (en) * | 1997-10-11 | 1999-03-25 | Degussa | Iodine recovery from aqueous solutions or waste water containing other salts |
| CN102992541A (en) * | 2012-11-23 | 2013-03-27 | 中国水产科学研究院黄海水产研究所 | Method for simultaneously extracting iodine and fucoidin from salted kelp blanching wastewater |
| CN104803503A (en) * | 2015-01-15 | 2015-07-29 | 珠海保税区丽珠合成制药有限公司 | Treatment device of ceftriaxone synthesis pharmaceutical production waste water |
| CN105439089A (en) * | 2016-01-11 | 2016-03-30 | 浙江海洲制药有限公司 | Method for recovering iodine from wastewater in medicine production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551760A (en) * | 2020-12-22 | 2021-03-26 | 上海鲲谷环保科技有限公司 | Method for removing iodine in wastewater |
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