CN106032294A - Method for treating residual heavy metal ions in organic reaction with dithiocarbamate - Google Patents
Method for treating residual heavy metal ions in organic reaction with dithiocarbamate Download PDFInfo
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- CN106032294A CN106032294A CN201510132011.XA CN201510132011A CN106032294A CN 106032294 A CN106032294 A CN 106032294A CN 201510132011 A CN201510132011 A CN 201510132011A CN 106032294 A CN106032294 A CN 106032294A
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Abstract
The invention provides a method of using a dithiocarbamates (DTCs) heavy metal ion trapping agent for treating residual heavy metal in organic reaction. Solid DTCs are used for chelating heavy metal ions to form insoluble substances, and then the insoluble substances are filtered out. By means of the method, Cu and other heavy metal residuals in the organic reaction is smaller than 15 ppm. The method has the advantages that the heavy metal ion trapping agent is low in toxicity, convenient, easy to obtain and operate, good in effect, high in stability, wide in application range and capable of being applied to industrial production.
Description
One, technical field:
The invention belongs to heavy metal ion agent for capturing technical field, relate to the heavy metal chelant in multiclass heavy-metal residual organic reaction, particularly relate to scorching (DTCs) the heavy metal ion agent for capturing of dithiocar-bamate and process Liv Ullmann coupling reaction, Heck coupling reaction, Sonogashira coupling reaction, the application of the kish catalyst in the organic reactions such as Rh catalytic hydrogen reduction reacts, DABALH reduction reaction.
Two, background technology:
Along with controlling gold, plating, medicine, pesticide, paint, the development of the industrial technologies such as pigment, cadmium, nickel, copper, zinc, chromium, lead, hydrargyrum, gold, silver, ferrum, the heavy metal ion such as aluminum is polluted day by day serious, is the most effectively administered heavy metal pollution and caused the attention of people.
The processing method of traditional effluent containing heavy metal ions mainly has: neutralize flocculent precipitation, sulphide precipitation, oxidation-reduction method, ion exchange etc..But because the concentration difference of effluent containing heavy metal ions is relatively big, comparison of ingredients is complicated, processing requirement up to standard very strict, the heavy metal ion agent for capturing consumption needed for traditional processing method is big, expensive, reacts slow and wayward.
Containing important coordination atom in DTCs organic molecule: N and S, its distributing position, substituted radical kind (alkyl or aromatic radical), the position of other heteroatomic existence and substituent group all can affect the removal effect of heavy metal ion.DTCs agent for capturing all has the strongest adhesion to different heavy metal ion, and post-processing approach simple (directly can throw on former chemical precipitation device), expense is low, can accomplish that contents of many kinds of heavy metal ion disposably processes in the case of coexisting, and the salt that coexists heavy metal ions in wastewater also can play one's part to the full with complex salt, and it is thick to have floccule body, precipitation is fast, and dehydration is fast, and post processing is easy, sludge quantity is few and stablizes nontoxic, does not has the features such as secondary public hazards.The type agent for capturing processes the transition metal ionss such as the Cu, Pb in industrial wastewater and has good effect, can reach ppb rank.
In organic reaction, needed for the restriction of reaction condition and protection reaction intermediate and product, the method for the heavy metal ion of residual in organic reaction that processes mainly has: pH value regulation method and oxidation-reduction method.Reactant liquor regulation need to be beneficial to precipitation of heavy metals ion to alkalescence by the former, but is not suitable for acid product；The latter the most likely destroys product.
In view of DCTs good result in the treatment of waste water, DCTs is extended to process the residual heavy metal in organic reaction by the present invention, and the method can reach≤15ppm for the Cu and other heavy metals removing residual in medicine.Such heavy metal ion agent for capturing toxicity is low, is conveniently easy to get, easy and simple to handle, and excellent effect and good stability are applied widely, can be applicable to industrialized production.
Three, summary of the invention:
It is an object of the invention to provide a class heavy metal ion and there is dithiocarbamates (DTCs) the heavy metal ion agent for capturing of excellent chelating ability, and applied in organic reaction, additionally provide the technique processing heavy metal ion simultaneously.
The technique remaining heavy metal ion in the present invention in DTCs heavy metal ion agent for capturing removal organic reaction is:
A. in the organic reaction containing heavy metal ion, DTCs is added；
The most continuously stirred；
Filter with the filter cloth of kieselguhr, 1 μm the most successively.
The DTCs heavy metal ion agent for capturing of the present invention is applied to organic reaction and has a characteristic that
1, the type of DTCs heavy metal ion agent for capturing includes but not limited to NaDEDTC, NaDMDTC, APDTC.
2, the organic reaction type of DTCs heavy metal ion agent for capturing application includes but not limited to Liv Ullmann coupling reaction, Heck coupling reaction, Sonogashira coupling reaction, and Rh catalytic hydrogen reduction reacts, DABALH reduction reaction.
3, the input amount of DTCs heavy metal ion agent for capturing is 0.5-10eq.
4, the temperature of stirring is 10-80 DEG C, and mixing time is 0.5-20h.
5, the heavy metal ion that DTCs heavy metal ion agent for capturing can be removed includes being not limited to Pd, Cu, Al, Fe, Ni, Rh, Ru.
6, DTCs heavy metal ion agent for capturing can remove two or more different heavy metal ion in the reaction of Rh catalytic hydrogen reduction and Sonogashira coupling reaction simultaneously.
7, the heavy metal ion result that the application organic reaction of DTCs heavy metal ion agent for capturing is removed: Pd, Cu, Al, Fe, Ni, Ru≤15ppm；Rh≤20ppm, Fe≤10ppm during Rh catalytic hydrogen reduction；DABALH reduction reaction Al≤20ppm.
8, the technique of the present invention is simple, easy to operate, low cost, it is easy to industrialization.
Below by description of test metal ion capturing agent to experimental scale, response type, the removal effect of heavy metal ion type
1.DCTs class heavy metal ion agent for capturing is to Cu in the ullmann reaction of different tests specification2+Removal effect.
At 5g, after the ullmann reaction of 120g, 25kg, 100kg, 170kg5 kind experiment specification terminates, adding APDTC metal ion capturing agent, stir 1-10h at 10-80 DEG C, kieselguhr filters, and the filter cloth of 1 μm tests Cu in organic solution after filtering2+Content.
2.APDTC heavy metal ion agent for capturing is to removal of heavy metal ions effects different in differential responses
Adding after different metal ion catalyst catalytic reactions terminates in organic reaction, add APDTC metal ion capturing agent, stir 1-10h at 10-80 DEG C, kieselguhr filters, and the filter cloth of 1 μm tests corresponding metal ion content in organic solution after filtering.
3.NaDEDTC heavy metal ion agent for capturing is to differential responses difference removal of heavy metal ions effect
Adding after different metal ion catalyst catalytic reactions terminates in organic reaction, add NaDEDTC metal ion capturing agent, stir 1-10h at 10-80 DEG C, kieselguhr filters, and the filter cloth of 1 μm tests corresponding metal ion content in organic solution after filtering.
4.APDTC heavy metal ion agent for capturing removes two heavy metal species ion remaval effects simultaneously
After Sonogashira coupling reaction terminates, adding APDTC metal ion capturing agent, stir 1-10h at 10-80 DEG C, kieselguhr filters, and the filter cloth of 1 μm tests Cu in organic solution after filtering2+, Pd2+Content.
After the reaction of Rh catalytic hydrogen reduction terminates, adding APDTC metal ion capturing agent, stir at 10-80 DEG C, kieselguhr filters, and the filter cloth of 1 μm tests Rh in organic solution after filtering2+, Fe2+Content.
Four, accompanying drawing explanation:
Fig. 1 DCTs class heavy metal ion agent for capturing is to Cu in the ullmann reaction of different tests specification2+Removal effect.
Fig. 2 APDTC class heavy metal ion agent for capturing is to differential responses difference removal of heavy metal ions effect
Fig. 3 NaDEDTC class heavy metal ion agent for capturing is to differential responses difference removal of heavy metal ions effect
Fig. 4 (a) APDTC heavy metal ion agent for capturing removes two heavy metal species ion remaval effects in Sonogashira coupling reaction simultaneously
Fig. 4 (b) APDTC heavy metal ion agent for capturing removes two heavy metal species ion remaval effects in the reaction of Rh catalytic hydrogen reduction simultaneously
Five, detailed description of the invention:
It is embodied as case one: to methyl bromobenzene (1mmol), Mg (48mg), MnCl2(0.1mmol, 12.6mg), Br2(1mmol), THF (4ml) joins in the dry three-necked bottle of 10ml, substitutes gas 3 times.24h is stirred at room temperature, adds saturated sodium bicarbonate (4ml) cancellation reaction.Disposable addition APDTC and H2O, after 10-80 DEG C of continuously stirred 1-10h, with Mn content in the filter filter mixed liquor post analysis solution of 1 μm.
It is embodied as case two: methacrylic acid (42mg, 0.25mmol), propylene bromide (121mg, 1mmol), CuCl2(28mg, 0.2mmol), Mg (110mg, 2mmol), THF (2ml), H2O (2ml) is at N2, the continuously stirred 16h of room temperature, add HCl (1M, 10mL) cancellation reaction.Disposable addition APDTC and H2O, after 10-80 DEG C of continuously stirred 1-10h, with Cu content in the filter filter mixed liquor post analysis solution of 1 μm.
It is embodied as case three: benzyl alcohol (0.5g), H2O (10mL), V2O5(0.05eq), H2O2(30%, 1.2-2.8eq), the mixed liquor of BTEAB (0.05eq), H2SO4The PH regulating this mixed liquor is about 4.0, is heated to reflux 3h, is cooled to room temperature, adds NaOH (20%, 5mL) cancellation reaction.Disposable addition APDTC and H2O, after 10-80 DEG C of continuously stirred 1-10h, with V content in the filter filter mixed liquor post analysis solution of 1 μm.
It is embodied as case four: β-bromonaphthalene (5mmol), CoCl2(5mol%), Mg (6mmol), anhydrous THF (10mL), after continuous heating is stirred at reflux 4h.Disposable addition APDTC and H2O, after 10-80 DEG C of continuously stirred 1-10h, with Co content in the filter filter mixed liquor post analysis solution of 1 μm.
It is embodied as case five: autoclave adds Rh (COD)2BF4(61mg, 0.15mmol), Josiphos (108mg, 0.20mmol), industry cyclohexyl-formamido methyl acetate (10.00mmol) and MeOH (50mL), pour N in reactor2And substitute gas 3 times, pour H2(40Psi), at 20 DEG C of continuously stirred 10h, stopped reaction, H is got rid of2.It is transferred in three-necked bottle, disposable addition APDTC and H2O, after 10-80 DEG C of continuously stirred 1-10h, with Rh and Fe content in the filter filter mixed liquor post analysis solution of 1 μm.
Claims (8)
1. residual heavy metal ion technique during dithiocarbamates (DTCs) heavy metal ion agent for capturing removes organic reaction:
A. in the organic reaction containing heavy metal ion, DTCs is added；
The most continuously stirred；
Filter with the filter cloth of kieselguhr, 1 μm the most successively.
2. the type of the DTCs heavy metal ion agent for capturing used as described in right 1 requires includes but not limited to NaDEDTC (sodium diethyldithiocarbamate), NaDMDTC (SDD), APDTC (APDC).
3. the organic reaction type of DTCs heavy metal ion agent for capturing application as described in right 1 requires includes but not limited to a Liv Ullmann coupling reaction, Heck coupling reaction, Sonogashira coupling reaction, and Rh catalytic hydrogen reduction reacts, DABALH reduction reaction.
4. the input amount of the DTCs heavy metal ion agent for capturing used as described in right 1 requires is 0.5-10eq.
5. the temperature of stirring as described in right 1 requires is 10-80 DEG C, and mixing time is 0.5-20h.
6. the heavy metal ion that DTCs heavy metal ion agent for capturing as described in right 1 requires can be removed includes being not limited to a Pd, Cu, Al, Fe, Ni, Rh, Ru.
7. a DTCs heavy metal ion agent for capturing as described in right 1 requires can remove two or more different heavy metal ion in the reaction of Rh catalytic hydrogen reduction and Sonogashira coupling reaction simultaneously.
8. the heavy metal ion result that DTCs heavy metal ion agent for capturing application organic reaction as described in right 1 requires is removed a: Pd, Cu, Al, Fe, Ni, Ru≤15ppm；Rh≤20ppm, Fe≤10ppm during Rh catalytic hydrogen reduction；DABALH reduction reaction Al≤20.
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Citations (7)
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| JP2003053343A (en) * | 2001-08-22 | 2003-02-25 | Kurita Water Ind Ltd | Method for treating waste water on decontamination or demolishing of incineration furnace facility for waste |
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| CN102627346A (en) * | 2011-02-04 | 2012-08-08 | 栗田工业株式会社 | Adding control method of heavy metal trapping agent |
| CN103466775A (en) * | 2013-09-27 | 2013-12-25 | 广西博世科环保科技股份有限公司 | Method for preparing heavy metal ion catching agent |
| CN104192968A (en) * | 2014-08-28 | 2014-12-10 | 中山市宏科化工有限公司 | Hyperbranched heavy metal capturing agent and preparation method thereof |
| CN104229757A (en) * | 2014-09-24 | 2014-12-24 | 云南驰宏锌锗股份有限公司 | Method for purifying waste acid and returning purified waste acid to flow for recycling |
| CN104370389A (en) * | 2014-11-14 | 2015-02-25 | 无锡伊佩克科技有限公司 | Process for removing fluorine in pickling waste liquid in steel and iron industry |
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2015
- 2015-03-19 CN CN201510132011.XA patent/CN106032294A/en active Pending
Patent Citations (7)
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|---|---|---|---|---|
| JP2003053343A (en) * | 2001-08-22 | 2003-02-25 | Kurita Water Ind Ltd | Method for treating waste water on decontamination or demolishing of incineration furnace facility for waste |
| CN101314493A (en) * | 2007-05-29 | 2008-12-03 | 陈德琪 | Method and equipment for treatment and high grade reutilization of heavy metal ion containing wastewater |
| CN102627346A (en) * | 2011-02-04 | 2012-08-08 | 栗田工业株式会社 | Adding control method of heavy metal trapping agent |
| CN103466775A (en) * | 2013-09-27 | 2013-12-25 | 广西博世科环保科技股份有限公司 | Method for preparing heavy metal ion catching agent |
| CN104192968A (en) * | 2014-08-28 | 2014-12-10 | 中山市宏科化工有限公司 | Hyperbranched heavy metal capturing agent and preparation method thereof |
| CN104229757A (en) * | 2014-09-24 | 2014-12-24 | 云南驰宏锌锗股份有限公司 | Method for purifying waste acid and returning purified waste acid to flow for recycling |
| CN104370389A (en) * | 2014-11-14 | 2015-02-25 | 无锡伊佩克科技有限公司 | Process for removing fluorine in pickling waste liquid in steel and iron industry |
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