CN102924726B - Method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation - Google Patents
Method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation Download PDFInfo
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- CN102924726B CN102924726B CN201210455611.6A CN201210455611A CN102924726B CN 102924726 B CN102924726 B CN 102924726B CN 201210455611 A CN201210455611 A CN 201210455611A CN 102924726 B CN102924726 B CN 102924726B
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Abstract
The invention relates to a method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation. The method comprises the following steps of: adding excessive salt substances as an ion strength regulating agent in a glue solution system after the PAMAN dendrimer packaged Rh nanoparticle catalytic NBR hydrogenation; dissolving mercaptan to a benzene type solvent and adding to the glue solution system; and oscillating for 3-5 minutes. Mercaptan is added with a mol ratio of mercapton to Rh of 1-200, and an ion strength regulating agent is added with a mol ratio of the ion strength regulating agent to Rh of 25-100. By the method, PAMAN dendrimer and Rh are recycled through a mercaptan extraction method, so that the PAMAN dendrimer, Rh nanoparticles and hydrogenised NBR of which the structures are not changed can be obtained; and the method has the advantages of hydrogenation in homogeneous phase and easiness in separation during the PAMAN dendrimer packaged Rh nanoparticle catalytic NBR hydrogenation.
Description
Technical field
The present invention relates to a kind of method reclaiming rhodium from the glue after dendrimer encapsulation rhodium nano particle catalysis NBR hydrogenation.
Background technology
Metal nanoparticle has optical, electrical, the performance such as magnetic and catalysis of many excellences because of its nano level grain size.Its specific surface area is large, have a lot of catalytic active center, have important application, but its particle diameter is less, specific surface energy is reunited more greatly, very easily in chemical reaction.Find suitable matrix and template is disperseed and protects metal nanoparticle, stop the reunion of metal nanoparticle to be the important research direction of nanotechnology always.The dendrimer polymkeric substance with highly branched structure can serve as the template of nanoparticle dispersion and protection effectively.
Polyamidoamine polyamidoamine (PAMAM) dendrimer is the hot topic studied in dendrimer polymkeric substance, it studies one of branch-shape polymer type the earliest, as far back as 1985, the people such as Tomalia just propose with methyl acrylate and amido Michael addition, and then prepare dendroid polymeric amide by the method for quadrol ammonia solution, it is except having the above-mentioned general character of dendrimer, dendritic polymer, there is again the advantage of many uniquenesses: the structure in its molecule is comparatively perfect, defect is little, a large amount of tertiary amine groups is contained in the inside of molecule, provide the hapto with complexing of metal ion, there is a large amount of amido outside, and the amido reactivity ratio of outside is inner strong, the character of inner amido can not be affected by changing outside amido.
In view of the unique advantage of PAMAM, take PAMAM as template, metal nanoparticle is packaged in the inside of dendritic macromole, can use as effective catalyst.The different-phase catalyst Pd-Gn-PAMAM(Gn that the people such as Gao Qiuming invent a kind of hydrogenation reaction of unsaturated hydrocarbon is the algebraic value of PAMAM) mesoporous catalyst be used for hydrogenation reaction of unsaturated hydrocarbon, in the hydrogenation reaction of unsaturated hydrocarbons, speed of response and selectivity can by changing different catalyzer to regulate.Niu Y. H etc. adopt different algebraically PAMAM dendrimer to be that side chain different enol in template action Pd nanocluster catalyst opposite end carries out hydrogenation, and wherein PAMAM dendrimer template action metallic catalyst has reactant and certain selects type.Daiamid (PAMAM) dendrimer that Chung etc. use forth generation terminal hydroxy group to modify is as template, prepare Pd/Rh bimetal nano particles catalyzer, obtain cyclooctene for the selective hydrogenation of 1,3-cyclooctadiene, transformation efficiency is up to 99%, and the recovery usability of catalyzer is better.This nanoparticle carries out hydrogenation to paracril, has certain hydrogenation activity, can obtain higher degree of hydrogenation.
But consider the price of the costliness of rhodium precious metal and be present in hydrogenated nitrile-butadiene rubber glue and can have a certain impact to its performance, having very important significance so remove rhodium.In hydrogenated nitrile-butadiene rubber glue, the recovery document of rhodium catalyst is less.Be referred to the catalyst removal of hydrogenated nitrile-butadiene rubber in United States Patent (USP) 3700637, the method for this patent is for using methyl alcohol repetitive scrubbing glue, and with Removal of catalyst, until washings takes on a red color, the amount of the method methyl alcohol used is very large, and operation sequence is loaded down with trivial details; Chinese patent application publication number CN13133441 provides and a kind ofly to remove in hydrogenated butyronitrile glue residual rhodium catalyst by aqueous phase technological line, with containing-NH in this patent
2be complexing agent with the organic compound of C=S, be extraction agent with carboxylic acid, join in glue, a metal-organic complex of formation enters in the aqueous solution from the glue of thickness, and the rate of recovery of the method can reach more than 98%; Chinese patent CN101704926A discloses a kind of extraction process and reclaims rhodium catalyst in hydrogenated butyronitrile glue, and the method will containing Sn
2+enveloping agent solution join in glue, complexing agent used is acidic aqueous solution, carry out removing reaction at 20 DEG C ~ 110 DEG C, the title complex removing reaction formation is extracted in the aqueous solution, wherein the mass concentration of enveloping agent solution is 3% ~ 50%, the consumption of enveloping agent solution is 5 ~ 200% of hydrogenated nitrile-butadiene rubber liquor capacity, and the reaction times is 1 ~ 8 hour, and the rate of recovery can reach more than 99%.
After hydrogenation in glue system, the existence of Rh has a certain impact to the performance of hydrogenated butyronitrile paracril and outward appearance.
Summary of the invention
The object of the present invention is to provide the recovery method of a kind of Rh, under feature is normal temperature, in the glue after dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add the toluene solution of a certain amount of mercaptan and a certain amount of ionic strength adjustor, vibration, thus realize the recovery of Rh.
Above and other object of the present invention, feature can be embodied in further elaboration of the present invention.
Method of the present invention comprises the steps:
A kind of method reclaiming Rh from PAMAM encapsulation Rh nano particle catalysis NBR hydrogenation glue, first in the glue system after dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add excessive salts substances as ionic strength adjustor in glue system, mercaptan is dissolved in benzene kind solvent, join in glue system, vibration 3-5 minute; Mercaptan adds with the Rh mol ratio of 1 ~ 200 times, and ionic strength toughener adds with the Rh mol ratio of 25 ~ 100 times.
Further, the dendrimer of use is the four generation end group daiamid type dendrimer PAMAM that are amido.It is characterized in that the consumption of mercaptan is 25 ~ 100 times of Rh mol ratios.
The mercaptan that the present invention uses is n-dodecyl mercaptan, positive hexylmercaptan or ethanethio, and described benzene kind solvent is chlorobenzene, bromobenzene, toluene or dimethylbenzene.
The spendable ionic strength adjustor of the present invention is sodium borohydride, sodium-chlor or calcium chloride.
The hydrogenated nitrile-butadiene rubber glue that the present invention uses is that glue hydrogenation under dendrimer encapsulation rhodium nano particle catalysis that NBR obtains after THF dissolves obtains.Get upper solution and measure rhodium content in upper solution.
The present invention reclaims dendrimer and Rh by adopting mercaptan extraction method, can obtain structure and have no the dendrimer of change, Rh nanoparticle and hydrogenated nitrile-butadiene rubber.Finally achieve Rh nanoparticle homogeneous hydrogenation, segregative advantage when catalyzing N BR hydrogenation of dendrimer encapsulation.
Accompanying drawing explanation
Figure 1 shows that the pure PAMAM aqueous solution (a) and the ultraviolet-visible light phenogram reclaiming PAMAM (b) in rear lower aqueous solution.
Embodiment
Detail has been listed in following embodiment.Following embodiment is for further illustrating the present invention, instead of is used for limiting the scope of the invention.
General step of the present invention:
Get a certain amount of hydrogenated nitrile-butadiene rubber glue and add test tube, then prepare certain density thiol solution, certain density ionic strength toughener, join respectively at normal temperatures in test tube, vibration, stratification.Get upper solution and carry out ultraviolet sign, and carry out structural characterization with high-resolution-ration transmission electric-lens, measure rhodium content in upper solution; Take off layer solution and carry out ultraviolet sign, and calculate the rate of recovery of PAMAM.
PAMAM encapsulates Rh in Rh nanoparticle and reclaims
Embodiment 1
By the general step of above-mentioned recovery, getting 100 times of n-dodecyl mercaptans Rh molar weight in hydrogenated nitrile-butadiene rubber glue is dissolved in toluene, 100 times of sodium borohydrides Rh molar weight in hydrogenated nitrile-butadiene rubber glue is soluble in water, join in the test tube that 5ml glue is housed, vibrate under normal temperature 5min, stratification, PAMAM and the Rh rate of recovery is in table 1.
Comparative example 1
By above-mentioned recovery method, do not add n-dodecyl mercaptan, the other the same as in Example 1, emulsion state, cannot be separated.
Comparative example 2
By above-mentioned recovery method, do not add sodium borohydride, the other the same as in Example 1, emulsion state, cannot be separated.
Table 1
| Type | Experimental example | The Rh rate of recovery/% |
| 1-1 | Embodiment 1 | 69.6 |
Embodiment 2
Change the n-dodecyl mercaptan in embodiment 1 into positive hexylmercaptan, ethanethio, vibrate under normal temperature 3min, and the other the same as in Example 1, the results are shown in Table 2
Table 2
| Type | Extraction agent | The Rh rate of recovery/% |
| 2-1 | Positive hexylmercaptan | 64.1 |
| 2-2 | Ethanethio | 65.4 |
| 2-3 | N-dodecyl mercaptan | 69.6 |
Embodiment 3
Change the sodium borohydride in embodiment 1 into sodium-chlor, calcium chloride, the other the same as in Example 1, the results are shown in Table 3.
Table 3
| Type | Ionic strength adjustor | The Rh rate of recovery/% |
| 3-1 | Sodium-chlor | 48.7 |
| 3-2 | Calcium chloride | 53.5 |
| 3-3 | Sodium borohydride | 69.6 |
Change the consumption of the n-dodecyl mercaptan in embodiment 1 into 25,50,75, the other the same as in Example 1, the results are shown in Table 4.
Table 4
| Type | The consumption of n-dodecyl mercaptan | The Rh rate of recovery/% |
| 4-1 | 25 | 61.4 |
| 4-2 | 50 | 65.8 |
| 4-3 | 75 | 65.2 |
| 4-4 | 100 | 69.6 |
Change the sodium borohydride consumption in embodiment 1 into 25,50,75, the other the same as in Example 1, the results are shown in Table 5.
Table 5
| Type | Sodium borohydride consumption | The Rh rate of recovery/% |
| 5-1 | 25 | 34.7 |
| 5-2 | 50 | 45.4 |
| 5-3 | 75 | 56.8 |
| 5-4 | 100 | 69.6 |
Embodiments of the invention method not only can reclaim rhodium, simultaneously can enter in water by the PAMAM extraction in glue, the PAMAM in the lower floor's solution obtained and pure PAMAM structure as broad as long.
Claims (5)
1. dendrimer encapsulates the recovery method of rhodium in rhodium nano particle catalysis NBR hydrogenation glue, it is characterized in that: in the glue system first after dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add excessive salts substances as ionic strength adjustor in glue system, mercaptan is dissolved in benzene kind solvent, join in glue system, vibration 3-5 minute; Mercaptan adds with the Rh mol ratio of 1 ~ 100 times, and ionic strength toughener adds with the Rh mol ratio of 25 ~ 100 times.
2. recovery method according to claim 1, is characterized in that mercaptan is n-dodecyl mercaptan, positive hexylmercaptan or ethanethio.
3. recovery method according to claim 1, it is characterized in that the dendrimer used be four generation the end group daiamid type dendrimer that is amido.
4. recovery method according to claim 1, is characterized in that the consumption of mercaptan is 25 ~ 100 times of Rh mol ratios.
5. recovery method according to claim 1, is characterized in that ionic strength adjustor is sodium-chlor, calcium chloride or sodium borohydride.
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| CN201210455611.6A CN102924726B (en) | 2012-11-13 | 2012-11-13 | Method for recycling rhodium (Rh) from glue solution of polyamidoamine (PAMAN) dendrimer packaged Rh nanoparticle catalytic NBR (nitrile-butadiene rubber) hydrogenation |
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| CN1313344A (en) * | 2000-03-10 | 2001-09-19 | 南帝化学工业股份有限公司 | Process for removing hydrocatalyst from unsaturated copolymer |
| CN1443784A (en) * | 2002-03-07 | 2003-09-24 | 中国石油天然气股份有限公司 | Method for removing residual rhodium catalyst from hydrogenated nitrile rubber |
| JP2005220435A (en) * | 2003-10-22 | 2005-08-18 | Mitsuboshi Belting Ltd | Method of producing metal nanoparticle and dispersion of metal nanoparticle |
| CN101463097A (en) * | 2007-12-21 | 2009-06-24 | 朗盛德国有限责任公司 | A process for removing iron-residues, rhodium- and ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber |
| CN101690898A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing rhodium complex catalyst from reaction waste solution of olefin carbonylation rhodium catalyst |
| TW201020027A (en) * | 2008-11-18 | 2010-06-01 | Oxea Gmbh | Process for recovering rhodium from aqueous solutions containing rhodium complexes |
| CN102335629A (en) * | 2011-07-21 | 2012-02-01 | 北京化工大学 | Preparation method of rhodium/ruthenium nanoparticle catalyst and application of rhodium/ruthenium nanoparticle catalyst in hydrogenation reaction |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313344A (en) * | 2000-03-10 | 2001-09-19 | 南帝化学工业股份有限公司 | Process for removing hydrocatalyst from unsaturated copolymer |
| CN1443784A (en) * | 2002-03-07 | 2003-09-24 | 中国石油天然气股份有限公司 | Method for removing residual rhodium catalyst from hydrogenated nitrile rubber |
| JP2005220435A (en) * | 2003-10-22 | 2005-08-18 | Mitsuboshi Belting Ltd | Method of producing metal nanoparticle and dispersion of metal nanoparticle |
| CN101463097A (en) * | 2007-12-21 | 2009-06-24 | 朗盛德国有限责任公司 | A process for removing iron-residues, rhodium- and ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber |
| TW201020027A (en) * | 2008-11-18 | 2010-06-01 | Oxea Gmbh | Process for recovering rhodium from aqueous solutions containing rhodium complexes |
| CN101690898A (en) * | 2009-10-21 | 2010-04-07 | 中国海洋石油总公司 | Method for preparing rhodium complex catalyst from reaction waste solution of olefin carbonylation rhodium catalyst |
| CN102335629A (en) * | 2011-07-21 | 2012-02-01 | 北京化工大学 | Preparation method of rhodium/ruthenium nanoparticle catalyst and application of rhodium/ruthenium nanoparticle catalyst in hydrogenation reaction |
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