CN102924726A - 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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- CN102924726A CN102924726A CN2012104556116A CN201210455611A CN102924726A CN 102924726 A CN102924726 A CN 102924726A CN 2012104556116 A CN2012104556116 A CN 2012104556116A CN 201210455611 A CN201210455611 A CN 201210455611A CN 102924726 A CN102924726 A CN 102924726A
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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 that from the glue behind the dendrimer encapsulation rhodium nano particle catalysis NBR hydrogenation, reclaims rhodium.
Background technology
Metal nanoparticle has the performances such as light, electricity, 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 centers, and important application is arranged in chemical reaction, but its particle diameter is less, specific surface energy more greatly, very easily reunite.Seek suitable matrix and template and disperse and protect metal nanoparticle, stop the reunion of metal nanoparticle is the important research direction of nanotechnology always.Dendrimer polymkeric substance with highly branched structure can serve as the template that nanoparticle disperses and protects effectively.
Polyamide-amide type polyamidoamine (PAMAM) dendrimer is the hot topic of studying in the dendrimer polymkeric substance, it is to study one of branch-shape polymer type the earliest, as far back as 1985, the people such as Tomalia have just proposed with methyl acrylate and amido Michael addition, and then prepare the dendroid polymeric amide with the method for quadrol ammonia solution, it is except having the above-mentioned general character of dendrimer, dendritic polymer, the advantage that has again many uniquenesses: the structure in its molecule is comparatively perfect, defective seldom, a large amount of tertiary amine groups is contained in the inside of molecule, hapto with complexing of metal ion is provided, there are a large amount of amidos the outside, and outside amido reactivity ratio is inner strong, can not affect by changing outside amido the character of inner amido.
In view of the unique advantage of PAMAM, take PAMAM as template, metal nanoparticle is packaged in the inside of dendritic macromole, can be used as effective catalyst and use.It is the algebraic value of PAMAM that the people such as Gao Qiuming invent a kind of different-phase catalyst Pd-Gn-PAMAM(Gn with hydrogenation reaction of unsaturated hydrocarbon) mesoporous catalyst is used for hydrogenation reaction of unsaturated hydrocarbon, in the hydrogenation reaction of unsaturated hydrocarbons, speed of response can be regulated by changing different catalyzer with selectivity.The different algebraically PAMAM of the employing dendrimers such as Niu Y. H are 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 certain type of selecting to reactant.Chung etc. with the 4th generation daiamid (PAMAM) dendrimer modified of terminal hydroxy group as template, prepared Pd/Rh bimetal nano particles catalyzer, be used for the selective hydrogenation of 1,3-cyclooctadiene and get cyclooctene, 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 rhodium precious metal costliness price and be present in the hydrogenated nitrile-butadiene rubber glue and can certain impact be arranged to its performance, have very important significance so remove rhodium.The recovery document of rhodium catalyst is less in the hydrogenated nitrile-butadiene rubber glue.Mentioned the catalyst removal of hydrogenated nitrile-butadiene rubber in the 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 used methyl alcohol of the method is very large, and operation sequence is loaded down with trivial details; Chinese patent application publication number CN13133441 provides a kind of and has removed rhodium catalyst residual in the hydrogenated butyronitrile glue by the water technological line, in this patent with containing-NH
2With the organic compound of C=S be complexing agent, take carboxylic acid as extraction agent, join in the glue, a metal-organic complex of formation enters in the aqueous solution from the glue of thickness, the rate of recovery of the method can reach more than 98%; Chinese patent CN101704926A discloses a kind of extraction process and has reclaimed rhodium catalyst in the hydrogenated butyronitrile glue, and the method will contain Sn
2+Enveloping agent solution join in the glue, used complexing agent is acidic aqueous solution, under 20 ℃ ~ 110 ℃, remove reaction, the title complex that removes 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%.
In the glue system, the existence of Rh has certain impact to performance and the outward appearance of hydrogenated butyronitrile paracril behind the hydrogenation.
Summary of the invention
The object of the present invention is to provide the recovery method of a kind of Rh, characteristics are under the normal temperature, in the glue behind dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add toluene solution and a certain amount of ionic strength adjustor of a certain amount of mercaptan, vibration, thereby the recovery of realization Rh.
Above and other purpose 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 that from PAMAM encapsulation Rh nano particle catalysis NBR hydrogenation glue, reclaims Rh, at first in the glue system behind dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add excessive salts substances as ionic strength adjustor in the glue system, mercaptan is dissolved in benzene kind solvent, join in the glue system, vibrated 3-5 minute; Mercaptan adds with 1 ~ 200 times Rh mol ratio, and the ionic strength toughener adds with 25 ~ 100 times Rh mol ratio.
Further, the dendrimer that uses be four generation end group be the daiamid type dendrimer PAMAM of amido.The consumption that it is characterized in that 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 the glue of NBR through obtaining after THF dissolving hydrogenation under dendrimer encapsulation rhodium nano particle catalysis obtains.Get upper solution and measure rhodium content in the upper solution.
The present invention can obtain dendrimer, Rh nanoparticle and hydrogenated nitrile-butadiene rubber that structure has no change by adopting the mercaptan extraction method that dendrimer and Rh are reclaimed.Rh nanoparticle homogeneous hydrogenation, segregative advantage when catalyzing N BR hydrogenation of dendrimer encapsulation have finally been realized.
Description of drawings
The ultraviolet-visible light phenogram of PAMAM (b) in the lower aqueous solution after Figure 1 shows that the pure PAMAM aqueous solution (a) and reclaiming.
Embodiment
Detail has been listed among the following embodiment.Following embodiment is be used to further specifying the present invention, rather than 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 joins respectively in the test tube at normal temperatures, vibration, standing demix.Get upper solution and carry out the ultraviolet sign, and carry out structural characterization with high-resolution-ration transmission electric-lens, measure rhodium content in the upper solution; Take off layer solution and carry out the ultraviolet sign, and calculate the rate of recovery of PAMAM.
Rh reclaims in the PAMAM encapsulation Rh nanoparticle
Embodiment 1
General step by above-mentioned recovery, getting 100 times of n-dodecyl mercaptans Rh molar weight in the hydrogenated nitrile-butadiene rubber glue is dissolved in the toluene, 100 times of sodium borohydrides Rh molar weight in the hydrogenated nitrile-butadiene rubber glue is soluble in water, join in the test tube that the 5ml glue is housed, 5min vibrates under the normal temperature, standing demix, PAMAM and the Rh rate of recovery see Table 1.
Comparative Examples 1
By above-mentioned recovery method, do not add n-dodecyl mercaptan, the other the same as in Example 1, emulsion state can't separate.
Comparative Examples 2
By above-mentioned recovery method, do not add sodium borohydride, the other the same as in Example 1, emulsion state can't separate.
Table 1
| Type | Experimental example | The Rh rate of recovery/% |
| 1-1 | Embodiment 1 | 69.6 |
Embodiment 2
Change the n-dodecyl mercaptan among the embodiment 1 into positive hexylmercaptan, ethanethio, the 3min that vibrates under the normal temperature, the other the same as in Example 1 the results are shown in Table 2
［ 0030 ］ 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 among the 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 among the 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 among the embodiment 1 into 25,50,75, the other the same as in Example 1 the results are shown in Table 5.
Table 5
| Type | The 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 |
The embodiments of the invention method not only can reclaim rhodium, the extraction of the PAMAM in the glue can be entered in the water simultaneously, and the PAMAM in the lower floor's solution that obtains and pure PAMAM structure are as broad as long.
Claims (5)
1. dendrimer encapsulates the recovery method of rhodium in the rhodium nano particle catalysis NBR hydrogenation glue, it is characterized in that: at first in the glue system behind dendrimer encapsulation Rh nano particle catalysis NBR hydrogenation, add excessive salts substances as ionic strength adjustor in the glue system, mercaptan is dissolved in benzene kind solvent, join in the glue system, vibrated 3-5 minute; Mercaptan adds with 1 ~ 200 times Rh mol ratio, and the ionic strength toughener adds with 25 ~ 100 times Rh mol ratio.
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 that uses be four generation end group be the daiamid type dendrimer of amido.
4. recovery method according to claim 1, the consumption that it is characterized in that 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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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020020677A1 (en) | 2018-07-23 | 2020-01-30 | Arlanxeo Deutschland Gmbh | Method for producing hydrogenated nitrile rubber and hnbr compositions thereof |
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020020677A1 (en) | 2018-07-23 | 2020-01-30 | Arlanxeo Deutschland Gmbh | Method for producing hydrogenated nitrile rubber and hnbr compositions thereof |
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