CN101767017A - Preparation of carbon-supported palladium alloy hydrogenated catalyst and technical technology of palladium extraction and recovery - Google Patents
Preparation of carbon-supported palladium alloy hydrogenated catalyst and technical technology of palladium extraction and recovery Download PDFInfo
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- CN101767017A CN101767017A CN200910058003A CN200910058003A CN101767017A CN 101767017 A CN101767017 A CN 101767017A CN 200910058003 A CN200910058003 A CN 200910058003A CN 200910058003 A CN200910058003 A CN 200910058003A CN 101767017 A CN101767017 A CN 101767017A
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Abstract
The invention provides preparation of carbon-supported palladium alloy hydrogenated catalyst and technical technology of palladium extraction and recovery. The base metal Ni, Fe or Sn is mixed with palladium and dipped into active carbon, and then reduced by potassium borohydride or sodium borohydride to form an alloy hydrogenation catalyst; the alloy hydrogenation catalyst is used in the process that 2-nitryl-1, 3-propanediol sodium salt is hydrogenated to compose serinol which has high activity and high yield. Palladium is extracted and recovered by thioether toluene or xylene solution. The invention has the advantages of high yield of palladium, high purity of palladium and less pollution to the environment, applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation and the technology that extracts the recovery palladium of carbon-supported palladium alloy hydrogenated catalyst of catalytic hydrogenation, catalyst of the present invention is used for 2-nitro-1, and the synthetic serinol of ammediol sodium salt hydrogenation has tangible high activity and yield.
Background technology
1, the synthetic serinol of 3-dihydroxy nitropropane sodium salt hydrogenation generally adopts Pd/C or Raney's nickel catalyst, DE2742981, the Pd/C catalytic hydrogenation 2-nitro-1 that US4448999 adopts, the ammediol sodium salt synthesizes serinol, its catalyst use amount is big, and the very difficult repeated use of Pd/C, thereby the synthetic cost of serinol is increased greatly.
US6509504 adopts 10%Pd/Al2O3 and 10%Ru/Al2O3 catalyst, adopts fixed bed reactors, hydrogenation 2-nitro-1, and the ammediol sodium salt synthesizes serinol, working pressure 850psig; This process catalyst amount is big, the pressure height, and investment is big.
The carbon-supported palladium alloy hydrogenated catalyst use amount that the present invention synthesizes is few, can recycle, and reaction pressure is low, and palladium reclaims convenient, and is pollution-free, and industrialization is easily gone.
Therefore, the objective of the invention is to: synthetic a kind of at low-voltage hydrogenation 2-nitro-1, the ammediol sodium salt prepares serinol carbon-supported palladium alloy catalyst, and the H2 working pressure is at 1～6kg.Between the catalyst use amount 0.5%～3%.
The base metal that palladium alloy catalysts of the present invention is used is Ni, Fe or Sn, wherein also can be two kinds of metals or three kinds of metals.
The present invention adopts extract and separate to reclaim palladium, and traditional noble metal separates and adopts the aqua regia dissolution noble metal, then selective reduction noble metal progressively; Produce a large amount of waste acid waters in process of production, the discharging large quantity of exhaust gas, along with requirement on environmental protection is more and more stricter, these technologies will progressively be eliminated.The present invention adopts chlorine and dissolving with hydrochloric acid palladium and base metal, and palladium, palladium recovery rate 99.99% are reclaimed in the extraction of thioether extractant then.
Summary of the invention
The technology that the present invention comprised: the base metal that the present invention mixed is Ni, Fe or Sn, wherein also can be two kinds of metals or three kinds of metals, and its use amount is 0.1～10% of an activated carbon, preferential 1～5%; The palladium load capacity is 1～10%, best 3～5%; Wherein Ni, Fe or Sn can be the hydrochlorates that desalts, acetate or nitrate; The alkali that adjusting PH uses can be sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH or potassium hydroxide, and preferably sodium carbonate and NaOH are regulated between PH to 7～10 with alkali.
Reducing agent uses potassium borohydride or sodium borohydride, 0～80 ℃ of reduction temperature, 15～50 ℃ of optimum temperatures.
Catalyst of the present invention is estimated its catalytic hydrogenation activity with hydrogenation 2-nitro-1, the synthetic serinol of ammediol sodium salt.
The palladium of catalyst of the present invention reclaims and adopts Cl2 and hydrochloric acid leaching palladium and base metal wherein, its detailed process is: dead catalyst ignites, slowly burn activated carbon, with 6mol/L hydrochloric acid and Cl2 dissolution of metals, use the palladium in the solution extraction acid mutually of the toluene of thioether or dimethylbenzene at last, the convenient base metal that separates; Palladium recovery rate 99.9%, purity 〉=99.95%.
Specific embodiment
Example 15%Pd2.5%Ni/C Preparation of catalysts
Take by weighing the 10g activated carbon, add 100ml distilled water and stir pulping, will contain 0.5gPd, the mixed aqueous solution of 0.25gNi joins in the activated carbon, stirs; Regulate PH=8.0 with 30% NaOH, slowly add the 0.5g potassium borohydride, 35 ℃ of reduction 1h filter, and the washing catalyst promptly gets the 5%Pd2.5%Ni%/C catalyst to neutral.
With 2-nitro-1, ammediol sodium salt 103.5g (0.5mol) joins 1000ml hydrogenation autoclave, 500ml methyl alcohol, 150ml distilled water, 21g (0.4mol) ammonium chloride, 1g (50% moisture) 5%Pd2.5%Ni%/C catalyst, H2 pressure 6kg, 80 ℃ of reaction 4h, serinol yield 78%.
Example 25%Pd5%Ni/C Preparation of catalysts
Nickel is adjusted to 0.5g, and all the other preparation methods are with example 1, and the catalyst activity evaluation is with example 1.
Example 35%Pd2.5%Fe/C Preparation of catalysts
All the other preparation methods are with example 1, and the catalyst activity evaluation is with example 1.
Example 45%Pd5%Fe/C Preparation of catalysts
All the other preparation methods are with example 1, and the catalyst activity evaluation is with example 1.
Example 55%Pd2.5%Sn/C Preparation of catalysts
All the other preparation methods are with example 1, and the catalyst activity evaluation is with example 1.
Example 65%Pd5%Sn/C Preparation of catalysts
All the other preparation methods are with example 1, and the catalyst activity evaluation is with example 1.
Example 2～6 catalytic hydrogenation result such as following tables
| Catalyst g | H2 pressure kg | Reaction time h | Serinol yield % | |
| Example 2 | ??1 | ??6 | ??4 | ??81 |
| Example 3 | ??1 | ??5 | ??4 | ??74 |
| Example 4 | ??1 | ??5 | ??4 | ??76 |
| Example 5 | ??1 | ??6 | ??4 | ??85 |
| Example 6 | ??1 | ??6 | ??4 | ??80 |
Example 7 is collected example 1 catalyst for reaction, add example 1 fresh catalyst 0.2g, with 2-nitro-1, ammediol sodium salt 103.5g (0.5mol) joins 1000ml hydrogenation autoclave, 500ml methyl alcohol, 150ml distilled water, 21g (0.4mol) ammonium chloride, H2 pressure 6kg, 80 ℃ of reaction 4h, serinol yield 76%.
Example 2 to example 6 catalyst are applied mechanically experimental result such as following table
| Mend catalyst g | H2 pressure kg | Reaction time h | Serinol yield % | |
| Cover example 2 | ??0.2 | ??6 | ??4 | ??82 |
| Mend catalyst g | H2 pressure kg | Reaction time h | Serinol yield % | |
| Cover example 3 | ??0.2 | ??5 | ??4 | ??73 |
| Cover example 4 | ??0.2 | ??5 | ??4 | ??77 |
| Cover example 5 | ??0.2 | ??6 | ??4 | ??83 |
| Cover example 6 | ??0.2 | ??6 | ??4 | ??81 |
The recovery of example 8 inactivation palladium alloy catalysts palladiums
Get 200g pilot scale decaying catalyst, after igniting, can burn by automatic slowly, after treating activated carbon burning fully, with 6mol/L hydrochloric acid and Cl2 dissolution of metals, the elimination insoluble residue steams demineralizing acid, and regulating acidity is the hydrochloric acid solution of 0.1mol/L, di-n-octyl thioether toluene solution aqueous phase extracted with 15%, palladium extraction yield 99.99%; Organic facies ammoniacal liquor back extraction, palladium enters in the ammoniacal liquor, adds hydrazine hydrate reduction and promptly gets palladium, and palladium purity is not less than 99.9%.
Example 9 changes the di-n-octyl thioether into the diisooctyl thioether, and all the other conditions are with example 8, palladium extraction yield 99.99%, palladium purity 〉=99.95%.
Claims (7)
1. the preparation technology of a palladium alloy catalysts is characterized in that Immesion active carbon is regulated between PH to 7～10 with alkali, promptly gets palladium alloy catalysts with the reducing agent reduction then with metal mixed such as the solution of palladous chloride and base metal Ni, Fe, Sn.
2. preparation technology as claimed in claim 1, it is characterized by alkali is sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH or potassium hydroxide.
3. preparation technology as claimed in claim 1, it is characterized by reducing agent is potassium borohydride or sodium borohydride.
4. the palladium alloy catalysts by the described preparation technology's preparation of claim 1 is characterized by palladium alloy catalysts and is used for 2-nitro-1, and the synthetic serinol of ammediol sodium salt hydrogenation has tangible high activity and yield.
5. press the described palladium alloy catalysts of claim 4 for one kind, the palladium that it is characterized by catalyst reclaims with separating of base metal and adopts the organic solvent extraction palladium, and back extraction palladium from organic facies reduces and promptly gets pure palladium then.
6. press the described palladium alloy catalysts of claim 4 for one kind, the solvent that it is characterized by extraction of palladium adopts thio-ether type compounds.
7. press the described palladium alloy catalysts of claim 4 for one kind, it is characterized by thio-ether type compounds is positive dioctyl thioether or diisooctyl thioether.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN102133527A (en) * | 2010-12-23 | 2011-07-27 | 西安凯立化工有限公司 | Palladium tin carbon catalyst for meropenem synthesis and preparation method |
| CN102731324A (en) * | 2012-07-13 | 2012-10-17 | 江西东邦药业有限公司 | Preparation method of serinol by normal-pressure catalytic reduction |
| CN103508905A (en) * | 2012-06-26 | 2014-01-15 | 北京华清润德科技有限公司 | New serinol synthesis technology |
| CN108311145A (en) * | 2017-01-17 | 2018-07-24 | 中国科学院上海高等研究院 | The preparation of palladium on carbon tin nanometer alloy catalyst and its application in carbon dioxide electro-catalysis reduction |
| CN113522275A (en) * | 2021-06-11 | 2021-10-22 | 谷育英 | Palladium-carbon catalyst for preparing disproportionated rosin and preparation method and application thereof |
| CN114308061A (en) * | 2020-09-29 | 2022-04-12 | 中国科学院大连化学物理研究所 | NiAu bimetallic alloy nano catalyst and synthesis and application thereof |
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2009
- 2009-01-04 CN CN200910058003A patent/CN101767017A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN101966455B (en) * | 2010-09-25 | 2012-07-04 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN102133527A (en) * | 2010-12-23 | 2011-07-27 | 西安凯立化工有限公司 | Palladium tin carbon catalyst for meropenem synthesis and preparation method |
| CN103508905A (en) * | 2012-06-26 | 2014-01-15 | 北京华清润德科技有限公司 | New serinol synthesis technology |
| CN103508905B (en) * | 2012-06-26 | 2017-12-12 | 北京华清润德科技有限公司 | A kind of new technology of serinol synthesis |
| CN102731324A (en) * | 2012-07-13 | 2012-10-17 | 江西东邦药业有限公司 | Preparation method of serinol by normal-pressure catalytic reduction |
| CN102731324B (en) * | 2012-07-13 | 2014-06-04 | 江西东邦药业有限公司 | Preparation method of serinol by normal-pressure catalytic reduction |
| CN108311145A (en) * | 2017-01-17 | 2018-07-24 | 中国科学院上海高等研究院 | The preparation of palladium on carbon tin nanometer alloy catalyst and its application in carbon dioxide electro-catalysis reduction |
| CN114308061A (en) * | 2020-09-29 | 2022-04-12 | 中国科学院大连化学物理研究所 | NiAu bimetallic alloy nano catalyst and synthesis and application thereof |
| CN114308061B (en) * | 2020-09-29 | 2023-08-22 | 中国科学院大连化学物理研究所 | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof |
| CN113522275A (en) * | 2021-06-11 | 2021-10-22 | 谷育英 | Palladium-carbon catalyst for preparing disproportionated rosin and preparation method and application thereof |
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