CN104610369A - Purifying method for acetylacetonatodicarbonyl rhodium - Google Patents
Purifying method for acetylacetonatodicarbonyl rhodium Download PDFInfo
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- CN104610369A CN104610369A CN201410637499.7A CN201410637499A CN104610369A CN 104610369 A CN104610369 A CN 104610369A CN 201410637499 A CN201410637499 A CN 201410637499A CN 104610369 A CN104610369 A CN 104610369A
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- rhodium
- silver nitrate
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- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims description 22
- 229910052703 rhodium Inorganic materials 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 241000370738 Chlorion Species 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- CPRFTFJQMGHRRM-UHFFFAOYSA-N carbon monoxide;pentane-2,4-dione;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].CC(=O)CC(C)=O CPRFTFJQMGHRRM-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001175 calcium sulphate Substances 0.000 claims description 2
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 230000002779 inactivation Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002516 radical scavenger Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a purifying method for acetylacetonatodicarbonyl rhodium. The method comprises the following concrete steps: (1) adding deionized water into a crude acetylacetonatodicarbonyl rhodium product, carrying out full stirring, then carrying out standing, dropwise adding a silver nitrate solution until supernatant is no longer turbid, then replenishing a certain amount of the silver nitrate solution, carrying out stirring and filtering, and washing the obtained filter cake with water; and (2) adding the filter cake into an appropriate organic solvent, adding a moisture scavenger under stirring, carrying out filtering, and treating the obtained filtrate in the manners like concentrating crystallization or cooling crystallization so as to obtain solid acetylacetonatodicarbonyl rhodium, or using the obtained filtrate as a further reaction solution for the preparation of acetylacetonatocarbonyltriphenylp hosphinerhodium. The method provided by the invention omits the step of drying in conventional preparation of acetylacetonatodicarbonyl rhodium; under the condition of no additional operation process, the problem of inactivation of an acetylacetonatodicarbonyl rhodium catalyst in hydroformylation reaction due to susceptibility to affection by chloride ions can be conveniently, quickly and effectively overcome; meanwhile, the method is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of method of purified hydrogen formylation reaction catalyst acetyl acetone dicarbonyl rhodium, belong to chemical field.
Background technology
Hydroformylation reaction refers to alkene and CO and H
2the reaction of aldehyde is generated under the effect of catalyzer.Because aldehyde and derived product thereof produce the starting raw material of the high added value fine chemicals such as various washing composition, tensio-active agent, medicine and spices; hydroformylation reaction has become one of most important industrial homogeneous catalytic reaction at present, and the aldehyde that the whole world is produced by hydroformylation reaction every year, the amount of alcohol are more than 1,000 ten thousand tons.
(chemical formula is Rh (C to rhodium dicarbonyl acetylacetonate
5h
7o
2) (CO)
2) be the important catalyged precursor compound of catalysis hydroformylation reaction.Such as; under excessive triphenylphosphine exists; rhodium dicarbonyl acetylacetonate catalyzing propone hydroformylation can generate important industrial chemicals butyraldehyde-n; this reaction believes the joint development success of company of Wan Feng company three by U.S. combinating carbide company and Dai Wei electric corporation of Britain and the village, and the relevant enterprise of current domestic production butyraldehyde-n substantially all adopts this to react.In addition, at present under study for action alkene asymmetric hydroformylation reaction be nearly all use rhodium dicarbonyl acetylacetonate as catalyged precursor compound.Therefore, rhodium dicarbonyl acetylacetonate occupies very important status in rhodium homogeneous catalyst.
The preparation method of rhodium dicarbonyl acetylacetonate is reported in 1964 by Englishize scholar Wilkinson the earliest, but the raw material [Rh (CO) of his employing
2cl]
2need to use the CO of severe toxicity and rhodium trichloride hydrate to react to obtain, overall yield is not high.Russianization scholar Varshavsky improves the synthetic method of rhodium dicarbonyl acetylacetonate subsequently, rhodium trichloride hydrate joins in dimethyl formamide by he, methyl ethyl diketone back flow reaction is added again after being heated to backflow, then cooled by reaction solution, the deionized water adding several times volume separates out red rhodium dicarbonyl acetylacetonate.The method is that namely raw material synthesizes target product by means of only single step reaction with rhodium trichloride hydrate, and yield significantly improves; In addition, reaction does not need to use the CO of severe toxicity as carbonyl source, the carbonyl source that to be solvent be also in target product of the dimethyl formamide in reaction system.Therefore, compare the synthetic method of Wilkinson, it has significant advantage.Since announcement, the method becomes the main method preparing rhodium dicarbonyl acetylacetonate gradually.
Although the synthetic method of rhodium dicarbonyl acetylacetonate has had very much progress in nearly decades; but synthetic methods all is at present all for raw material with the muriate of rhodium; chlorion is just inevitably brought in final product by this; even if repeatedly recrystallization is also difficult to chlorion to remove, and chlorion is the toxicant of catalyzer in hydroformylation reaction.Research shows, chlorion and chloride organic solvent all can react with rhodium catalyst and cause the permanent poisoning and deactivation of rhodium catalyst (Xia Yunju in catalyst system, Liu Jinyao, Liu Dianqiu, the see chlorine of complex catalysis propene hydroformylation reaction of rhodium causes inactivation and study mechanism thereof, gas chemical industry's (C1 chemistry and chemical industry), (4), 10-20,1984; Liu Jinyao, Xia Yunju, Yuan Wei, etc. rhodium phosphine complex catalyst deactivation mechanism is studied, Journal of Molecular Catalysis, 1 (2), 101-107,1987).Therefore, controlling its chloride ion content when preparing rhodium dicarbonyl acetylacetonate is also the matter of utmost importance that will solve.
Method conventional is at present that rhodium dicarbonyl acetylacetonate is further converted to acetylacetonatodicarrhodium rhodium again, chloride ion content can be reduced to enough low level (below 100ppm) by this, but also make the preparation flow of catalyzer extend, add preparation difficulty and Financial cost.
CN 103709201A discloses a kind of preparation method of rhodium dicarbonyl acetylacetonate, first Trichlororhodium and alkali reaction are produced rhodium hydroxide and are precipitated by the method, then wash with water and be precipitated to chloride ion content lower than 1000ppm, then prepare rhodium dicarbonyl acetylacetonate according to the synthetic method of Varshavsky.Chlorion can be reduced to below 100ppm by the method effectively, but the rhodium hydroxide in the method is very easy to wear filter in filtration, washing process, chlorion is washed till below 1000ppm very difficult, in addition, this step increased will also can increase cost and affect total yield, therefore, the method is unfavorable for suitability for industrialized production.
Summary of the invention
The object of the invention is to solve rhodium dicarbonyl acetylacetonate catalyzer in hydroformylation reaction, be subject to chlorion impact and the problem of inactivation; a kind of method of effective purifying acetylacetone dicarbonyl rhodium is provided; chloride ion content can be reduced to below 50ppm convenient and simple, effective and rapidly; additionally can not increase Financial cost, suitability for industrialized is produced simultaneously.
Method of purification of the present invention, is characterized in that comprising:
(1) rhodium dicarbonyl acetylacetonate crude product is added deionized water fully to stir, leave standstill, after dropping silver nitrate solution to supernatant liquor no longer produces muddiness, then add a certain amount of silver nitrate solution, stir, filter, wash filter cake with water;
(2) filter cake is joined in suitable organic solvent, under agitation add water-removal agent, filter, the mode process that filtrate can be familiar with according to those skilled in the art obtains rhodium dicarbonyl acetylacetonate solid, also can prepare acetylacetonatodicarrhodium rhodium as the solution of reaction further.
Method of purification more specifically of the present invention, is characterized in that comprising:
(1) by rhodium dicarbonyl acetylacetonate crude product, add the deionized water of its quality 1 ~ 3 times, abundant stirring, leave standstill, start after precipitation (or floating), after dropping silver nitrate solution to supernatant liquor no longer produces muddiness until rhodium dicarbonyl acetylacetonate, add the silver nitrate solution of dripping quantity 10% ~ 50% again, abundant stirring, filters, removes dried up washing leaching cake 2 ~ 3 times by its quality 1 ~ 3 times;
(2) filter cake is joined in suitable organic solvent, under agitation add suitable water-removal agent, 10% ~ 50% of addition is added again after no longer luming to water-removal agent, the consumption that situation controls solvent is dissolved according to it, also solubleness can be improved by heating, filter, filter cake organic solvent washing 1 ~ 2 time, be incorporated in filtrate, filtrate the process of the mode such as condensing crystal or decrease temperature crystalline can obtain rhodium dicarbonyl acetylacetonate solid, also can be used as the solution of reaction further to prepare acetylacetonatodicarrhodium rhodium.
The present invention's silver nitrate solution used can prepare proper concn according to actual needs.
One or several arbitrary combination can dissolved in the solvent of rhodium dicarbonyl acetylacetonate that the present invention's organic solvent used can be familiar with for those skilled in the art such as benzene, toluene, Skellysolve A, normal hexane, normal heptane, pentamethylene, hexanaphthene, suberane.
The present invention's water-removal agent used can be one or several arbitrary combination in the water-removal agents such as anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, anhydrous magnesium sulfate, anhydrous sodium sulphate, anhydrous calciumsulphate.
Preferred the present invention silver nitrate solution concentration used is 0.5% ~ 5%.
Preferred the present invention organic solvent used is one or several arbitrary combination in Skellysolve A, normal hexane, normal heptane, pentamethylene, hexanaphthene, suberane.
Preferred the present invention water-removal agent used can be one or several arbitrary combination in anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium hydroxide, potassium hydroxide.
Feature of the present invention first precipitates the chlorion in rhodium dicarbonyl acetylacetonate crude product with excessive Silver Nitrate, then by the silver that washing removing is excessive, finally adds water-removal agent and remove moisture on the one hand, remove remaining Trace Silver on the other hand.Not only by routine, the drying step prepared in rhodium dicarbonyl acetylacetonate saves the method, and additionally do not increase operating process and just can remove chlorion in rhodium dicarbonyl acetylacetonate, can convenient, fast, effectively chloride ion content is reduced to below 50ppm, silver ion content is less than 5ppm, additionally can not increase Financial cost, suitability for industrialized is produced simultaneously.
The rhodium dicarbonyl acetylacetonate that the present invention purifies, mainly for the red crude product that Varshavsky synthetic method obtains, adopts Wilkinson method to synthesize the green crude product obtained in organic solvent in principle and is suitable for too.
Embodiment
Embodiment 1
Take 50.0 grams of rhodium trichloride hydrates (rhodium content is 38.2%), join in 1 liter of dimethyl formamide, stir after 10 minutes, slowly be heated to backflow, continue back flow reaction after adding 100 milliliters of methyl ethyl diketones 1 hour, be cooled to room temperature, add 5 liters of deionized waters, filter, use 200ml water washing, obtain red rhodium dicarbonyl acetylacetonate crude product.
By above-mentioned rhodium dicarbonyl acetylacetonate crude product, add 100ml deionized water, abundant stirring, leave standstill, start after precipitation (part float) until rhodium dicarbonyl acetylacetonate, drip mass concentration be 0.5% silver nitrate solution to supernatant liquor no longer produce muddiness after, add 10% of dripping quantity again, abundant stirring, filters, with 200ml deionized water wash 2 times.
Filter cake joins in 1.5 liters of normal hexanes, adds anhydrous sodium carbonate, add 50% of addition after no longer luming to sodium carbonate again under constantly stirring, reflux is all dissolved to rhodium dicarbonyl acetylacetonate, filtered while hot, filter cake 100 milliliters of hot n-hexane 2 times, are incorporated in filtrate, cool after filtrate reduced in volume to 1/3 volume, filter, with the washing of 50ml cold methanol, dry, obtain 44.8 grams of green rhodium dicarbonyl acetylacetonate solids, productive rate 93%.
Cl content after measured in rhodium dicarbonyl acetylacetonate is 45ppm, and silver content is less than 5ppm.
Feature structure parameter: <1> ultimate analysis: measured value C 32.4%, H 2.6%, Rh 39.7% is consistent with theoretical value C 32.58%, H2.73%, Rh 39.88%; <2>
1h NMR (CDCl
3, 500MHz): 2.04 (6H, 2CH
3), 5.58 (1H, CH).<3>
13C NMR(CDCl
3,100MHz):26.9(CH
3),101.7(CH),183.8(C＝O),187.4(s,C≡O)。<4>IR(cm
-1,KBr):ν
C≡O:1984(w),2086(s),2013(s)；ν
C＝O:1558(s),1524(s),1379(s),1361(s)。
Comparative example 1
Take 50.0 grams of rhodium trichloride hydrates (rhodium content is 38.2%), except not dripping except Silver Nitrate, all the other operate according to embodiment 1 completely, obtain 44.7 grams of green rhodium dicarbonyl acetylacetonate solids, productive rate 93%.
Cl content after measured in rhodium dicarbonyl acetylacetonate is 1600ppm.
Embodiment 2
Take 100.0 grams of rhodium trichloride hydrates (rhodium content is 38.2%), join in 2 liters of dimethyl formamides, stir after 10 minutes, slowly be heated to backflow, continue back flow reaction after adding 200ml methyl ethyl diketone 1 hour, be cooled to room temperature, add 10 liters of deionized waters, filter, use 200ml water washing, obtain red rhodium dicarbonyl acetylacetonate crude product.
By above-mentioned rhodium dicarbonyl acetylacetonate crude product, add 200ml deionized water, abundant stirring, leave standstill, start after precipitation (part float) until rhodium dicarbonyl acetylacetonate, drip mass concentration be 2% silver nitrate solution to supernatant liquor no longer produce muddiness after, add 30% of dripping quantity again, abundant stirring, filters, with 200ml deionized water wash 2 times.
Filter cake joins in 4 liters of hexanaphthenes, adds Anhydrous potassium carbonate, add 30% of addition after no longer luming to salt of wormwood again under constantly stirring, reflux is all dissolved to rhodium dicarbonyl acetylacetonate, filtered while hot, the hot hexanaphthene of filter cake 500ml washs 2 times, is incorporated in filtrate, cool after filtrate reduced in volume to 1/3 volume, filter, with the washing of 100ml cold methanol, dry, obtain 90.7 grams of green rhodium dicarbonyl acetylacetonate solids, productive rate 94%.
Cl content after measured in rhodium dicarbonyl acetylacetonate is 32ppm, and silver content is less than 5ppm.
Feature structure parameter: <1> ultimate analysis: measured value C 32.5%, H 2.7%, Rh 39.6% is consistent with theoretical value C 32.58%, H2.73%, Rh 39.88%.
Embodiment 3
Take 50.0 grams of rhodium trichloride hydrates (rhodium content is 38.2%), join in 1 liter of dimethyl formamide, stir after 10 minutes, slowly be heated to backflow, continue back flow reaction after adding 100 milliliters of methyl ethyl diketones 1 hour, be cooled to room temperature, add 5 liters of deionized waters, filter, use 200ml water washing, obtain red rhodium dicarbonyl acetylacetonate crude product.
By above-mentioned rhodium dicarbonyl acetylacetonate crude product, add 100ml deionized water, abundant stirring, leave standstill, start after precipitation (part float) until rhodium dicarbonyl acetylacetonate, drip mass concentration be 1% silver nitrate solution to supernatant liquor no longer produce muddiness after, add 50% of dripping quantity again, abundant stirring, filters, with 200ml deionized water wash 2 times.
Filter cake joins in 1.5 liters of normal hexanes, adds anhydrous sodium carbonate, add 10% of addition after no longer luming to sodium carbonate again under constantly stirring, reflux is all dissolved to rhodium dicarbonyl acetylacetonate, filtered while hot, filter cake 200 milliliters of hot n-hexane 2 times, are incorporated in filtrate.
Above-mentioned filtrate and washing lotion under reflux conditions slowly add the solution that 50.0 grams of triphenylphosphines are dissolved in normal hexane, stirring reaction continues reaction 10 minutes after no longer including bubble formation, be cooled to room temperature, filter, dry, obtain 84.1 grams of yellow acetylacetonatodicarrhodium rhodiums, productive rate is calculated as 92% with rhodium trichloride hydrate.
Cl content after measured in acetylacetonatodicarrhodium rhodium is 16ppm, and silver does not detect.
Feature structure parameter: <1> ultimate analysis: measured value C58.2%, H 4.3%, Rh 20.5% is consistent with theoretical value C 58.55%, H4.50%, Rh 20.90%; <2>
1h NMR (CDCl
3, 500MHz): 1.60 (3H, CH
3) 2.10 (3H, CH
3), 5.44 (1H, CH), 7.37-7.70 (15H, Ph-H).<3>IR(cm
-1,KBr):ν
C≡O:1982(s)；ν
C＝O:1568(s),1385(s)。
Claims (5)
1. a method for purifying acetylacetone dicarbonyl rhodium, is characterized in that comprising following two steps:
(1) by rhodium dicarbonyl acetylacetonate crude product, add the deionized water of its quality 1 ~ 3 times, abundant stirring, leave standstill, start after precipitation (or floating), after dropping silver nitrate solution to supernatant liquor no longer produces muddiness until rhodium dicarbonyl acetylacetonate, add the silver nitrate solution of dripping quantity 10% ~ 50% again, abundant stirring, filters, removes dried up washing leaching cake 2 ~ 3 times by its quality 1 ~ 3 times;
(2) filter cake is joined in suitable organic solvent, under agitation add suitable water-removal agent, 10% ~ 50% of addition is added again after no longer luming to water-removal agent, the consumption that situation controls solvent is dissolved according to it, also solubleness can be improved by heating, filter, filter cake organic solvent washing 1 ~ 2 time, be incorporated in filtrate, filtrate the process of the mode such as condensing crystal or decrease temperature crystalline can obtain rhodium dicarbonyl acetylacetonate solid, also can be used as the solution of reaction further to prepare acetylacetonatodicarrhodium rhodium.
2. the method for purifying acetylacetone dicarbonyl rhodium according to claim 1, it is characterized in that: the silver nitrate solution described in step (1) can prepare proper concn according to actual needs, the present invention's silver nitrate solution concentration used is 0.5% ~ 5%.
3. the method for purifying acetylacetone dicarbonyl rhodium according to claim 1, is characterized in that: the water-removal agent described in step (2) can for one or several arbitrary combination in the water-removal agents such as anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, anhydrous magnesium sulfate, anhydrous sodium sulphate, anhydrous calciumsulphate.
4. the method for purifying acetylacetone dicarbonyl rhodium according to claim 1, is characterized in that: the organic solvent described in step (2) is one or several arbitrary combination in benzene, toluene, Skellysolve A, normal hexane, normal heptane, pentamethylene, hexanaphthene, suberane solvent.
5. the method for purifying acetylacetone dicarbonyl rhodium according to claim 1, is characterized in that: after adopting chlorion residual in Silver Nitrate removing rhodium dicarbonyl acetylacetonate crude product, add the moisture in water-removal agent removing crude product and Trace Silver in organic solvent.
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| CN111978353A (en) * | 2020-07-30 | 2020-11-24 | 西安凯立新材料股份有限公司 | Preparation method of rhodium complex |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104526A (en) * | 1994-09-30 | 1996-04-23 | Tanaka Kikinzoku Kogyo Kk | Production of rhodium nitrate solution |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104526A (en) * | 1994-09-30 | 1996-04-23 | Tanaka Kikinzoku Kogyo Kk | Production of rhodium nitrate solution |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978353A (en) * | 2020-07-30 | 2020-11-24 | 西安凯立新材料股份有限公司 | Preparation method of rhodium complex |
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