CN103769225B - The renovation process of carbonylation inactivation or part inactivation Rhodium Phosphine catalyst - Google Patents
The renovation process of carbonylation inactivation or part inactivation Rhodium Phosphine catalyst Download PDFInfo
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Abstract
The renovation process of a kind of carbonylation inactivation of the present invention or part inactivation Rhodium Phosphine catalyst, comprise the following steps: (1) is under non-carbonylation condition, reactant liquor containing inactivation or part inactivation Rhodium Phosphine catalyst mixes with the aliphatic carboxylic acid with chemical formula RCOOH with the alkynol or its ester containing 3 ~ 6 carbon atoms, carry out regenerative response, after hybrid reaction, obtain the regenerative response liquid containing Rhodium Phosphine catalyst; (2) under atmosphere of inert gases, add containing the cycloalkane of 6 ~ 9 carbon atoms or containing the alkane of 5 ~ 20 carbon atoms and polar organic solvent in the regenerative response liquid that step one obtains, extract, be separated into two-phase, polar organic solvent mutually in obtain regenerate Rhodium Phosphine catalyst solution.The present invention, through the Rhodium Phosphine catalyst of combined technical method process inactivation of regeneration and extract and separate, can directly obtain highly active Rhodium Phosphine catalyst.Reaction condition relaxes, and technological process is easy.
Description
Technical field
The invention belongs to technical field of catalyst treatment, particularly the renovation process of a kind of carbonylation inactivation or part inactivation Rhodium Phosphine catalyst.。
Background technology
Carbonylation, is also called hydroformylation reaction or hydrogen aldehyde reaction.In the technique of low-pressure process carbonyl synthesizing aldehyde, the catalyst adopted in course of reaction is rhodium-phosphine complex.Adopt this catalyst, reaction pressure is low, and side reaction is few, and this is well-known technically.But along with the carrying out of continuous print carbongl group synthesis reaction, even if substantially there is not external source catalyst poison, Rhodium Phosphine catalyst also can lose activity or part inactivation gradually.Reaction process condition is as the comprehensive function of reaction temperature, reactant partial pressure, phosphine ligand/rhodium mol ratio, rhodium concentration etc., and can cause the generation of torpescence rhodium cluster compound, such catalysqt deactivation cannot be avoided completely.The activation process of inactivation or part inactivation Rhodium Phosphine catalyst is very important for raising device benefit, the consumption of reduction rhodium.
In existing patent and document, JP56002994A provides a kind of method of Extraction of Rhodium phosphine catalyst from carbonylation liquid.In carbonylation processes, the high-boiling point alcohol aldehyde condensate constantly generated can build up, and more difficultly separates, and affects catalyst activity.So mode that is continuous or interval will be adopted to be discharged to outside reaction system by partially catalyzed agent reactant liquor, then fresh makeup catalyst is active to maintain it.Add alkane or cycloalkane and polar organic solvent and carry out extract and separate in the catalyst solution of discharging, solution is divided into two-phase, and Rhodium Phosphine catalyst is extracted in polar organic solvent, achieves and being separated of high-boiling point alcohol aldehyde condensate.After distillation separates polar organic solvent, the Rhodium Phosphine catalyst obtained directly returns carbonylation system and recycles.What this method solve high-boiling point alcohol aldehyde condensate and Rhodium Phosphine catalyst is separated a difficult problem, but be only applicable to because the inhibitor such as high boiling point condensate exist the recycling of the inactivation Rhodium Phosphine catalyst caused, or the cycling and reutilization of high activity Rhodium Phosphine catalyst, but cannot improve because rhodium cluster compound forms the activity causing the Rhodium Phosphine catalyst of inactivation.
US4861918 discloses the method for a kind of rhodium-tertiary organophosphite ligand compound carbonylating catalyst regeneration, comprising: the composition catalyst containing above-mentioned part inactivation, under the carbonylation conditions of non-water, mixes with organic reagent by (1); (2) catalyst-initiator formed in (1) is removed.Regenerative response reagent used in patent is expensive, is difficult to obtain, is unfavorable for commercial Application.
CN1040746 provides a kind of reactivating process method of carbonylating catalyst, under being included in non-carbonylation conditions, preferably in the presence of nitrogen, mix by the ligand catalyst containing partial deactivation with from the liquid medium starting material of other components of carbonylation process with organic reagent, organic reagent is selected from: benzene sulfonic acid alkynes propyl ester, propargyl chloride, propargyl acetate etc., be preferably ethyl propiolate.This reagent dosage is large, and price, is unfavorable for commercial Application.
CN1074632, EP0552797, US5237106 belong to patent families; describe a kind of propargyl alcohol and carboxylic acid processing section inactivation rhodium phosphine hydroformylation catalyst to improve the process of its catalytic activity; this patent with propargyl alcohol and acetic acid for reaction reagent; the mol ratio of propargyl alcohol and rhodium is 25 ~ 100:1, has reacted rear triethanolamine solution and has neutralized.The difficult point of this reaction how to suppress the polymerization of propargyl alcohol in regenerative response process, improves the activity of regenerated catalyst.Reaction reagent propargyl alcohol consumption involved in patent is large, not remarkable to the treatment effect of high-boiling point alcohol aldehyde condensate in inactivation Rhodium Phosphine catalyst and multinuclear rhodium cluster compound.
Summary of the invention
Technical problem to be solved by this invention is the Rhodium Phosphine catalyst feature for inactivation or part inactivation in existing process units, there is provided a kind of can recovered part rhodium cluster compound active, realize the catalyst recovery process that homogeneous phase Rhodium Phosphine catalyst is separated with aldol(s), fundamentally improve the catalytic activity of inactivation Rhodium Phosphine catalyst, whole catalyst regeneration process condition relaxes, rhodium loss is few, and is easy to industrial implementation.
The renovation process of a kind of carbonylation inactivation of the present invention or part inactivation Rhodium Phosphine catalyst, described carbonylation refers to and adopts non-water homogeneous phase technique, with the carbonylation that carbon monoxide, hydrogen and alkane compound carry out for raw material production aldehyde compound, it is characterized in that comprising the following steps:
(1) under non-carbonylation condition, reactant liquor containing inactivation or part inactivation Rhodium Phosphine catalyst mixes with the aliphatic carboxylic acid with chemical formula RCOOH with the alkynol or its ester containing 3 ~ 6 carbon atoms, carry out regenerative response, R wherein in RCOOH represents the alkyl of hydrogen, 1 ~ 5 carbon atom, obtains the regenerative response liquid containing Rhodium Phosphine catalyst after hybrid reaction;
(2) under atmosphere of inert gases, add containing the cycloalkane of 6 ~ 9 carbon atoms or containing the alkane of 5 ~ 20 carbon atoms and polar organic solvent in the regenerative response liquid that step one obtains, extract, be separated into two-phase, polar organic solvent mutually in obtain regenerate Rhodium Phosphine catalyst solution.
According to the reactant liquor of the inactivation handled by the present invention or part inactivation Rhodium Phosphine catalyst, refer under Rhodium Phosphine catalyst exists, adopt non-water homogeneous phase technique, produce aldehyde compound with carbon monoxide, hydrogen and alkane compound for raw material carries out carbonylation, this reaction has proceeded to original use the degree of at least part of inactivation of catalyst and the catalyst reaction liquid that produces.Regeneration process generally can be carried out when catalyst activity reaches below 40%.
" non-water " of the present invention means the carbonylation carried out under water substantially non-existent situation, and namely described reactant liquor only has organic phase, does not comprise an independently moisture or aqueous phase.Those components generated corresponding to carbonylation are comprised, at least containing three kinds of quantitative key components: the Rhodium Phosphine catalyst of inactivation or part inactivation, free organophosphine ligand, organic solvent in reactant liquor.Containing a certain amount of aldehyde compound in described reactant liquor, can a small amount of annexing ingredient be contained, as unreacted olefine initiation material, alkane accessory substance, higher boiling aldehyde condensation by-products, Phosphine ligands accessory substance.I.e. every compound that can exist in carbonylation processes, also can corresponding being present in reactant liquor starting material of the present invention.
As mentioned above, the reactant liquor starting material of present invention process is containing a certain amount of aldehyde compound, and such aldehyde can contain 3 ~ 31 carbon atoms, and comprises the aldehyde product that the alkane compound containing 2 ~ 30 carbon atoms is obtained through carbonylation.Good alkane compound is containing 2 ~ 20 carbon atoms, is more preferably the α-olefine containing 3 ~ 14 carbon atoms.The mass content of aldehyde compound in reactant liquor starting material is 0 ~ 80%, is preferably 30 ~ 70%.
Inactivation contained in reactant liquor or part inactivation Rhodium Phosphine catalyst (calculating by rhodium metal), content is 1 ~ 50000mg/kg, is preferably 100 ~ 2000mg/kg.
Step of the present invention (1) relates to the Rhodium Phosphine catalyst of inactivation or part inactivation in the alkynol or its ester using and contain 3 ~ 6 carbon atoms and the carboxylic acid compound processing reaction liquid with following chemical formula: RCOOH, in formula, R represents the alkyl of hydrogen or 1 ~ 5 carbon atom.Good alkynol or ester are propargyl alcohol, ethyl propiolate, propargyl acetate, are preferably propargyl alcohol.Good carboxylic acid compound is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid and benzoic acid, is preferably acetic acid.
In step of the present invention (2), as cycloalkane or alkane, can be the carbon numbers such as pentane, n-hexane, isohexane, normal heptane, normal octane, isooctane, n-nonane, positive flow silane at the alkane of 5 ~ 20, be preferably n-hexane, normal heptane, normal octane and n-nonane; Carbon number, at the cycloalkane of 6 ~ 9, can be cyclohexane, cycloheptane, cyclooctane etc., be preferably cyclohexane and cycloheptane.The volume ratio containing Rhodium Phosphine catalyst reactant liquor after the activation that cycloalkane or alkane and step 1 obtain is 0.5 ~ 8:1, is preferably 1 ~ 4:1.
Polar organic solvent described in step (2) refers to selects one or both as polar solvent in lower aliphatic nitrile, low-grade alkane alcohol, lower fatty acid, low alkyl group sulfoxide or alkylamide.Good lower aliphatic nitrile to be carbon number be 2 ~ 6 Arneel SD, as acetonitrile, propionitrile, butyronitrile; Good low-grade alkane alcohol can be the alkylol containing 1 ~ 6 carbon atom such as methyl alcohol, ethanol, isopropyl alcohol, butanols.Good lower fatty acid can be the aliphatic acid containing 1 ~ 5 carbon atom such as formic acid, acetic acid, propionic acid, butyric acid.
Good alkyl sulfoxide is dimethyl sulfoxide (DMSO), diethyl sulfoxide, dibutyl sulfoxide; As alkylamide, can be dimethyl formamide, dimethylacetylamide, diethyl acetamide etc.
The consumption of these polar solvents is 0.5 ~ 6:1 with the volume ratio containing Rhodium Phosphine catalyst reactant liquor, is preferably 1 ~ 4:1.Through the regenerative response of step (1), a small amount of water can be produced.When extracting with alkane, cycloalkane and polar solvent, be more difficultly separated into two-phase.The existence of a small amount of water, facilitates and is separated, and makes to form two-phase relatively easily in extraction process.
Described polar organic solvent can be one or both composite solvents.The fatty acid cpds added in step (1), as acetic acid, propionic acid, can use as the polar solvent in step (2), use composite with Arneel SD, low-grade alkane alcohol, alkyl sulfoxide or alkylamide, effect of extracting is better, therefore first need not neutralize removal.
Concrete Rhodium Phosphine catalyst reactant liquor regeneration step is as follows:
The first step, there is no synthesis gas (CO+H
2) condition under, by joining in reactor containing the alkynol of 3 ~ 6 carbon atoms or the reactant liquor of ester, carboxylic acid and (part) inactivation rhodium-and-phosphine composition catalyst, slowly stir, regenerative response is carried out in heating.Good charging sequence is the reactant liquor first adding inactivation rhodium-and-phosphine composition catalyst, then adds carboxylic acid, finally adds the alkynol containing 3 ~ 6 carbon atoms or ester.Reaction pressure is normal pressure, is preferably and first uses nitrogen purge, and reaction is carried out under nitrogen (or other inert gases be applicable to) atmosphere.Reaction temperature 20 ~ 140 DEG C is 1:1 ~ 30:1 containing the alkynol of 3 ~ 6 carbon atoms or the mol ratio of ester and rhodium metal, and the mol ratio of alkynol or ester and carboxylic acid is 5:1 ~ 1:5, reaction time 5 ~ 20h.
Second step, under atmosphere of inert gases, adds cycloalkane or alkane and polar organic solvent, carries out extract and separate in above-mentioned regenerative response liquid, to obtain active high Rhodium Phosphine catalyst solution, and realizes and being separated of high-boiling point alcohol aldehyde condensation products.
In extraction process, operating temperature 0 ~ 90 DEG C, is preferably 20 ~ 60 DEG C.Operating temperature is higher, in extraction process, easily produce aldehyde condensation by-products; And temperature is lower, more easily form emulsion, not easily layering.Extraction time is 0.5 ~ 4h preferably.
Described inert gas, can be nitrogen, argon gas, carbon dioxide, be preferably nitrogen.The object passing into inert gas prevents from producing oxidation reaction in extraction process.
After extracting operation terminates, leave standstill, mixture is separated into two obvious liquid phases, and alkane or cycloalkanes hydrocarbon phase are on upper strata, and polar organic solvent is in lower floor.Rhodium Phosphine catalyst extraction is in polar organic solvent phase, and aldehyde compound, high-boiling point alcohol aldehyde condensation products are extracted in upper liquid.
Reclaiming Rhodium Phosphine catalyst mutually from polar organic solvent is be relatively easy to, first, adopt in known technology and solvent mutually in acid.Available common inorganic base or organic base neutralize, and make solvent mutually in neutral.Inorganic base can be NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate, is preferably NaOH.Organic base can be triethanolamine, diethanol amine, three b propanol amine, methyl diethanolamine, is preferably triethanolamine; Mass concentration that is inorganic and the organic base aqueous solution is 5% ~ 30%, and alkali consumption is: alkali: sour mol ratio is 1.0 ~ 1.2:1, neutralization reaction temperature room temperature ~ 60 DEG C, neutralization reaction time 0.5 ~ 2h.
After having reacted, stratification, is separated removing saline solution.Organic phase can obtain highly active Rhodium Phosphine catalyst after adopting conventional distillating method to remove polar organic solvent.
According to the process of regenerating of carbonyl reaction catalyst provided by the invention, only need stop adding synthesis gas in carbonylation reactor, after residual reactants complete reaction wherein, stop the carbonylation carrying out in reactor.Then in reactor, add reaction reagent and extractant, carry out regeneration and the extract and separate of catalyst, isolate after polar organic solvent through simple distillation, can directly obtain Rhodium Phosphine catalyst active body.The regeneration process of catalyst and carbonylation carry out in same reactor.After the regeneration process of catalyst completes, continuous print carbonylation can be restarted.Also from reactor, extraction section can contain the reactant liquor of inactivation or part inactivation Rhodium Phosphine catalyst, in other reactor, carry out side line regeneration process, do not stop continuous carbonylation reacting.Then the Rhodium Phosphine catalyst will obtained after regeneration process, be mixed with solution with iron-free butyraldehyde, send back in reactor in the same fashion, regeneration technology is simple and practical.Renovation process of the present invention, greatly reduce reaction reagent (alkynol or esters containing 3 ~ 6 carbon atoms) consumption that price is more expensive, toxicity is large, reaction condition relaxes, technological process is easy, after extracting and demixing, achieve being separated of Rhodium Phosphine catalyst and high-boiling point alcohol aldehyde condensate, can directly obtain Rhodium Phosphine catalyst active body, catalyst activity after regeneration is high, is easier to industrialization.
Compared with prior art, beneficial effect of the present invention is:
(1) through the Rhodium Phosphine catalyst of combined technical method process inactivation of regeneration and extract and separate, mainly because of formed catalysqt deactivation that rhodium cluster compound causes be improved significantly, and efficiently solve Rhodium Phosphine catalyst and its inhibitor high-boiling point alcohol aldehyde condensate be separated a difficult problem.Highly active Rhodium Phosphine catalyst can be directly obtained after regeneration and extract and separate.
(2) reduce priming reaction reagent (alkynol or esters containing 3 ~ 6 carbon atoms) consumption that price is more expensive, toxicity is large, reaction condition relaxes, and technological process is easy, and disposal cost is lower.
(3) regeneration of catalyst and carbonylation can carry out in same reactor.
(4) the on-line regeneration process of catalyst can be carried out under the condition not stopping continuous carbonylation reacting.
(5) can improve or improve simultaneously because of external source halide or carboxylic acid fouled catalyst activity.
Detailed description of the invention
Embodiment 1 ~ 5 and comparative example 1:
In the butyraldehyde reactant liquor that industry butyl octanol unit produces, Rhodium Phosphine catalyst activity is reduced to 27% of fresh catalyst from 100%, and after removing part butyraldehyde, rhodium content is about 1000mg/kg, and triphenylphosphine content is about 11%(mass concentration).This reactant liquor (reactant liquor to be regenerated) 50g containing inactivation Rhodium Phosphine catalyst is joined in the reactor of 500ml, use nitrogen purge, then add the alkynol containing 3 ~ 6 carbon atoms as shown in table 1 or its ester and carboxylic acid and carry out chemical regeneration reaction, in reactor, add alkane or cycloalkane and polar organic solvent after reaction terminates again, carry out extract and separate.Then leave standstill, solution settles into two obvious liquid phases, is separated and obtains the upper organic phase containing aldol(s) and the lower floor's polar organic solvent phase containing Rhodium Phosphine catalyst.To polar organic solvent mutually in add the aqueous solution that is inorganic or organic base, neutralization removing carboxylic acid, makes organic solvent mutually in neutral; Stratification removing saline solution again, the organic phase obtained moves in reactor, first purges with nitrogen, then carries out after distillation removes polar organic solvent, obtaining highly active Rhodium Phosphine catalyst.
After embodiment, comparative example experimental condition and regeneration process, the activity of Rhodium Phosphine catalyst is in table 1.
The Activity evaluation of Rhodium Phosphine catalyst under table 1 different tests condition
Illustrate: fresh catalyst activity is 100%, the inactivation rhodium catalyst activity of pending (regeneration) is 27%; Inorganic base or organic base mass content is in aqueous 20%.Rhodium Phosphine catalyst extraction yield refers to that in polar organic solvent, the amount of Rhodium Phosphine catalyst accounts for the percentage (molar amount with rhodium) of total amount in regenerative response liquid.
In the reactant liquor of the inactivation Rhodium Phosphine catalyst do not regenerated, chlorinity 20mg/kg, after regeneration, Chlorine in Solution content is 4mg/kg.Therefore, eliminate in the reactant liquor after regeneration because external source halide is poisoning and carboxylic acid inhibitor simultaneously.
Claims (16)
1. the renovation process of a carbonylation inactivation or part inactivation Rhodium Phosphine catalyst, described carbonylation refers to and adopts non-water homogeneous phase technique, with the carbonylation that carbon monoxide, hydrogen and alkane compound carry out for raw material production aldehyde compound, it is characterized in that comprising the following steps:
(1) under non-carbonylation condition, reactant liquor containing inactivation or part inactivation Rhodium Phosphine catalyst mixes with the aliphatic carboxylic acid with chemical formula RCOOH with the alkynol or its ester containing 3 ~ 6 carbon atoms, carry out regenerative response, R wherein in RCOOH represents the alkyl of hydrogen, 1 ~ 5 carbon atom, obtains the regenerative response liquid containing Rhodium Phosphine catalyst after hybrid reaction; In Rhodium Phosphine catalyst, rhodium content is 1000mg/kg; Rhodium Phosphine catalyst activity is 27%;
(2) under atmosphere of inert gases, add containing the cycloalkane of 6 ~ 9 carbon atoms or containing the alkane of 5 ~ 20 carbon atoms and polar organic solvent in the regenerative response liquid that step one obtains, extract, be separated into two-phase, polar organic solvent mutually in obtain regenerate Rhodium Phosphine catalyst solution.
2. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, is characterized in that regenerative response described in step one is at ambient pressure, reacts 5 ~ 20h at temperature 20 ~ 140 DEG C.
3. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, to it is characterized in that described in step one containing the alkynol of 3 ~ 6 carbon atoms or the mol ratio of its ester and rhodium metal being 1:1 ~ 30:1, the mol ratio of alkynol or its ester and carboxylic acid is 5:1 ~ 1:5.
4. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, is characterized in that regenerative response described in step one carries out under atmosphere of inert gases.
5. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, it is characterized in that the charging sequence of regenerative response described in step one is the reactant liquor first adding inactivation Rhodium Phosphine catalyst, add carboxylic acid again, finally add the alkynol containing 3 ~ 6 carbon atoms or ester.
6. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, it is characterized in that alkynol described in step one or its ester are selected from propargyl alcohol, ethyl propiolate, propargyl acetate, carboxylic acid is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid or benzoic acid.
7. the renovation process of carbonylation inactivation according to claim 6 or part inactivation Rhodium Phosphine catalyst, it is characterized in that described alkynol is propargyl alcohol, carboxylic acid is acetic acid.
8. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, it is characterized in that aldehyde compound mass content in reactant liquor is 0 ~ 80%, this aldehyde compound contains 3 ~ 31 carbon atoms, and comprises the aldehyde product that the alkane compound containing 2 ~ 30 carbon atoms is obtained through carbonylation.
9. the renovation process of carbonylation inactivation according to claim 8 or part inactivation Rhodium Phosphine catalyst, is characterized in that described alkane compound is the α-olefine containing 3 ~ 14 carbon atoms.
10. the renovation process of carbonylation inactivation according to claim 1 or part inactivation Rhodium Phosphine catalyst, to it is characterized in that described in cycloalkane described in step 2 or alkane and step one containing the volume ratio of inactivation or part inactivation Rhodium Phosphine catalyst reactant liquor being 0.5 ~ 8:1, described polar solvent is 0.5 ~ 6:1 with the volume ratio containing inactivation or part inactivation Rhodium Phosphine catalyst reactant liquor.
The renovation process of 11. carbonylation inactivations according to claim 10 or part inactivation Rhodium Phosphine catalyst, it is characterized in that inactivation described in cycloalkane described in step 2 or alkane and step one or part inactivation are 1 ~ 4:1 containing the volume ratio of Rhodium Phosphine catalyst reactant liquor, described polar solvent is 1 ~ 4:1 with the volume ratio containing inactivation or part inactivation Rhodium Phosphine catalyst reactant liquor.
The renovation process of 12. carbonylation inactivations according to claim 1 or part inactivation Rhodium Phosphine catalyst, it is characterized in that the cycloalkane containing 6 ~ 9 carbon atoms described in step 2 is cyclohexane, cycloheptane or cyclooctane, the alkane containing 5 ~ 20 carbon atoms is pentane, n-hexane, isohexane, normal heptane, normal octane, isooctane, n-nonane or positive flow silane.
The renovation process of 13. carbonylation inactivations according to claim 1 or part inactivation Rhodium Phosphine catalyst, it is characterized in that polar organic solvent described in step 2 refer to carbon number be 2 ~ 6 Arneel SD, the alkylol containing 1 ~ 6 carbon atom, the aliphatic acid containing 1 ~ 5 carbon atom, carbon number be 2 ~ 8 low alkyl group sulfoxide or alkylamide in select one or both as polar solvent.
The renovation process of 14. carbonylation inactivations according to claim 13 or part inactivation Rhodium Phosphine catalyst, it is characterized in that described Arneel SD adopts acetonitrile, propionitrile or butyronitrile, described alkylol adopts methyl alcohol, ethanol, isopropyl alcohol or butanols, described aliphatic acid adopts formic acid, acetic acid, propionic acid or butyric acid, described low alkyl group sulfoxide adopts dimethyl sulfoxide (DMSO), diethyl sulfoxide or dibutyl sulfoxide, and described alkylamide adopts dimethyl formamide, dimethylacetylamide or diethyl acetamide.
The renovation process of 15. carbonylation inactivations according to claim 13 or part inactivation Rhodium Phosphine catalyst, it is characterized in that the aliphatic carboxylic acid added in step one uses as the polar organic solvent in step 2, use composite with Arneel SD, alkylol, alkyl sulfoxide or alkylamide.
The renovation process of 16. carbonylation inactivations according to claim 1 or part inactivation Rhodium Phosphine catalyst, is characterized in that in extraction process described in step 2, operating temperature 0 ~ 90 DEG C, extraction time 0.5 ~ 4h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473655A (en) * | 1981-01-22 | 1984-09-25 | Mitsubishi Chemical Industries, Limited | Method for the recovery of rhodium complexes |
| CN1040746A (en) * | 1988-08-12 | 1990-03-28 | 联合碳化化学品及塑料有限公司 | The reactivation of carbonylating catalyst |
| CN1074632A (en) * | 1992-01-24 | 1993-07-28 | 联合碳化化学品及塑料技术公司 | The reactivation of hydroformylation catalyst |
| CN102373335A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS562994A (en) * | 1979-06-22 | 1981-01-13 | Mitsubishi Chem Ind Ltd | Extraction and separation of rhodium complex |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473655A (en) * | 1981-01-22 | 1984-09-25 | Mitsubishi Chemical Industries, Limited | Method for the recovery of rhodium complexes |
| CN1040746A (en) * | 1988-08-12 | 1990-03-28 | 联合碳化化学品及塑料有限公司 | The reactivation of carbonylating catalyst |
| CN1074632A (en) * | 1992-01-24 | 1993-07-28 | 联合碳化化学品及塑料技术公司 | The reactivation of hydroformylation catalyst |
| CN102373335A (en) * | 2010-08-27 | 2012-03-14 | 中国石油化工股份有限公司 | Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst |
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