CN102950028B - Regeneration method for inactivated rh-p (rhodium-phosphine) complex catalyst for carbonylation reaction - Google Patents
Regeneration method for inactivated rh-p (rhodium-phosphine) complex catalyst for carbonylation reaction Download PDFInfo
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Abstract
The invention relates to a regeneration method for inactivated rh-p (rhodium-phosphine) complex catalyst for carbonylation reaction, which comprises the following steps of: firstly, carrying out hybrid reaction on inactivated rh complex catalyst reaction liquid with 3-6 carbon atom containing alkynol or ester and a carboxylic acid; then, adding a tertiary alkanolamine aqueous solution into the obtained reaction liquid, so that unreacted carboxylic acids or halides are neutralized, and then a water soluble salt is generated; carrying out settling separation on the water soluble salt so as to obtain a rh-p complex catalyst containing organic phase; and washing the separated organic phase with water so as to obtain a rh complex catalyst containing solution which has higher catalytic activity in comparison with the inactivated rh complex catalyst. According to the regeneration method provided by the invention, the application amount of an expensive-price and large-toxicity regenerated reaction reagent (3-6 carbon atom containing alkynol or ester) can be greatly reduced; the reaction conditions are moderate, so that the online regeneration of catalysts can be performed under the condition of not stopping the continuous carbonylation reaction; and the technological process is simple, and the activity of the catalyst subjected to regeneration is high, thereby solving the problem that the regeneration cost of the catalyst is high.
Description
Technical field
The invention belongs to catalyst regeneration techniques field, particularly a kind of renovation process of carbonylation inactivation rhodium-and-phosphine composition catalyst.
Background technology
" OXO " reaction and carbongl group synthesis reaction, be 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.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 complex bunch, such catalysqt deactivation cannot be avoided completely.The regeneration of part decaying catalyst is very important for raising device benefit, the consumption of reduction rhodium.
In existing patent, CN1403604 provides a kind of method of Footwall drift rhodium from waste olefine carbonylating catalyst liquid, this patent be adopt decompression distillation, the method for evaporation and ashing reclaims metal rhodium, ideal for the recovering effect of rhodium in low concentration rhodium waste liquid especially.After reclaiming rhodium powder, then synthesize using rhodium complex catalysts.The method be based on Rhodium Phosphine catalyst complete deactivation after reclaim again, technological process is long, and rhodium loses greatly in whole removal process.
CN101690898 discloses a kind of method from preparing rhodium complex catalyst from reaction waste solution of olefin carbonylation rhodium catalyst, be characterized in adopting the mixed solution of nitric acid and hydrogen peroxide to process the rhodium-containing waste reaction solution preparing olefine carbonylating catalyst, by the same triphenylphosphine of the aqueous solution, hydrochloric acid and the reaction of carbon monoxide that obtain, obtain two (triphenylphosphine) carbonyl radium chloride precipitation, isolated precipitation is treated is converted into triphenylphosphine acetylacetone,2,4-pentanedione rhodium carbonyl or three (triphenylphosphine) carbonyl hydrogenated rhodium catalyst.The method process be prepare the waste reaction solution produced in Rhodium Phosphine catalyst process, obviously different compared with the decaying catalyst reactant liquor produced in process units: component is simple, and level of deactivation is little.Although therefore the method can obtain active higher catalyst, reaction process is many, long flow path, and in precipitation process, rhodium loss is large, and catalyst inactivation is larger, and rhodium loss is more.
US4297239 discloses a kind of renovation process of rhodium catalyst, removes inhibitor through twice to four vacuum evaporation, evaporating temperature 20 ~ 350 DEG C, pressure 1000mmHg ~ 1 × 10
-6mmHg, in evaporation rear catalyst solution, rhodium content is 0.1 ~ 30%, improves catalyst activity from removing the inhibitor angle generated carbongl group synthesis reaction.This regeneration technology comparative maturity, but evaporation conditions is harsher, and energy consumption is high, especially when in catalyst solution during heavy constituent content height, harsh to vacuum requirement, rhodium loss late is large, and in evaporation process, easily aggravate the formation of rhodium cluster complex, cause catalyst activity reduction on the contrary.
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.
US5183943 provides a kind of process for reactivation of carbonylation reaction catalyst, mainly a kind of because of halide and/or carboxylic acid poisoning and cause the renovation process of the rhodium-and-phosphine composition catalyst of part inactivation, the method is by the rhodium-and-phosphine composition catalyst reactant liquor containing part inactivation and the aqueous solution containing about 1-25wt% tertiary alkanol amine, the mixture generated settles into two obvious liquid phases, layering, wash organic phase with water, containing rhodium-and-phosphine composition catalyst in organic phase, the activity of this catalyst improves after regeneration.This patent only adopts the rhodium catalyst of tertiary alkanol amine process inactivation, and catalyst activity improves not obvious, cannot solve because rhodium cluster compound forms the catalysqt deactivation caused.
US5237106 describes a kind of propargyl alcohol and carboxylic acid processing section inactivation rhodium-and-phosphine composition 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 toxicity involved in patent is polymerized greatly, easily, and patent does not openly suppress the method for propargyl alcohol polymerization, and propargyl alcohol consumption is large, there is certain difficulty on the implementation.
Summary of the invention
Technical problem to be solved by this invention is the Rhodium Phosphine catalyst for inactivation in existing process units, provides a kind of catalyst recovery process being easy to industrial implementation, and after regeneration, Rhodium Phosphine catalyst activity is high, and rhodium loss is few.
The renovation process of a kind of inactivation rhodium-and-phosphine composition catalyst for carbonylation of the present invention, is characterized in that comprising the steps:
(1) with carbon monoxide, hydrogen and alkane compound are that raw material carries out in the technique of carbonylation production aldehyde compound, containing the reactant liquor of inactivation rhodium-and-phosphine composition catalyst, under non-carbonylation condition, mix with the carboxylic acid with chemical formula RCOOH with the alkynol or ester that contain 3 ~ 6 carbon atoms, the mol ratio of alkynol or ester and rhodium is 1 ~ 25: 1, the mol ratio of rhodium and carboxylic acid is 5: 1 ~ 1: 5, hybrid reaction time 5 ~ 20h, R wherein in RCOOH represents hydrogen or an alkyl or aryl, the treated reactant liquor containing rhodium-and-phosphine composition catalyst is obtained after hybrid reaction,
(2) add tertiary alkanol amine aqueous solution in the reactant liquor obtained to step 1, neutralize unreacted carboxylic acid or halide, generate water soluble salt, wherein tertiary alkanol amine general formula is RN (R
1r
2), in formula, R represents the hydroxyalkyl of band 2 ~ 4 carbon atoms, R
1and R
2represent the alkyl of band 1 ~ 4 carbon atom, the hydroxyalkyl of 2 ~ 4 carbon atoms or the group of phenyl;
(3) make the mixture generated in step 2 settle into two obvious liquid phases, be separated and obtain salt aqueous solution phase and the organic phase containing rhodium-and-phosphine composition catalyst;
(4) wash isolated organic phase with water, obtain a kind of solution containing rhodium-and-phosphine composition catalyst having more high catalytic activity than aforementioned inactivation Rhodium Phosphine catalyst.
According to the reactant liquor of (part) inactivation rhodium-and-phosphine composition catalyst handled by the present invention, refer under rhodium-and-phosphine composition 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.The degree (or catalyst activity) of this type of catalysqt deactivation can characterize with the reaction time, namely, in identical reaction pressure excursion, adopt this type of catalyst to carry out carbonylation generation aldehyde compound required time and compared with the time adopted required for fresh catalyst.Reaction time is shorter, then catalyst activity is higher.
Upper described " non-water " 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.At least containing three kinds of quantitative key components in reactant liquor: the rhodium-and-phosphine composition catalyst of part inactivation, free organophosphine ligand, described composition catalyst and the organic solvent containing free ligand, described component corresponds to those components that carbonylation generates preferably.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 alpha-olefin containing 3 ~ 14 carbon atoms.Aldehyde compound content in reactant liquor starting material is 0 ~ 80%, is preferably 30 ~ 70%.
(part) inactivation rhodium catalyst (calculating by rhodium metal) contained in reactant liquor, content is 1 ~ 50000mg/kg, is preferably 100 ~ 2000mg/kg.
Step of the present invention (1) relates to (part) inactivation rhodium-and-phosphine composition catalyst: RCOOH in the alkynol or ester using and contain 3 ~ 6 carbon atoms and the carboxylic acid compound processing reaction liquid with following chemical formula, in formula, R represents hydrogen or an alkyl or aryl, and especially one contains alkyl or a phenyl of 1 ~ 4 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), tertiary alkanol amine mass content is in aqueous 1 ~ 25%, reaction temperature 30 ~ 90 DEG C, the treated volume ratio containing rhodium-and-phosphine composition catalyst reactant liquor that tertiary alkanol amine aqueous solution consumption and step 1 obtain is 0.5 ~ 5: 1.
Concrete preparation process is as follows:
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 stirring, adding thermal response.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 atmosphere.Reaction temperature 20 ~ 140 DEG C is 1: 1 ~ 25: 1 containing the alkynol of 3 ~ 6 carbon atoms or the mol ratio of ester and rhodium metal, and the mol ratio of rhodium and carboxylic acid is 5: 1 ~ 1: 5.Reaction time 5 ~ 20h.
Renovation process of the present invention, reaction reagent (alkynol or esters containing 3 ~ 6 carbon atoms) consumption that price is more expensive, toxicity is large reduces greatly, and the catalyst activity through regeneration is high, and reaction condition relaxes, and technological process is easy, is easier to industrialization.
Treated contains unreacted carboxylic acid containing in the reactant liquor of rhodium-and-phosphine composition catalyst, adds tertiary alkanol amine aqueous solution, neutralizes unreacted carboxylic acid or halide, generate a kind of water soluble salt in reactant liquor.Wherein tertiary alkanol amine general formula is RN (R
1r
2), in formula, R represents the hydroxyalkyl of band 2 ~ 4 carbon atoms, R
1and R
2each alkyl, the hydroxyalkyl of 2 ~ 4 carbon atoms or group of phenyl representing band 1 ~ 4 carbon atom respectively.Can be triethanolamine, three b propanol amine, methyl diethanolamine, phenyldiethanol-amine, preferred triethanolamine.Tertiary alkanol amine mass content is in aqueous 1 ~ 25%, is preferably 5 ~ 15%.Reaction temperature 30 ~ 90 DEG C, is preferably 40 ~ 70 DEG C.Reaction temperature is higher, and the amount that aldehyde condensation by-products generates is larger; And temperature is lower, more easily form emulsion, not easily layering.Reaction time is 0.5 ~ 5h preferably.The treated volume ratio containing rhodium-and-phosphine composition catalyst reactant liquor that tertiary alkanol amine aqueous solution consumption and step 1 obtain is 0.5 ~ 5: 1.
After neutralization reaction terminates, static, make the mixture of generation settle into two obvious liquid phases, be separated and obtain salt aqueous solution phase and the organic phase containing rhodium complex catalyst.In organic phase, add water washing, the volume ratio of organic phase/water is 0.5 ~ 5, and washing pressure is normal pressure, washing temperature 30 ~ 90 DEG C, preferably 40 ~ 80 DEG C.Washing times is 1 ~ 2 time.
After washing step completes, carry out sedimentation, get rid of end phase (aqueous phase), isolate organic phase, namely obtain a kind of solution containing rhodium complex catalyst having larger catalytic activity than aforementioned inactivation rhodium catalyst.
According to renovation process 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, carry out the regeneration of catalyst.The regeneration of catalyst and carbonylation carry out in same reactor.After the regeneration of catalyst completes, continuous print carbonylation can be restarted.Also can extraction section containing the reactant liquor of decaying catalyst, in other reactor, carry out on-line regeneration, do not stop continuous carbonylation reacting from reactor.Then sent back in the same fashion in reactor by the reactant liquor after regeneration, treatment process is simple and practical.
Compared with prior art, the present invention has following beneficial effect:
(1) regenerative response reagent (alkynol or esters containing 3 ~ 6 carbon atoms) consumption that price is more expensive, toxicity is large reduces greatly, and reaction condition relaxes, and technological process is easy, and the catalyst activity through regeneration is high, solves a regeneration difficult problem costly.
(2) regeneration of catalyst and carbonylation can carry out in same reactor.
(3) on-line regeneration of catalyst can be carried out under the condition not stopping continuous carbonylation reacting.
(4) can improve or improve simultaneously because of external source halide or carboxylic acid fouled catalyst activity.
Detailed description of the invention
Below by embodiment, the invention will be further described, but the present invention is not limited only to these examples.Essence of the present invention and invention scope can be fully understood by these embodiments, understand the feature of catalyst recovery process of the present invention further.
Embodiment 1 ~ 6 and comparative example 7:
In the butyraldehyde reactant liquor that industry butyl octanol unit produces, rhodium catalyst activity is reduced to about 25% of fresh catalyst from 100%, and after removing part butyraldehyde, rhodium content is about 1100mg/kg, triphenylphosphine content about 10%.This reactant liquor 50g containing part decaying catalyst is joined in the reactor of 100ml, use nitrogen purge, then reacting containing the alkynol of 3 ~ 6 carbon atoms or ester and carboxylic acid of different ratio as shown in table 1 is added, in reactor, the triethanolamine aqueous solution of 10% is added again after reaction terminates, neutralize unreacted carboxylic acid or halide, generate water soluble salt.
After neutralization reaction terminates, quiescent settling becomes two obvious liquid phases, is separated and obtains salt aqueous solution phase and the organic phase containing rhodium complex catalyst.Organic phase moved in reactor, nitrogen adds water washing after purging, and then carries out sedimentation, gets rid of end phase (aqueous phase), isolates organic phase, namely obtains a kind of solution containing rhodium complex catalyst of regeneration.
The activity of regenerated catalyst under table 1 different condition
Illustrate: fresh catalyst activity is 100%, pending inactivation rhodium catalyst activity about 25%.
What do not regenerate contains in the reactant liquor of part decaying catalyst, and chlorinity 25mg/kg, after regeneration, Chlorine in Solution content is 6mg/kg.Therefore, eliminate in the reactant liquor after regeneration because external source halide is poisoning and carboxylic acid inhibitor simultaneously.
Claims (10)
1., for a renovation process for the inactivation rhodium-and-phosphine composition catalyst of carbonylation, it is characterized in that comprising the steps:
(1) with carbon monoxide, hydrogen and alkane compound are that raw material carries out in the technique of carbonylation production aldehyde compound, containing the reactant liquor of inactivation rhodium-and-phosphine composition catalyst, inactivation Rhodium Phosphine catalyst activity is wherein 25%, calculate by rhodium metal, content is 1100mg/kg, under non-carbonylation condition, mix with the carboxylic acid compound with chemical formula RCOOH with the alkynol or ester that contain 3 ~ 6 carbon atoms, the mol ratio of alkynol or ester and rhodium is 1 ~ 5:1, the mol ratio of rhodium and carboxylic acid is 5:1 ~ 1:5, hybrid reaction time 5 ~ 20h, R wherein in RCOOH represents hydrogen or an alkyl or aryl, the treated reactant liquor containing rhodium-and-phosphine composition catalyst is obtained after hybrid reaction,
(2) add tertiary alkanol amine aqueous solution in the reactant liquor obtained to step (1), neutralize unreacted carboxylic acid or halide, generate water soluble salt, wherein tertiary alkanol amine general formula is RN (R
1r
2), in formula, R represents the hydroxyalkyl of band 2 ~ 4 carbon atoms, R
1and R
2represent the alkyl of band 1 ~ 4 carbon atom, the hydroxyalkyl of 2 ~ 4 carbon atoms or the group of phenyl;
(3) make the mixture generated in step (2) settle into two obvious liquid phases, be separated and obtain salt aqueous solution phase and the organic phase containing rhodium-and-phosphine composition catalyst;
(4) wash isolated organic phase with water, obtain a kind of solution containing rhodium-and-phosphine composition catalyst having more high catalytic activity than aforementioned inactivation rhodium-and-phosphine composition catalyst.
2. renovation process according to claim 1, is characterized in that described is 0 ~ 80% containing aldehyde compound mass content in the reactant liquor of inactivation rhodium-and-phosphine composition catalyst.
3. renovation process according to claim 2, is characterized in that described is 30 ~ 70% containing aldehyde compound mass content in the reactant liquor of inactivation rhodium-and-phosphine composition catalyst.
4. renovation process according to claim 1, is characterized in that described carboxylic acid RCOOH, and in formula, R represents alkyl or the phenyl that contains 1 ~ 4 carbon atom.
5. renovation process according to claim 4, is characterized in that described carboxylic acid compound is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid or benzoic acid.
6. renovation process according to claim 4, is characterized in that described carboxylic acid compound is acetic acid.
7. renovation process according to claim 1, is characterized in that described alkynol or ester are propargyl alcohol, ethyl propiolate or propargyl acetate.
8. renovation process according to claim 1, it is characterized in that tertiary alkanol amine mass content is in aqueous 1 ~ 25%, reaction temperature 30 ~ 90 DEG C, the treated volume ratio containing rhodium-and-phosphine composition catalyst reactant liquor that tertiary alkanol amine aqueous solution consumption and step (1) obtain is 0.5 ~ 5:1.
9. the renovation process according to claim 1 or 8, is characterized in that described tertiary alkanol amine is triethanolamine, three b propanol amine, methyl diethanolamine or phenyldiethanol-amine.
10. renovation process according to claim 1, is characterized in that step (4) adds water washing in organic phase, and the volume ratio of organic phase/water is 0.5 ~ 5:1, and washing pressure is normal pressure, washing temperature 30 ~ 90 DEG C, and washing times is 1 ~ 2 time.
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| CN109647527A (en) * | 2018-12-12 | 2019-04-19 | 北京科技大学 | A method of scrapping rhodium homogeneous catalyst regeneration |
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| CN104248994B (en) * | 2013-06-25 | 2018-03-20 | 中国石油化工股份有限公司 | The method for activation recovering of Rhodium Phosphine catalyst is carbonylated |
| CN104028311B (en) * | 2014-07-02 | 2016-06-15 | 天津渤化永利化工股份有限公司 | A kind of octyl alconyl oxo catalyst chemical regeneration method |
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| US5183943A (en) * | 1991-03-18 | 1993-02-02 | Union Carbide Chemicals & Plastics Technology Corporation | Reactivation of hydroformylation catalysts |
| US5237106A (en) * | 1992-01-24 | 1993-08-17 | Union Carbide Chemicals & Plastics Technology Corporation | Reactivation of hydroformylation catalysts |
| CN102115433B (en) * | 2010-12-06 | 2013-09-11 | 淄博诺奥化工有限公司 | Synthesis method of propionaldehyde by low-pressure carbonyl of ethylene |
| CN102950027B (en) * | 2011-08-30 | 2015-03-25 | 中国石油化工股份有限公司 | Regeneration method of inactivated rhodium complex catalyst used for carbonyl reaction |
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