CN102950028A - 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 the catalyst regeneration technical field, particularly a kind of renovation process of carbonylation inactivation rhodium-and-phosphine composition catalyst.
Background technology
" OXO " reaction is carbongl group synthesis reaction, is called again hydroformylation reaction or hydrogen aldehyde reaction.In the technique of low-pressure process carbonyl synthesizing aldehyde, the catalyst that adopts in the course of reaction is rhodium phosphine catalyst system.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 carbongl group synthesis reaction, even basically there is not the external source catalyst poison, the rhodium phosphine catalyst also can lose activity or the part inactivation.The comprehensive function of reaction process condition such as reaction temperature, reactant partial pressure, phosphine ligand/rhodium mol ratio, rhodium concentration etc. can cause the generation of torpescence complex bunch, and such catalysqt deactivation can't be avoided fully.The regeneration of part decaying catalyst is very important for raising device benefit, the consumption of reduction rhodium.
In the existing patent, CN1403604 provides a kind of method that reclaims metal rhodium from waste olefine carbonylating catalyst liquid, this patent is to adopt the method for decompression distillation, evaporation and ashing that metal rhodium is reclaimed, and is comparatively desirable for the recovering effect of rhodium in the low concentration rhodium waste liquid especially.After reclaiming the rhodium powder, synthesize again using rhodium complex catalysts.The method is based on the again recovery behind the rhodium phosphine catalyst complete deactivation, and technological process is long, and rhodium loses in whole removal process greatly.
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 that the rhodium-containing waste reaction solution of preparation olefine carbonylating catalyst is processed, with the same triphenylphosphine of the aqueous solution that obtains, hydrochloric acid and reaction of carbon monoxide, obtain two (triphenylphosphine) carbonyl radium chloride precipitation, the treated carbonyl hydrogenated rhodium catalyst of triphenylphosphine acetylacetone,2,4-pentanedione rhodium carbonyl or three (triphenylphosphine) that is converted into of isolated precipitation.What the method was processed is the waste reaction solution that produces in the preparation rhodium phosphine catalyst process, and compare obviously different from the decaying catalyst reactant liquor that produces in the 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 rhodium loses greatly in the precipitation process, and catalyst inactivation is larger, and the rhodium loss is more.
US4297239 discloses a kind of renovation process of rhodium catalyst, removes inhibitor through twice to four times vacuum evaporation, 20～350 ℃ of evaporating temperatures, pressure 1000mmHg～1 * 10
-6MmHg, rhodium content is 0.1～30% in the evaporation rear catalyst solution, the inhibitor angle that generates from remove carbongl group synthesis reaction improves catalyst activity.This regeneration technology comparative maturity, but evaporation conditions is harsh, and energy consumption is high, especially when restructuring minute content is high in the catalyst solution, vacuum is required harshness, the rhodium loss late is large, and the easily formation of aggravation rhodium cluster complex in evaporation process causes catalyst activity reduction on the contrary.
US4861918 discloses the method for a kind of rhodium-uncle's organophosphite ligand compound carbonylating catalyst regeneration, and comprising: under the carbonylation condition of non-water, the composition catalyst that will contain above-mentioned part inactivation mixes with organic reagent (1); (2) remove the catalyst-initiator that forms in (1).Regenerative response reagent used in the patent is expensive, is difficult to obtain, and is unfavorable for commercial Application.
US5183943 provides a kind of process for reactivation of carbonylation reaction catalyst, mainly be a kind of because of the poison renovation process of the rhodium-and-phosphine composition catalyst that causes the part inactivation of halide and/or carboxylic acid, the method is to contain the rhodium-and-phosphine composition catalyst reactant liquor and the aqueous solution that contains about 1-25wt% tertiary alkanol amine of part inactivation, the mixture that generates settles into two obvious liquid phases, layering, wash organic phase with water, contain rhodium-and-phosphine composition catalyst in the organic phase, the activity of this catalyst improves after regeneration.This patent only adopts tertiary alkanol amine to process the rhodium catalyst of inactivation, and catalyst activity improves not obvious, can't solve the catalysqt deactivation that causes because of the formation of rhodium cluster compound.
US5237106 introduced a kind of with propargyl alcohol and carboxylic acid processing section inactivation rhodium-and-phosphine composition hydroformylation catalyst to improve the process of its catalytic activity; this patent is take propargyl alcohol and acetic acid as reaction reagent; the mol ratio of propargyl alcohol and rhodium is 25～100: 1, neutralizes with triethanolamine solution after reaction is finished.The difficult point of this reaction is how to suppress the polymerization of propargyl alcohol in the regenerative response process, improves the activity of regenerated catalyst.Large, the easily polymerization of reaction reagent toxicity related in the patent, patent does not openly suppress the method for propargyl alcohol polymerization, and the propargyl alcohol consumption is large, has on the implementation certain difficulty.
Summary of the invention
Technical problem to be solved by this invention is for the rhodium phosphine catalyst of inactivation in the existing process units, and a kind of catalyst recovery process that is easy to industrial implementation is provided, and the rhodium phosphine catalyst is active high after the regeneration, and the 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, the reactant liquor that contains the inactivation rhodium-and-phosphine composition catalyst, under non-carbonylation condition, mix with the carboxylic acid with chemical formula RCOOH with the alkynol that contains 3～6 carbon atoms or ester, 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, wherein the R among the RCOOH represents hydrogen or an alkyl or aryl, obtains the treated reactant liquor that contains rhodium-and-phosphine composition catalyst after the hybrid reaction;
(2) add the tertiary alkanol amine aqueous solution in the reactant liquor that obtains to step 1, neutralize unreacted carboxylic acid or halide generate water soluble salt, and wherein tertiary alkanol amine general formula is RN (R
1R
2), R represents the hydroxyalkyl with 2～4 carbon atoms, R in the formula
1And R
2Expression is with the hydroxyalkyl of the alkyl of 1～4 carbon atom, 2～4 carbon atoms or the group of phenyl;
(3) make the mixture that generates in the step 2 settle into two obvious liquid phases, separate the organic phase that obtains salt aqueous solution phase and contain rhodium-and-phosphine composition catalyst;
(4) wash isolated organic phase with water, obtaining a kind ofly has the more solution that contains rhodium-and-phosphine composition catalyst of high catalytic activity than aforementioned inactivation rhodium phosphine catalyst.
Reactant liquor according to the present invention's handled (part) inactivation rhodium-and-phosphine composition catalyst, refer in the presence of rhodium-and-phosphine composition catalyst, adopt non-water homogeneous phase technique, carry out carbonylation take carbon monoxide, hydrogen and alkane compound as raw material and produce aldehyde compound, this reaction has proceeded to the original catalyst reaction liquid that uses the degree of at least part of inactivation of catalyst and produce.The degree of this type of catalysqt deactivation (or catalyst activity) can characterize with the reaction time, namely in identical reaction pressure excursion, adopt this type of catalyst to carry out carbonylation and generate the aldehyde compound required time and adopt the needed time of fresh catalyst to be compared.Reaction time is shorter, and then catalyst activity is higher.
" the non-water " of the above means the carbonylation that basically carries out in the non-existent situation at water, and namely described reactant liquor only has organic phase, does not comprise an independently moisture or water.At least contain three kinds of quantitative key components in the reactant liquor: the rhodium-and-phosphine composition catalyst of part inactivation, free organic phosphine coordination body, described composition catalyst and contain the organic solvent of free ligand, those components that described component generates corresponding to carbonylation preferably.Contain a certain amount of aldehyde compound in the described reactant liquor, can contain a small amount of annexing ingredient, such as unreacted olefine initiation material, alkane accessory substance, higher boiling aldehyde condensation by-product, phosphine part accessory substance.Be every compound that can in carbonylation processes, exist, also can corresponding being present in the reactant liquor starting material of the present invention.
As mentioned above, the reactant liquor starting material of technique of the present invention contains a certain amount of aldehyde compound, and such aldehyde can contain 3～31 carbon atoms, and comprises the aldehyde product that the alkane compound that contains 2～30 carbon atoms is obtained through carbonylation.Alkane compound is to contain 2～20 carbon atoms preferably, is more preferably the alpha-olefin that contains 3～14 carbon atoms.Aldehyde compound content in the reactant liquor starting material is 0～80%, is preferably 30～70%.
Contained (part) inactivation rhodium catalyst in the reactant liquor (pressing rhodium metal calculates), content is 1～50000mg/kg, is preferably 100～2000mg/kg.
Step of the present invention (1) relates to uses (part) inactivation rhodium-and-phosphine composition catalyst: RCOOH in alkynol or the ester that contains 3～6 carbon atoms and the carboxylic acid compound processing reaction liquid with following chemical formula, R represents hydrogen or an alkyl or aryl in the formula, especially alkyl or a phenyl that contains 1～4 carbon atom.Alkynol or ester are propargyl alcohol, ethyl propiolate, propargyl acetate preferably, are preferably propargyl alcohol.Carboxylic acid compound is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid and benzoic acid preferably, is preferably acetic acid.
In the step of the present invention (2), the mass content of tertiary alkanol amine in the aqueous solution is 1～25%, 30～90 ℃ of reaction temperatures, the treated volume ratio that contains the 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, will contain the alkynol of 3～6 carbon atoms or the reactant liquor of ester, carboxylic acid and (part) inactivation rhodium-and-phosphine composition catalyst and join in the reactor, slowly stir, add thermal response.Charging sequence is the reactant liquor that adds first the inactivation rhodium-and-phosphine composition catalyst preferably, adds carboxylic acid again, adds at last alkynol or the ester that contains 3～6 carbon atoms.Reaction pressure is normal pressure, is preferably to use first the nitrogen blowing reactor, and reaction is carried out under nitrogen atmosphere.20～140 ℃ of reaction temperatures, containing the alkynol of 3～6 carbon atoms or the mol ratio of ester and rhodium metal is 1: 1～25: 1, the mol ratio of rhodium and carboxylic acid is 5: 1～1: 5.Reaction time 5～20h.
Renovation process of the present invention, the reaction reagent that price is more expensive, toxicity is large (alkynol or the ester that contain 3～6 carbon atoms) consumption reduces greatly, and high through the catalyst activity of regeneration, reaction condition relaxes, and technological process is easy, is easier to industrialization.
Contain unreacted carboxylic acid in the treated reactant liquor that contains rhodium-and-phosphine composition catalyst, add the tertiary alkanol amine aqueous solution in reactant liquor, neutralize unreacted carboxylic acid or halide generate a kind of water soluble salt.Wherein tertiary alkanol amine general formula is RN (R
1R
2), R represents the hydroxyalkyl with 2～4 carbon atoms, R in the formula
1And R
2Each represents respectively alkyl, the hydroxyalkyl of 2～4 carbon atoms or the group of phenyl with 1～4 carbon atom.Can be triethanolamine, three b propanol amine, methyl diethanolamine, phenyldiethanol-amine, preferred triethanolamine.The mass content of tertiary alkanol amine in the aqueous solution is 1～25%, is preferably 5～15%.30～90 ℃ of reaction temperatures are preferably 40～70 ℃.Reaction temperature is higher, and the amount that the aldehyde condensation by-product generates is just larger; And temperature is lower, and easier formation emulsion is difficult for layering.Preferred 0.5～5h of reaction time.The treated volume ratio that contains the 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 finishes, static, make the mixture of generation settle into two obvious liquid phases, separate the organic phase that obtains salt aqueous solution phase and contain rhodium complex catalyst.Add water washing in organic phase, the volume ratio of organic phase/water is 0.5～5, and washing pressure is normal pressure, 30～90 ℃ of washing temperature, preferred 40～80 ℃.Washing times is 1～2 time.
After washing step is finished, carry out sedimentation, get rid of end phase (water), isolate organic phase, namely obtain a kind of solution that contains rhodium complex catalyst that larger catalytic activity is arranged than aforementioned inactivation rhodium catalyst.
According to renovation process provided by the invention, only need to stop in carbonylation reactor, adding synthesis gas, after residual reactants complete reaction wherein, stop the carbonylation that carries out in the 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 is finished, can restart continuous carbonylation.Also can from reactor, extract the reactant liquor that part contains decaying catalyst out, in other reactor, carry out on-line regeneration, not stop the continuous carbonylation reaction.Then the reactant liquor after will regenerating sends back in the reactor with the same manner, and treatment process is simple and practical.
Compared with prior art, the present invention has following beneficial effect:
(1) the regenerative response reagent that price is more expensive, toxicity is large (alkynol or the ester that contain 3～6 carbon atoms) consumption reduces greatly, and reaction condition relaxes, and technological process is easy, and is high through the catalyst activity of regeneration, solved the high difficult problem of regeneration expense.
(2) regeneration of catalyst and carbonylation can carry out in same reactor.
(3) can be at the on-line regeneration that does not stop to carry out under the condition of continuous carbonylation reaction catalyst.
(4) can improve or improve simultaneously because of external source halide or carboxylic acid fouled catalyst activity.
The specific embodiment
The invention will be further described below by embodiment, but the present invention is not limited only to these examples.Can fully understand essence of the present invention and invention scope by these embodiment, further understand the characteristics of catalyst recovery process of the present invention.
Embodiment 1～6 and Comparative Examples 7:
In the butyraldehyde reactant liquor that the industry butyl octanol unit produces, the rhodium catalyst activity is reduced to the about 25% of fresh catalyst from 100%, removes the about 1100mg/kg of rhodium content behind the part butyraldehyde, triphenylphosphine content about 10%.This reactant liquor 50g that contains the part decaying catalyst is joined in the reactor of 100ml, use the nitrogen blowing reactor, then adding the alkynol that contains 3～6 carbon atoms of different proportionings as shown in table 1 or ester and carboxylic acid reacts, after finishing, reaction adds again 10% the triethanolamine aqueous solution in the reactor, neutralize unreacted carboxylic acid or halide generate water soluble salt.
After neutralization reaction finished, quiescent settling became two obvious liquid phases, separated the organic phase that obtains salt aqueous solution phase and contain rhodium complex catalyst.Organic phase is moved in the reactor, add water washing behind the nitrogen blowing, then carry out sedimentation, get rid of end phase (water), isolate organic phase, namely obtain a kind of solution that contains rhodium complex catalyst of regeneration.
The activity of regenerated catalyst under table 1 different condition
Illustrate: the fresh catalyst activity is 100%, pending inactivation rhodium catalyst active about 25%.
In the reactant liquor that contains the part decaying catalyst of not regenerating, chlorinity 25mg/kg, Chlorine in Solution content is 6mg/kg after the regeneration.Therefore, eliminated simultaneously in the reactant liquor after the regeneration because of the poisoning of external source halide and carboxylic acid inhibitor.
Claims (10)
1. a renovation process that is used for the inactivation rhodium-and-phosphine composition catalyst of carbonylation 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, the reactant liquor that contains the inactivation rhodium-and-phosphine composition catalyst, under non-carbonylation condition, mix with the carboxylic acid with chemical formula RCOOH with the alkynol that contains 3～6 carbon atoms or ester, 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, wherein the R among the RCOOH represents hydrogen or an alkyl or aryl, obtains the treated reactant liquor that contains rhodium-and-phosphine composition catalyst after the hybrid reaction;
(2) add the tertiary alkanol amine aqueous solution in the reactant liquor that obtains to step 1, neutralize unreacted carboxylic acid or halide generate water soluble salt, and wherein tertiary alkanol amine general formula is RN (R
1R
2), R represents the hydroxyalkyl with 2～4 carbon atoms, R in the formula
1And R
2Expression is with the hydroxyalkyl of the alkyl of 1～4 carbon atom, 2～4 carbon atoms or the group of phenyl;
(3) make the mixture that generates in the step 2 settle into two obvious liquid phases, separate the organic phase that obtains salt aqueous solution phase and contain rhodium-and-phosphine composition catalyst;
(4) wash isolated organic phase with water, obtaining a kind ofly has the more solution that contains rhodium-and-phosphine composition catalyst of high catalytic activity than aforementioned inactivation rhodium phosphine catalyst.
2. renovation process according to claim 1 is characterized in that containing that the aldehyde compound mass content is 0～80% in the reactant liquor of inactivation rhodium-and-phosphine composition catalyst, and inactivation rhodium phosphine catalyst is pressed rhodium metal and calculated, and content is 1～50000mg/kg.
3. renovation process according to claim 2 is characterized in that containing that the aldehyde compound mass content is 30～70%% in the reactant liquor of inactivation rhodium-and-phosphine composition catalyst, and inactivation rhodium phosphine catalyst is pressed rhodium metal and calculated, and content is 100～2000mg/kg.
4. renovation process according to claim 1 is characterized in that described carboxylic acid RCOOH, and R represents alkyl or a phenyl that contains 1～4 carbon atom in the formula.
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 the mass content of tertiary alkanol amine in the aqueous solution is 1～25%, 30～90 ℃ of reaction temperatures, the treated volume ratio that contains the rhodium-and-phosphine composition catalyst reactant liquor that tertiary alkanol amine aqueous solution consumption and step 1 obtain is 0.5～5: 1.
9. according to claim 1 or 8 described renovation process, it 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, and washing pressure is normal pressure, 30～90 ℃ of washing temperature, and, washing times is 1～2 time.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104028311A (en) * | 2014-07-02 | 2014-09-10 | 天津渤化永利化工股份有限公司 | Chemical regeneration method of catalyst for oxo-synthesis of butanol and octanol |
| CN104248994A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Method for recovering activity of carbonylation Rh-P catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647527B (en) * | 2018-12-12 | 2020-10-23 | 北京科技大学 | Method for recycling scrap rhodium homogeneous catalyst |
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| CN104248994A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Method for recovering activity of carbonylation Rh-P catalyst |
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| 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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