CN102950027A - Regeneration method of inactivated rhodium complex catalyst used for carbonyl reaction - Google Patents
Regeneration method of inactivated rhodium complex catalyst used for carbonyl reaction Download PDFInfo
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Abstract
The invention belongs to the technical field of the catalyst regeneration, and particularly relates to a regeneration method of an inactivated rhodium complex catalyst used for a carbonyl reaction. The regeneration method of the inactivated rhodium complex catalyst comprises the steps of: firstly mixing a reaction liquid containing an inactivated rhodium complex catalyst with alkynol or ester containing 3-6 carbon atoms, and carboxylic acid, and carrying out the regeneration reaction in the existence of hydrogen or nitrogen at the reaction pressure of 0.1-1.0MPa; then adding an aqueous tertiary alkanol amine solution into the obtained reaction liquid, neutralizing unreacted carboxylic acid or halide to generate water soluble salt; then carrying out the settlement separation to obtain an organic phase containing a rhodium complex catalyst; and washing the organic phase with water to obtain a solution containing the rhodium complex catalyst, the catalytic activity of which is higher than the catalytic activity of the existing inactivated rhodium catalyst. The regeneration method of the inactivated rhodium complex catalyst solves the polymerization problem in the regeneration process of the alkynol or the ester containing 3-6 carbon atoms. The regeneration method of the inactivated rhodium complex catalyst has the advantages of low reagent dosage, mild reaction conditions, easiness in technological process, and high generated catalyst activity, and also has the advantage that the regeneration method of the inactivated rhodium complex can carry out online regeneration of the catalyst under the condition that the carbonyl reaction can be continuously carried out without any pauses.
Description
Technical field
The invention belongs to the catalyst regeneration technical field, particularly the used inactivation of a kind of carbonylation or the renovation process of part inactivation rhodium complex 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, rhodium complex 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 inactivation rhodium complex 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 adopts 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 rhodium complex catalyst.The method is based on the again recovery of rhodium powder in the rhodium complex catalyst waste liquid, and technological process is long, and the rhodium powder loses in whole removal process greatly.
CN101690898 discloses a kind of method for preparing rhodium complex catalyst from carbonylation of olefin rhodium catalyst waste reaction solution.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 complex 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.
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.
US5237106 introduced a kind of with propargyl alcohol and carboxylic acid processing section inactivation carbonylation rhodium complex catalyst to improve the process of its catalytic activity.This patent is take propargyl alcohol and acetic acid as reaction reagent, and reaction pressure is normal pressure, 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.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 the carbonylation reaction catalyst for inactivation in the existing process units, a kind of catalyst recovery process that is easy to industrial implementation is provided, by in course of reaction, passing into gas, changing reaction pressure, solved the difficult problem of the easy polymerization of reactant in the regenerative process, regeneration rear catalyst activity is high.
The renovation process of described inactivation rhodium complex catalyst for carbonylation comprises 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 complex catalyst, under non-carbonylation condition, mix with the carboxylic acid compound with chemical formula RCOOH with the alkynol that contains 3～6 carbon atoms or ester, under hydrogen or condition of nitrogen gas, carry out regenerative response, obtain the treated reactant liquor that contains rhodium complex catalyst, wherein the mol ratio of alkynol or ester and rhodium is 1～100: 1, the mol ratio of alkynol or ester and carboxylic acid is 5: 1～1: 5, reaction time 5～20h, 20～140 ℃ of reaction temperatures, reaction pressure 0.1～1.0MPa, the R among the RCOOH represent hydrogen or an alkyl or aryl;
(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 complex catalyst;
(4) wash isolated organic phase with water, obtaining a kind ofly has the more solution that contains rhodium complex catalyst of high catalytic activity than aforementioned inactivation rhodium complex catalyst.
The reactant liquor of part inactivation of the present invention/inactivation rhodium complex catalyst, refer in the presence of rhodium complex 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.
" non-water " of the present invention 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 complex 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.
Reactant liquor starting material of the present invention contains a certain amount of aldehyde product, 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.The preference chain olefin(e) compound is to contain 2～20 carbon atoms, most preferably contains the alpha-olefin of 3～14 carbon atoms.Aldehyde product mass content in the reactant liquor starting material is 0～80%, preferred 30～70%.
Contained part inactivation in the reactant liquor/inactivation rhodium complex catalyst (pressing rhodium metal calculates), content is 1～50000mg/kg, preferred 100～2000mg/kg.
Described alkynol or the ester that contains 3～6 carbon atoms, preferred propargyl alcohol, ethyl propiolate, propargyl acetate, most preferably propargyl alcohol.
In the described carboxylic acid compound with chemical formula RCOOH, R represents hydrogen or an alkyl or aryl in the formula, especially alkyl or phenyl that contains 1～4 carbon atom, optimization acid's compound is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid or benzoic acid, most preferably acetic acid.
Concrete test method is as follows:
To contain the alkynol of 3～6 carbon atoms or the reactant liquor of ester, carboxylic acid and part inactivation/inactivation rhodium complex catalyst joins in the reactor, then closed reactor passes into nitrogen or hydrogen purge, behind the interior certain pressure of maintenance reactor, beginning slowly stirs, and adds thermal response.Charging sequence is to add first reactant liquor preferably, adds carboxylic acid again, adds at last alkynol or the ester that contains 3～6 carbon atoms.Reaction pressure is 0.1～1.0MPa, preferred 0.1～0.6MPa, most preferably 0.1～0.4MPa.20～140 ℃ of reaction temperatures, reaction time 5～20h.Containing the alkynol of 3～6 carbon atoms or the mol ratio of ester and rhodium metal is 1～100: 1, preferred 1～25: 1, and containing the alkynol of 3～6 carbon atoms or the mol ratio of ester and carboxylic acid is 5: 1～1: 5.
Contain unreacted carboxylic acid in the treated reactant liquor that contains rhodium complex 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%, preferred 5～15%.30～90 ℃ of neutralization reaction temperature, preferred 40～70 ℃, neutralization reaction time 0.5～5h.Reaction temperature is higher, and the amount that the aldehyde condensation by-product generates is just larger; And temperature is lower, more easily forms emulsion, is difficult for layering.The treated volume ratio that contains the rhodium complex 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: 1, 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 complex catalyst.
Renovation process of the present invention has been controlled the polymerisation of reaction reagent (alkynol or the ester that contain 3～6 carbon atoms) preferably, thereby its consumption reduces in course of reaction, and the catalyst activity after the regeneration is high, and technological process is easy, is easier to industrialization.
According to renovation process of the present 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, keep certain reaction pressure after passing into gas, 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) solved the polymerization difficult problem of regenerative response reagent (alkynol or the ester that contain 3～6 carbon atoms) in regenerative process, its consumption reduces, and reaction condition relaxes, and technological process is easy, and is high through the catalyst activity of regeneration.
(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.
Embodiment 1～8
In the butyraldehyde reactant liquor that the industry butyl octanol unit produces, the rhodium complex catalyst activity is reduced to approximately 28% (comparing with fresh rhodium complex catalyst) from 100%, removes behind the part butyraldehyde approximately 1000mg/kg of rhodium content, triphenylphosphine content approximately 10%.This reactant liquor 60g that contains the part decaying catalyst is joined in the reactor of 100ml, use the nitrogen blowing reactor, then add the alkynol that contains 3～6 carbon atoms of different proportionings as shown in table 1 or ester and carboxylic acid and react, under certain pressure and temperature, carry out regenerative response.Add 10% the triethanolamine aqueous solution after reaction finishes in the reactor, neutralize unreacted carboxylic acid or halide generate water soluble salt again.
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.
Embodiment experiment condition and catalyst activity evaluation see Table 1.
Embodiment 5 is pressurized to 0.2MPa with hydrogen, and other embodiment all uses nitrogen.
Embodiment 8 used carboxylic acids are n-butyric acie, and other embodiment all uses acetic acid.
Table 1 experiment condition and catalyst activity evaluation table
Illustrate: fresh rhodium complex catalyst activity is 100%, pending inactivation rhodium complex catalyst activity 28%.
In the reactant liquor that contains part inactivation rhodium complex catalyst that detects not regeneration, chlorinity 29mg/kg, Chlorine in Solution content is 7mg/kg after the regeneration.Therefore, compared with prior art, the process that the present invention adopts, eliminated simultaneously in the reactant liquor after the regeneration because of the poisoning of external source halide and carboxylic acid inhibitor, regenerative response reagent (alkynol or the ester that contain 3～6 carbon atoms) consumption is low, reaction condition relaxes, and technological process is easy, and is high through the catalyst activity of regeneration.
Claims (10)
1. a renovation process that is used for the inactivation rhodium complex 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 complex catalyst, under non-carbonylation condition, mix with the carboxylic acid compound with chemical formula RCOOH with the alkynol that contains 3～6 carbon atoms or ester, under hydrogen or condition of nitrogen gas, carry out regenerative response, obtain the treated reactant liquor that contains rhodium complex catalyst, wherein the mol ratio of alkynol or ester and rhodium is 1～100: 1, the mol ratio of alkynol or ester and carboxylic acid is 5: 1～1: 5, reaction time 5～20h, 20～140 ℃ of reaction temperatures, reaction pressure 0.1～1.0MPa, the R among the RCOOH represent hydrogen or an alkyl or aryl;
(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 complex catalyst;
(4) wash isolated organic phase with water, obtaining a kind ofly has the more solution that contains rhodium complex catalyst of high catalytic activity than aforementioned inactivation rhodium complex catalyst.
2. renovation process according to claim 1 is characterized in that the aldehyde compound mass content is 0～80% in the described reactant liquor that contains the inactivation rhodium complex catalyst, and the inactivation rhodium complex catalyst is pressed rhodium metal and calculated, and content is 1～50000mg/kg.
3. renovation process according to claim 2 is characterized in that the aldehyde compound mass content is 30～70% in the described reactant liquor that contains the inactivation rhodium complex catalyst, and the inactivation rhodium complex 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 compound with chemical formula 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 with chemical formula RCOOH is formic acid, acetic acid, propionic acid, n-butyric acie, isobutyric acid or benzoic acid.
6. renovation process according to claim 1, the mol ratio that it is characterized in that described alkynol or ester and rhodium is 1～25: 1, reaction pressure 0.1～0.4MPa.
7. renovation process according to claim 1 is characterized in that described alkynol or ester are propargyl alcohol, ethyl propiolate or propargyl acetate, preferred propargyl alcohol.
8. renovation process according to claim 1, it is characterized in that the mass content of the described tertiary alkanol amine of step (2) in the aqueous solution is 1～25%, 30～90 ℃ of neutralization reaction temperature, neutralization reaction time 0.5～5h, the treated volume ratio that contains the rhodium complex catalyst reactant liquor that tertiary alkanol amine aqueous solution consumption and step (1) obtain is 0.5～5: 1.
9. renovation process according to claim 1 is characterized in that described tertiary alkanol amine is triethanolamine, three b propanol amine, methyl diethanolamine or phenyldiethanol-amine, preferred triethanolamine.
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, 30～90 ℃ of washing temperature, and washing times is 1～2 time.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950028A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Regeneration method for inactivated rh-p (rhodium-phosphine) complex catalyst for carbonylation reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5183943A (en) * | 1991-03-18 | 1993-02-02 | Union Carbide Chemicals & Plastics Technology Corporation | Reactivation of hydroformylation catalysts |
| 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 |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5183943A (en) * | 1991-03-18 | 1993-02-02 | Union Carbide Chemicals & Plastics Technology Corporation | Reactivation of hydroformylation catalysts |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102950028A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Regeneration method for inactivated rh-p (rhodium-phosphine) complex catalyst for carbonylation reaction |
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