CN108080030A - A kind of immobilized method of olefin hydroformylation catalyst - Google Patents
A kind of immobilized method of olefin hydroformylation catalyst Download PDFInfo
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- CN108080030A CN108080030A CN201711393196.5A CN201711393196A CN108080030A CN 108080030 A CN108080030 A CN 108080030A CN 201711393196 A CN201711393196 A CN 201711393196A CN 108080030 A CN108080030 A CN 108080030A
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- catalyst
- rhodium
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- olefin hydroformylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of olefin hydroformylation catalyst and its immobilized methods, and the rhodium in rhodium carbonyl catalyst and other metals are formed metal solid solution so as to be fixed on the surface of porous carrier, obtain a kind of novel carriers catalyst for olefin hydroformylation.So as to solve the immobilized problem to be solved of hydroformylation catalyst.The carried catalyst has the performance similar with immobilized preceding homogeneous catalyst, and active component is not lost in substantially in single reaction, while immobilized cost is relatively low.
Description
Technical field
The present invention relates to technical field of organic chemistry, are related to a kind of immobilized method of olefin hydroformylation catalyst.
Background technology
The development of hydroformylation technology mainly has benefited from the development of coal chemical industry and the promotion of petrochemical industry, petroleum cracking production
The olefin compounds such as raw substantial amounts of ethylene, propylene, butylene, substantial amounts of alkene can be also made by Fischer-Tropsch techniques
Raw material, these olefines provide important substance basis for the development of hydroformylation.
The principal product aldehyde of hydroformylation reaction as a kind of chemical intermediate, can synthetic ester, carboxylic acid and fatty amine etc.,
Its hydrogenation products alcohol can be used as surfactant, plasticizer, solvent etc., be widely used in field of fine chemical, have non-
Often wide application value.
It is traditional prepare valeral, amylalcohol, there are side reaction is more, damage ratio is more serious, the receipts of product for the production technology of valeric acid
Rate and the more low shortcoming of selectivity, and hydroformylation reaction is a Green Chemical Engineering Process, belongs to atomic economy reaction, tool
Body meaning is that the atom in product is all transferred in product, will not generate discarded object and environmentally harmful substance.With dirt
Dye is few, high selectivity, and catalyst activity is high and the advantages that can realizing catalyst circulation, is acknowledged as the generation of friendly process
Table is the field for the chemical industry and primary study given priority to both at home and abroad at present.Hydroformylation reaction is to probe into transiens gold
Belong to as the catalyst choice of active component and the typical reaction of activity.The hydroformylation for studying C4 and high alpha-olefin is anti-
The research answered is to represent very much meaning, and hydroformylation reaction is often associated with some side reactions, such as hydrogenation, isomerization.It is just different
The height of the degree of the ratio of structure, isomerization and hydrogenation is largely to rely on the species of selected catalyst.
So far, hydroformylation catalyst is largely homogeneous catalyst, such as following table
The activity of homogeneous catalyst, selectivity are all higher, reaction mechanism and dynamic (dynamical) research be easy to deeply, be easy into
Row characterization.In addition, homogeneous catalyst reaction condition is mild, the pressure and temperature of reaction is of less demanding, be easy to control, side reaction is few
The advantages that, however still there are many shortcomings for homogeneous catalyst：
L, catalyst molecule structure is more complicated, and synthesis is difficult, to air-sensitive；
2nd, activated centre atom is mostly precious metal element, and price is costly；
3rd, thermal stability is poor, and catalyst attrition is bigger；
4th, homogeneous catalyst is recycled and separated cumbersome；
The defects of homogeneous catalyst is due on nature causes it to be restricted in commercial Application.Heterogeneous catalyst
Selectivity, activity for homogeneous catalyst than relatively low.But heterogeneous catalyst has, and preparation process is more convenient, Yi Yurong
The advantages that agent separates.Therefore it both can be concentrated advantage by homogeneous catalyst is immobilized.
Current existing immobilized technology is usually all by being modified to carrier, loads ligand in advance in carrier surface
Or in duct, then the ligand of immobilization and metal is complexed, but it is excessively high to be limited to the immobilized technical costs, at present still without
The example of industrial applications.And directly using homogeneous catalyst impregnated made from carried catalyst it is tight there are metal loss
The problem of weight, not only increase cost, while will also result in environmental pollution.And the aldehyde yield of simple metals carried catalyst is low, because
The immobilized of this catalyst needs to solve the problems, such as the holding for being catalyst performance, reduces the turnover rate of active component and immobilized
The cost of change.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of immobilized method of olefin hydroformylation catalyst, by carbonyl
Rhodium in base rhodium catalyst forms metal solid solution so as to be fixed on the surface of porous carrier with other metals, obtains one kind and is used for
The novel carriers catalyst of olefin hydroformylation.So as to solve the immobilized problem to be solved of hydroformylation catalyst.
To realize above-mentioned target, the first aspect of the present invention provides olefin hydroformylation catalyst, including 0.01~
At least one of 30% rhodium carbonyl, 0.01~30% platinum, palladium, ruthenium, gold, rare earth or alkaline-earth metal, surplus are porous carrier,
The porous carrier is selected from least one of aluminium oxide, silica, diatomite, titanium oxide, zirconium oxide, activated carbon.
Preferably, the rhodium carbonyl catalyst is:
Preferably, R is selected from：In one kind.
Preferably, the rhodium carbonyl catalyst is acetylacetonatodicarrhodium rhodium and/or acetylacetone,2,4-pentanedione rhodium carbonyl.
Second aspect of the present invention provides the immobilized method of olefin hydroformylation catalyst, includes the following steps：
It (1), will after water or organic solvent dissolving by rhodium carbonyl or the wherein metal salt of mesosome and one or more of non-rhodiums
Solution is added in porous carrier, is stirred evenly, and obtains suspension A；
(2) suspension A is heated, after solvent evaporated, residue is added in into alkaline solution, adjustings pH is 8-14；
(3) a certain amount of reducing agent is added in the residue, reduces the metal salt of the foregoing non-rhodium of one or more
For metallic state, filter cake is obtained after filtering drying；
(4) filter cake of step (3) is added in into ligand needed for rhodium carbonyl catalyst, catalyst is obtained after filtering drying.
The metal salt of one or more of non-rhodiums, one kind in nitric acid metal salt, chlorination metal salt, sulfuric acid metal salt or
It is several；Preferably, metal salt is one or more of cobalt nitrate, ruthenic chloride.
In step (3), addition reducing agent is sodium borohydride.
Third aspect present invention provides the height that foregoing olefin hydroformylation catalyst is applied to hydroformylation of olefin
In the olefine reaction of molecular weight.
Carried catalyst of the present invention, can be powder or preformed catalyst,
The carried catalyst has the performance similar with immobilized preceding homogeneous catalyst, active component base in single reaction
This is not lost in, while immobilized cost is relatively low.
Specific embodiment
In order to make it easy to understand, the present invention will be described in detail by specific embodiment below.It needs to refer in particular to
Go out, the description that these descriptions are merely exemplary, and be not meant to limit the scope of the invention.Opinion according to this specification
It states, many variations of the invention, change will be apparent from for one of ordinary skill in the art.
Embodiment 1
After the ruthenic chloride dissolving of the acetylacetone,2,4-pentanedione rhodium carbonyl containing 1 gram of rhodium and 1 gram of ruthenium, 98 grams of activated carbons are added in, at 100 DEG C
Stirring is evaporated to solvent, and pH to 10 is adjusted using potassium hydroxide solution, after filtration washing, adds in the sodium borohydride of theoretical amount 20%
Solution is reduced, and after filtering drying, filter cake is added in the cyclohexane solution of the triphenylphosphine of 2 times of theoretical amounts, in nitrogen at 60 DEG C
Filtering drying obtains catalyst after stirring half an hour under gas shielded.
Embodiment 2
After the cobalt nitrate dissolving of the acetylacetone,2,4-pentanedione rhodium carbonyl containing 1 gram of rhodium and 1 gram of cobalt, 98 grams of activated carbons are added in, at 100 DEG C
Stirring is evaporated to solvent, and pH to 10 is adjusted using potassium hydroxide solution, after filtration washing, adds in the sodium borohydride of theoretical amount 20%
Solution is reduced, and after filtering drying, filter cake is added in the cyclohexane solution of the triphenylphosphine of 2 times of theoretical amounts, in nitrogen at 60 DEG C
Filtering drying obtains catalyst after stirring half an hour under gas shielded.
Embodiment 3
After the acetylacetone,2,4-pentanedione rhodium carbonyl containing 1 gram of rhodium, the cobalt nitrate containing 1 gram of cobalt and the ruthenic chloride dissolving containing 1 gram of ruthenium, add in
98 grams of activated carbons, stirring to solvent is evaporated under 100 degrees Celsius, is adjusted pH to 10 using potassium hydroxide solution, after filtration washing, is added
The sodium borohydride solution for entering theoretical amount 20% is reduced, and after filtering drying, filter cake is added in the triphenylphosphine of 2 times of theoretical amounts
Cyclohexane solution, filtering drying obtains catalyst after stirring half an hour under nitrogen protection at 60 DEG C.
Embodiment 4
Catalyst made from Examples 1 to 3 is added in autoclave, adds in mixed olefins, adds in carbon monoxide and hydrogen,
The ratio of carbon monoxide and hydrogen is 1：1, pressure is 0.2~5.0MPa, and reaction temperature is 80-120 DEG C, mixing speed
500rpm is reacted to system pressure and no longer declined.Liquid product is taken to determine using compounds GC-MS system (GC-MS) product
Property.As a result the conversion ratio of 3 kinds of catalyst and selectivity are as follows, and by-product is mainly double-bond hydrogenation resulting paraffins.
| Catalyst is numbered | Olefin conversion | Selectivity |
| Embodiment 1 | 96% | 99% |
| Embodiment 2 | 97% | 100% |
| Embodiment 3 | 99% | 98% |
Embodiment 5
After the acetylacetone,2,4-pentanedione rhodium carbonyl containing 1 gram of rhodium, the cobalt nitrate containing 1 gram of cobalt and the ruthenic chloride dissolving containing 1 gram of ruthenium, add in
98 grams of granular activated carbons, stirring to solvent is evaporated at 100 DEG C, is adjusted pH to 10 using potassium hydroxide solution, after filtration washing, is added
The sodium borohydride solution for entering theoretical amount 20% is reduced, and after filtering drying, filter cake is added in the triphenylphosphine of 2 times of theoretical amounts
Cyclohexane solution, filtering drying obtains catalyst after stirring half an hour under nitrogen protection at 60 DEG C.
Embodiment 6
Catalyst made from embodiment 5 is added in fixed bed, is passed through mixed olefins and carbon monoxide and hydrogen, an oxidation
The ratio of carbon and hydrogen is 1：1, gas liquid ratio 1000, air speed 4, pressure is 0.2~5.0MPa, and reaction temperature is 80-120 DEG C, is taken
Liquid product carries out product using compounds GC-MS system (GC-MS) qualitative.As a result the conversion ratio of catalyst is 100%, selection
Property 97%, by-product is mainly double-bond hydrogenation resulting paraffins.
Embodiment 7
After the acetylacetone,2,4-pentanedione rhodium carbonyl containing 1 gram of rhodium, the cobalt nitrate containing 1 gram of cobalt and the ruthenic chloride dissolving containing 1 gram of ruthenium, add in
98 grams of granular activated carbons, stirring to solvent is evaporated at 100 DEG C, is adjusted pH to 10 using potassium hydroxide solution, after filtration washing, is added
The sodium borohydride solution for entering theoretical amount 20% is reduced, and after filtering drying, filter cake is added in the triphenylphosphine benzene of 2 times of theoretical amounts
The aqueous solution of sodium sulfonate, filtering drying obtains catalyst after stirring half an hour under nitrogen protection at 60 DEG C.
Embodiment 8
Catalyst made from embodiment 5 is added in fixed bed, is passed through mixed olefins and carbon monoxide and hydrogen, an oxidation
The ratio of carbon and hydrogen is 1：1, gas liquid ratio 1000, air speed 4, pressure is 0.2~5.0MPa, and reaction temperature is 80-120 DEG C, is taken
Liquid product carries out product using compounds GC-MS system (GC-MS) qualitative.As a result the conversion ratio of catalyst is 100%, selection
Property 99%, by-product is mainly double-bond hydrogenation resulting paraffins.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
Present disclosure can be understood and implemented according to this, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (6)
1. olefin hydroformylation catalyst, which is characterized in that it includes 0.01~30% rhodium carbonyl, 0.01~30% platinum, palladium,
At least one of ruthenium, gold, rare earth or alkaline-earth metal, surplus are porous carrier, and the porous carrier is selected from aluminium oxide, oxidation
At least one of silicon, diatomite, titanium oxide, zirconium oxide, activated carbon.
2. olefin hydroformylation catalyst according to claim 1, which is characterized in that the rhodium carbonyl catalyst is:
3. olefin hydroformylation catalyst according to claim 2, which is characterized in that R is selected from：
In one kind.
4. olefin hydroformylation catalyst according to claim 1, which is characterized in that the carbonyl
Base rhodium catalyst is acetylacetonatodicarrhodium rhodium and/or acetylacetone,2,4-pentanedione rhodium carbonyl.
5. such as the immobilized method of claim 1-4 any one of them olefin hydroformylation catalyst, include the following steps：
(1) by rhodium carbonyl or the wherein metal salt of mesosome and one or more of non-rhodiums, with water or organic molten
After agent dissolving, solution is added in porous carrier, is stirred evenly, obtains suspension A；
(2) suspension A is heated, after solvent evaporated, residue is added in into alkaline solution, adjusts pH
For 8-14；
(3) a certain amount of reducing agent is added in the residue, makes the foregoing non-rhodium of one or more
Metal salt is reduced to metallic state, and filter cake is obtained after filtering drying；
(4) filter cake of step (3) is added in into ligand needed for rhodium carbonyl catalyst, is obtained after filtering drying
Catalyst.
6. olefin hydroformylation catalyst described in claim 1 is applied to the alkene of the high molecular weight of hydroformylation of olefin
In reaction.
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| CN201711393196.5A CN108080030A (en) | 2017-12-21 | 2017-12-21 | A kind of immobilized method of olefin hydroformylation catalyst |
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| CN201711393196.5A CN108080030A (en) | 2017-12-21 | 2017-12-21 | A kind of immobilized method of olefin hydroformylation catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433065A (en) * | 2022-08-22 | 2022-12-06 | 万华化学集团股份有限公司 | Preparation method of 1,3-butanediol |
| CN115672407A (en) * | 2022-11-23 | 2023-02-03 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monatomic rhodium catalyst and preparation and application methods thereof |
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| CN106622374A (en) * | 2016-11-30 | 2017-05-10 | 福州大学 | Resin-based immobilized rhodium-phosphine complex catalyst as well as preparation method and application of catalyst |
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| CN115672407A (en) * | 2022-11-23 | 2023-02-03 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monatomic rhodium catalyst and preparation and application methods thereof |
| CN115672407B (en) * | 2022-11-23 | 2024-02-02 | 中国石油大学(华东) | Phosphine ligand modified carbon-supported monoatomic rhodium catalyst and preparation and application methods thereof |
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