CN1781603A - Loaded complex catalyst for isobutylene hydrogen formylation reaction - Google Patents
Loaded complex catalyst for isobutylene hydrogen formylation reaction Download PDFInfo
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- CN1781603A CN1781603A CN 200410081353 CN200410081353A CN1781603A CN 1781603 A CN1781603 A CN 1781603A CN 200410081353 CN200410081353 CN 200410081353 CN 200410081353 A CN200410081353 A CN 200410081353A CN 1781603 A CN1781603 A CN 1781603A
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Abstract
The present invention features that loaded rhodium and cobalt bimetal complex catalyst has the advantages of high activity of rhodium catalyst and low cost of cobalt catalyst combined and excellent reaction effect. Through reaction at the reaction condition of 2.5 MPa for 5 hr, isobutylene converting rate can reach 62%, isovaleraldehyde selectivity can reach 89%, optimized isovaleraldehyde producing rate may reach 1257 mol/mol-Rh each hour, and no side product tert-valeraldehyde is produced. In the same time, the catalyst preparing process has been optimized.
Description
Technical background
The invention relates to a kind of isobutene hydroformylation new catalyst, a kind of more precisely support type rhodium cobalt dual-metal complex compound catalyst.
Hydroformylation of olefin is industrial important method by olefin production aldehyde and correspondent alcohol, and its used catalyst mainly is group VIII metal or its compound.The olefin hydroformylation catalyst of Shi Yonging is cobalt and compound thereof the earliest, has developed rhodium catalyst afterwards.Compare with Co catalysts, that rhodium catalyst has is active high, selectivity is good, reaction condition is gentle, linear chain aldehyde content advantages of higher in the product, becomes the focus that the researcher pays close attention to.In the commercial Application process, rhodium catalyst is dissolved in the form of phosphine complex compound and forms homogeneous catalysis system in the reactant, and this has brought difficulty just for reaction afterproduct and catalyst separation.For 5 rudimentary chain hydrocarbons below the carbon, usually adopt the method for distillation to realize separating, but for 6 long-chain olefins more than the carbon, because the product boiling point is higher, distillation can cause problems such as product polymerization, catalyst decomposes inactivation, so distillating method is not suitable for long-chain olefin.For addressing this problem, the researcher has proposed water-oily biphasic catalysis system, catalyst is at water, reactant and product are at oil phase, reaction back standing demix just can reach the purpose of separation, and is very big but this system is influenced by the solubility of alkene in water, along with the growth of carbochain, the solubility of alkene in water descends, and the speed of this system catalytic reaction also sharply descends.There is the researcher to increase the solubility of alkene, but brought a series of problems such as emulsification by adding surfactant.
The heterogeneous post processing that turns to hydroformylation reaction of catalyst provides a new approach.The researcher loads on catalytic complexes on the various carriers, developed to support the liquid film catalyst and support the moisture film catalyst, but this class catalyst activity component runs off seriously in reaction, and complicated process of preparation, reaction condition is harsh, has influenced it and has applied.And relevant directly reactive metal being carried on also rarely has report with the ligand modified patent that makes catalyst on the carrier again, and relevant isobutene hydroformylation reaction also is blank with the patent report of support type rhodium cobalt dual-metal complex compound catalyst.
The invention provides a kind of isobutene hydroformylation reaction efficient catalyst.This catalyst is in conjunction with Rh high activity of catalyst and the cheap characteristics of Co catalyst, the hydroformylation activity height, and selectivity is good, and catalyst separation is easy, and recycling is convenient.The catalyst of the present invention's report and the good catalytic effect in the isobutene hydroformylation reaction thereof are not seen reported in literature as yet, have tangible innovative significance.
Summary of the invention
The invention is characterized in industrial SiO
2Be carrier, with the rhodium cobalt dual-metal as active component (is precursor with rhodium base salt), adopt the immersion process for preparing catalyst precarsor, flood the part triphenylphosphine after the roasting again, obtain efficient catalyst, it is active and selectivity is all high a lot of than unit loads type rhodium catalyst, and the conversion ratio of isobutene 5h reaches 62.0%, the selectivity of isopentyl aldehyde reaches 89.3%, does not have the generation of the special valeral of accessory substance.
Feature of the present invention also is: the mol comparison catalyst performance influence of cobalt rhodium is bigger, and the mol ratio of suitable cobalt rhodium is 0～20, is preferably 1～10; Rh content has considerable influence to catalyst performance, and suitable rhodium content is (with Rh
2O
3The mass content meter) is 0.01%～5%, is preferably 0.05%～1%; Sintering temperature and calcination atmosphere are bigger to catalyst performance influence, in the nitrogen atmosphere 100 ℃～600 ℃ better, be preferably 300 ℃～600 ℃; PPh
3With the mol ratio of Rh be 0～50, be preferably 0～20.
Catalyst among the present invention is used for the isobutene hydroformylation reaction, investigates and carries out in stainless steel cauldron, and product is analyzed with gas chromatograph.
Embodiment
The invention will be further described below in conjunction with embodiment:
Reference example one:
(1) Preparation of Catalyst
Weighing 0.253g Co (NO
3)
26H
2O is dissolved in the distilled water, adds the SiO of 2.928g
2Carrier impregnation 45min, evaporate to dryness in 80 ℃ of water-baths then, dry 24h in 120 ℃ of baking ovens, 400 ℃ of roasting 3h in the nitrogen protection pipe type stove.The solid that obtains is used the acetone soln dipping 30min that contains the 0.124g triphenylphosphine under the nitrogen protection in Rotary Evaporators after, acetone is removed in vacuum drying, obtains supporting the cobalt-based complex compound catalyst, is labeled as CO1Si-TPP; Store for future use in the inert atmosphere.
(2) activity of such catalysts is investigated
The isobutene hydroformylation reaction stirs in the autoclave in the 250ml magnetically-actuated and carries out.In reactor, add 80ml solvent xylene and 1.0g catalyst, close autoclave, the air in the usefulness nitrogen replacement system three times, more once with the synthesis gas displacement, add a certain amount of isobutene liquid then in still, charge into about 1MPa synthesis gas, charge into synthesis gas to 2.5MPa after stirring is warmed up to 100 ℃, quicken to stir, the reaction timing, pressure is charged to 2.5MPa after dropping to 2.0MPa again, reaction time 5h, and reaction finishes back water-cooled to room temperature and drives still.Reactant liquor is analyzed with the SC-200 gas chromatograph, GDX-401 post, carrier gas Ar.
The result shows that this supports, and conversion for isobutene is 30.16% on the cobalt-based complex compound catalyst, and the selectivity of isopentyl aldehyde is 38.52%.
Reference example two
Weighing 0.073g RhCl
33H
2O and 2.964g SiO
2, concrete steps are with the Preparation of Catalyst in the reference example one, and activity of such catalysts is investigated with reference example one.The result shows that conversion for isobutene is 44.66%, and the selectivity of isopentyl aldehyde is 77.43%.
Embodiment one
Weighing 0.073g RhCl
33H
2O, 0.253g Co (NO
3)
26H
2O and 2.892g SiO
2, concrete steps are with the Preparation of Catalyst in the reference example one, and activity of such catalysts is investigated with reference example one.The result shows that conversion for isobutene is 62.0%, and the selectivity of isopentyl aldehyde is 89.3%.
Embodiment two
Preparation of catalysts is similar to embodiment one, fixing cobalt rhodium proportioning, and the rhodium content of regulating catalyst is (with Rh
2O
3The weight percentage meter): 1.2%; 0.39%; 0.19%; 0.096%, make catalyst series, the active investigation ditto.Concrete reaction result sees Table 1.
Table 1 rhodium content is (with Rh
2O
3The weight percentage meter) to the influence of catalytic performance
| Rh content (Rh 2O 3wt％) | 0.096 | 0.19 | 0.39 | 1.2 |
| ASTYa (mol/mol-Rh·h) | 1257.5 | 994.5 | 465.1 | 209.8 |
The average generating rate of isopentyl aldehyde on a unit Rh atom activated centre
Implementation column three
Preparation of catalysts is similar to embodiment one, the Co/Rh of catalyst (mol)=2, PPh
3/ Rh (mol)=5, the sintering temperature and the calcination atmosphere of change catalyst, preparation catalyst series.Activity of such catalysts is investigated and is similar to embodiment one, and the reactor size is 100mL, and the dimethylbenzene consumption is 40mL.Concrete reaction result sees Table 2.
Table 2 sintering temperature and calcination atmosphere are to the influence of catalyst performance
| Sintering temperature (℃) | Calcination atmosphere | Isobutene conversion (%) | Isopentyl aldehyde selectivity (%) | Isopentyl aldehyde productive rate (%) | ASTY a (mol/mol-Rh.h) |
| 300 400 500 400 | N 2 N 2 N 2Air | 25.65 37.82 11.20 29.82 | 72.23 76.58 62.08 71.16 | 18.52 28.96 6.96 21.22 | 238.9 448.4 114.9 352.2 |
The average generating rate of isopentyl aldehyde on a unit catalyst Rh atom activated centre
Therefore, 400 ℃ of N
2In the atmosphere catalyst of roasting catalytic reaction in the time of 5 hours the isopentyl aldehyde selectivity be 76.6%, space-time yield is 448mol/mol-Rh/h.
Claims (5)
1 one kinds of new catalysts that are used for the isobutene hydroformylation reaction is characterized in that adopting SiO
2As carrier, the rhodium cobalt dual-metal is as its active component, triphenylphosphine (PPh
3) as part; The selectivity of isopentyl aldehyde is up to 89% in the isobutene hydroformylation reaction; , generating rate reaches more than the 1200mol/mol-Rh.h.
2 new catalysts as claimed in claim 1 is characterized in that the mol comparison catalyst performance influence of cobalt rhodium is bigger, and the mol ratio of suitable cobalt rhodium is 0～20, is preferably 2～10.
3 new catalysts as claimed in claim 1 is characterized in that Rh content has considerable influence to catalyst performance, and suitable rhodium content is (with Rh
2O
3The mass content meter) is 0.01%～5%, is preferably 0.05%～1%.
4 new catalysts as claimed in claim 1 is characterized in that sintering temperature and calcination atmosphere are bigger to catalyst performance influence, in the nitrogen atmosphere 100 ℃～600 ℃ better, be preferably 300 ℃～600 ℃.
5 new catalysts as claimed in claim 1 is characterized in that PPh
3With the mol ratio of Rh be 0～50, be preferably 1～20.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410081353 CN1781603A (en) | 2004-11-30 | 2004-11-30 | Loaded complex catalyst for isobutylene hydrogen formylation reaction |
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|---|---|---|---|
| CN 200410081353 CN1781603A (en) | 2004-11-30 | 2004-11-30 | Loaded complex catalyst for isobutylene hydrogen formylation reaction |
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ID=36772448
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100496736C (en) * | 2007-05-31 | 2009-06-10 | 南京大学 | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation |
| CN109894147A (en) * | 2019-02-21 | 2019-06-18 | 中科合成油技术有限公司 | A kind of load type cobalt-base catalyst and preparation method thereof and application method |
| CN111085198A (en) * | 2019-11-28 | 2020-05-01 | 山东新和成维生素有限公司 | Hydroformylation catalyst and preparation method and application thereof |
| CN115805102A (en) * | 2022-11-25 | 2023-03-17 | 中科合成油技术股份有限公司 | Heterogeneous catalyst for preparing high-carbon aldehyde by hydroformylation of medium-long chain alpha-olefin and preparation method thereof |
-
2004
- 2004-11-30 CN CN 200410081353 patent/CN1781603A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100496736C (en) * | 2007-05-31 | 2009-06-10 | 南京大学 | Water soluble ligand rhodium complex catalyst used for preparing aldehyde with dicyclopentadiene hydroformylation |
| CN109894147A (en) * | 2019-02-21 | 2019-06-18 | 中科合成油技术有限公司 | A kind of load type cobalt-base catalyst and preparation method thereof and application method |
| CN111085198A (en) * | 2019-11-28 | 2020-05-01 | 山东新和成维生素有限公司 | Hydroformylation catalyst and preparation method and application thereof |
| CN111085198B (en) * | 2019-11-28 | 2022-11-08 | 山东新和成维生素有限公司 | Hydroformylation catalyst and preparation method and application thereof |
| CN115805102A (en) * | 2022-11-25 | 2023-03-17 | 中科合成油技术股份有限公司 | Heterogeneous catalyst for preparing high-carbon aldehyde by hydroformylation of medium-long chain alpha-olefin and preparation method thereof |
| CN115805102B (en) * | 2022-11-25 | 2024-04-05 | 中科合成油技术股份有限公司 | Heterogeneous catalyst for preparing high-carbon aldehyde by hydroformylation of medium-long chain alpha-olefin and preparation method thereof |
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