Olefin two-phase hydroformylation method

Abstract

The invention relates to an olefin two-phase hydroformylation method, which consists of three parts: polyether guanidine mesylate ionic liquid (PGMILs) with room temperature solidifiable characteristics, complex catalysts (Rh-TPPTS) formed by RhCl3.3H2O or dicarbonylacetylacetonato rhodium and triphenylphosphine sodium trithionate (TPPTS), and reactants of C6-C14 straight chain 1-olefin, wherein the Rh-TPPTS is dissolved in the PGMILs to form a lower layer catalyst phase, the C6-C14 straight chain 1-olefin or product aldehyde forms an upper layer organic phase, the selectivity of high-carbon aldehyde is 85 to 99 percent, the mol ratio of normal aldehyde to isomerism aldehyde is 2.0 to 2.4, the PGMILs phase containing Rh-TPPTS can be cyclically used for 35 times, the activity and the selectivity are unchanged, the accumulated conversion number (TON) reaches higher than 30000, rhodium flowing to the product phase is 0.04 percent to 0.07 percent, and ultra-long-period catalysis activity and selectivity can be realized.

Description

[0001] technical field

[0002] The invention relates to the technical field of chemistry and chemical engineering, in particular to a two-phase hydroformylation method of olefins, in particular to a two-phase hydroformylation process of high-carbon olefin ionic liquid and its catalyst separation and circulation process.

[0003] Background technique

[0004] The rhodium-catalyzed hydroformylation of olefins is a typical atom-economic reaction, and it is also one of the most reported and researched frontier fields of chemistry. It has become an ideal method for the preparation of high-carbon aldehydes / alcohols. However, the recovery and recycling of expensive rhodium catalysts from hydroformylation products has been a great challenge and the focus of attention for nearly three decades. In order to solve the problem of recovery and recycling of rhodium catalyst in hydroformylation reaction, "homogeneous catalysis heterogeneous" has attracted much attention. The liquid / liqui...

Examples

Embodiment 1

[0018] Two-phase 1-octene hydroformylation of PGMILs

[0019] Under nitrogen or argon atmosphere, add TPPTS, Rh(acac)(CO) into a 60mL stainless steel autoclave 2 and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / Rh(acac)(CO) 2 =10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / Rh(acac)(CO) 2 =1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurize to 5.0MPa, the reaction temperature is 85°C, the reaction time is 24 hours, then lower to room temperature, vent the synthesis gas and open the kettle, add 1-octene and internal standard cyclohexyl under nitrogen or argon atmosphere alkanes in the ratio 1-octene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After e...

Embodiment 2

[0021] Two-phase 1-decene hydroformylation of PGMILs

[0022] Under nitrogen or argon atmosphere, add TPPTS and RhCl to a 60mL stainless steel autoclave 3 ·3H 2 O and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / RhCl 3 ·3H 2 O=10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / RhCl 3 ·3H 2 O=1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurized to 5.0MPa, reaction temperature 85°C, reaction time 24 hours, then lowered to room temperature, vented synthesis gas and opened the kettle, added 1-decene and internal standard n-octyl under nitrogen or argon atmosphere alkanes in the ratio 1-decene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After extraction ...

Embodiment 3

[0024] Two-phase 1-dodecene hydroformylation of PGMILs

[0025] Under nitrogen or argon atmosphere, add TPPTS and RhCl to a 60mL stainless steel autoclave 3 ·3H 2 O and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / RhCl 3 ·3H 2 O=10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / RhCl 3 ·3H 2 O=1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurize to 5.0MPa, reaction temperature 85°C, reaction time 24 hours, then lower to room temperature, vent the synthesis gas and open the kettle, add 1-dodecene and internal standard normal under nitrogen or argon atmosphere Decane in the ratio 1-dodecene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After extraction w...

[0001] technical field

[0002] The invention relates to the technical field of chemistry and chemical engineering, in particular to a two-phase hydroformylation method of olefins, in particular to a two-phase hydroformylation process of high-carbon olefin ionic liquid and its catalyst separation and circulation process.

[0003] Background technique

[0004] The rhodium-catalyzed hydroformylation of olefins is a typical atom-economic reaction, and it is also one of the most reported and researched frontier fields of chemistry. It has become an ideal method for the preparation of high-carbon aldehydes / alcohols. However, the recovery and recycling of expensive rhodium catalysts from hydroformylation products has been a great challenge and the focus of attention for nearly three decades. In order to solve the problem of recovery and recycling of rhodium catalyst in hydroformylation reaction, "homogeneous catalysis heterogeneous" has attracted much attention. The liquid / liqui...

Examples

Embodiment 1

[0018] Two-phase 1-octene hydroformylation of PGMILs

[0019] Under nitrogen or argon atmosphere, add TPPTS, Rh(acac)(CO) into a 60mL stainless steel autoclave 2 and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / Rh(acac)(CO) 2 =10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / Rh(acac)(CO) 2 =1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurize to 5.0MPa, the reaction temperature is 85°C, the reaction time is 24 hours, then lower to room temperature, vent the synthesis gas and open the kettle, add 1-octene and internal standard cyclohexyl under nitrogen or argon atmosphere alkanes in the ratio 1-octene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After e...

Embodiment 2

[0021] Two-phase 1-decene hydroformylation of PGMILs

[0022] Under nitrogen or argon atmosphere, add TPPTS and RhCl to a 60mL stainless steel autoclave 3 ·3H 2 O and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / RhCl 3 ·3H 2 O=10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / RhCl 3 ·3H 2 O=1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurized to 5.0MPa, reaction temperature 85°C, reaction time 24 hours, then lowered to room temperature, vented synthesis gas and opened the kettle, added 1-decene and internal standard n-octyl under nitrogen or argon atmosphere alkanes in the ratio 1-decene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After extraction ...

Embodiment 3

[0024] Two-phase 1-dodecene hydroformylation of PGMILs

[0025] Under nitrogen or argon atmosphere, add TPPTS and RhCl to a 60mL stainless steel autoclave 3 ·3H 2 O and [Me(EO) 16 TMG] OMs. Its ratio is: TPPTS / RhCl 3 ·3H 2 O=10 / 1 (molar ratio), [Me(EO) 16 TMG]OMs / RhCl 3 ·3H 2 O=1000 / 1 (mass ratio). Replace the air with nitrogen or argon 4 to 6 times, and then use synthesis gas (H 2 / CO=1:1) pressurize to 5.0MPa, reaction temperature 85°C, reaction time 24 hours, then lower to room temperature, vent the synthesis gas and open the kettle, add 1-dodecene and internal standard normal under nitrogen or argon atmosphere Decane in the ratio 1-dodecene / RhCl 3 ·3H 2 O=1000 / 1 (molar ratio). Then again with syngas (H 2 / CO=1:1) Pressurize to 5.0MPa, react at 85°C for 5 hours, then cool down to below 20°C, vent the synthesis gas and open the kettle, the lower PGMILs phase solidifies, the upper product aldehyde can be separated by decantation, or use normal After extraction w...

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