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One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand

A catalyst and heterocycle technology, applied in the field of one-step production of 1,3-propanediol from ethylene oxide and synthesis gas using catalysts with N-heterocycle ligands, which can solve the problem of expensive phosphine ligands and achieve good oxidation The effect of stability

Inactive Publication Date: 2008-10-01
SHELL INT RES MAATSCHAPPIJ BV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, phosphine ligands are relatively expensive, and it is desirable to have alternative ligand systems that provide the above advantages but are less expensive

Method used

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  • One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand
  • One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand
  • One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a N-heterocyclic ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-20

[0069] Examples 1-20 were carried out in a 300 cc capacity Parr reactor system connected to a syngas manifold. In Examples 1-12 the N-heterocyclic ligand was changed but only two cyclic ether solvents were used. The solvents were varied in Examples 13-20. Changes to other components and conditions are noted in the notes. The test data are given in Tables 1 and 2.

[0070] As mentioned above, 2,2'-bipyridine (DIPY), 2,2'-bipyrimidine (BPYM) and 2,4,6-tripyridyl-s-triazine (TPTZ) work particularly well. Table 1 presents the data using these three N-heterocycles and 1,10-phenanthroline (PHEN) in the one-step PDO synthesis. Wherein the PDO yield is calculated in moles based on the amount of ethylene oxide added, and the selectivity of PDO is estimated by gas chromatography (GC) analysis of the crude product fraction. Major by-products include ethanol (major by-product fraction), HPA intermediates, acetaldehyde and small amounts including 3-hydroxypropyl-2-hydroxyethyl ether, 3...

Embodiment 21

[0076] A typical lifetime study of the catalyst complex was performed in Example 21. The octacarbonyl dicobalt-dodecacarbonyl triruthenium-2,2'-bipyridine catalyst dissolved in 1,3-dioxolane was used as the catalyst precursor, EO was added 18 times and PDO distillation was carried out 4 times. Where the initial Co-Ru-DIPY stoichiometric ratio is 1:1:1, each EO hydroformylation is at 1 / 4 (CO / H 2 ) under syngas. Typical steps are as follows:

[0077] 1. Four additions of EO to a Co-Ru-N-heterocyclic catalyst in a cyclic ether solvent, each addition of EO was converted to PDO by hydroformylation / hydrogenation as described above.

[0078] 2. After removing the solvent, recover PDO by vacuum distillation.

[0079] 3. The bottom Co-Ru-N-heterocyclic catalyst solution in the PDO is circulated with fresh ether solvent.

[0080] The data are shown in Table 3:

[0081] table 3

[0082]

[0083] In general, a slow accumulation of organic heavy components, especially 3-hyd...

Embodiment 22

[0085] A series of experiments very similar to Example 21 was also performed in which intermediate solids formed during multiple cycles were removed by filtration (before distillation of PDO) and a small amount of make-up catalyst was added after 18 additions of EO. Add 4 more EOs for a total of 22. The EO uptake times for this second catalyst lifetime study are shown in FIG. 5 .

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Abstract

Disclosed is a new catalyst composition comprising a bimetallic Co-Ru catalyst complexed with a N-heterocylcic ligand that is effective, economical, and provides improvements in oxidative stability in the one step synthesis of 1,3-propanediol (1,3-PDO) from ethylene oxide and synthesis gas. For example, cobalt-ruthenium-2,2'-bipyrimidine, 2,2'-dipyridyl, or 2,4,6-tripridyl-s-triazine catalyst precursors in cyclic ether solvents, such as 1,3-dioxolane, 1,4-dioxolane, 1,4-dioxane, and 2-ethyl-2-methyl-1,3-dioxolane, provide good yields of 1,3-PDO in a one step synthesis.

Description

field of invention [0001] The present invention relates to the one-step synthesis of aliphatic 1,3-diols, especially 1,3-propanediol, from ethylene oxide and synthesis gas. More specifically, the present invention relates to a catalyst that provides high yield under mild conditions in the one-step synthesis of 1,3-propanediol and also has advantages in terms of cost and oxidation stability. The catalyst of the present invention comprises a homogeneous bimetallic cobalt-ruthenium catalyst having a bidentate N-heterocyclic ligand or a multidentate N-heterocyclic ligand. Background of the invention [0002] Aliphatic 1,3-diols, especially 1,3-propanediol, are widely used as monomer units of polyester and polyurethane, and as raw materials for synthesizing cyclic compounds. For example, CORTERRA (trademark) polymer, a polyester with outstanding properties, is prepared from 1,3-propanediol (hereinafter abbreviated as 1,3-PDO) and terephthalic acid. What attracts more attention ...

Claims

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Application Information

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IPC IPC(8): B01J31/18B01J31/20C07C45/58C07C29/141C07F15/00C07F15/06B01J31/28C07B61/00C07C29/16C07C29/44C07C31/20
CPCB01J2531/025B01J2231/48B01J31/28C07C29/16B01J2531/845B01J31/20B01J31/1815B01J2531/0208B01J2531/821B01J31/181B01J31/183Y02P20/52C07C31/205
Inventor K·D·艾伦T·G·詹姆斯J·F·尼夫顿J·B·鲍威尔L·H·斯劳P·R·韦德尔T·S·威廉姆斯
Owner SHELL INT RES MAATSCHAPPIJ BV
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