Removal of impurities formed during the production of 1,3-propanediol

A technology of propylene glycol and MW132, which is applied in the preparation of hydroxyl compounds, the preparation of organic compounds, chemical instruments and methods, etc., can solve the problems of reducing the recovery rate and purity of PDO, and the low rate of combined formation.

Inactive Publication Date: 2005-12-14
SHELL INT RES MAATSCHAPPIJ BV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

2:1 (mole) syngas at 110°C and 1000 psig (6900kPa), the selectivity is as high as 47 mole%, but the combined formation rate of PDO and 3-hydroxypropanal is quite low, which is 0.05-1 per liter per hour. 0.07 mol
Its formation reduces the overall recovery and purity of PDO

Method used

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  • Removal of impurities formed during the production of 1,3-propanediol
  • Removal of impurities formed during the production of 1,3-propanediol
  • Removal of impurities formed during the production of 1,3-propanediol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 176-1

[0059] The results in Table 2 show that treatment of a PDO sample contaminated with MW176 acetal at ambient temperature using the acid form of USY type zeolite was not effective in reverse conversion of the MW176 acetal. Room temperature inversion was demonstrated using strong acid resin A15 (AMBERLYST 15 from Rohm and Haas). High temperature treatment with zeolite overnight at 150°C resulted in elimination of MW176 to form 2-methyl-1,3-dioxane. But the formation of polyPDO (di-1,3-propanediol) with higher oligomers occurs at higher concentrations than the original MW176 acetal. Although the more difficult to isolate MW176 acetal was eliminated, the overall purity and yield decreased.

[0060] Additional timing studies were performed at 100°C using USY H+ type zeolite. The results showed the reaction conversion of MW176 acetal, especially the first gc (gas chromatography) peak MW176-1, which reacted to almost complete extent within 5 hours (MW176 acetal showed 3 peaks in gc / ...

Embodiment 176-2

[0066] The MW176 acetal impurity was treated at room temperature using a strong cationic acid ion exchange resin (AMBERLYST A35 from Rohm and Haas). The results shown in Table 3 show that the degradation of MW176 acetal forms MW102 acetal, MW18(H 2 O) and MW132 acetal.

[0067] wt%

name

MW

start

Finish

2-Methyl cyclic acetal

102

0.00

0.10

Cyclic acetal

132

0.05

0.29

Cyclic acetal diol

176

0.24

0.01

water

18

0.02

1.02

PDO

76

99.47

98.39

other

162

0.02

0.00

other

176

0.02

0.01

99.81

99.83

Molar balance

1.31

1.35

[0068] Solid acid treatment of PDO contaminated with MW176 acetal degrades this impurity into a lighter component (MW102 unhydroxylated acetal) that can be easily separated by distillation. Strong cationi...

Embodiment 132-1

[0070] Embodiment 132-1 (comparative example)

[0071] Acid resin treatment before distillation

[0072] This experiment required 1500 grams of crude PDO to be treated with 43.5 grams of dry A15 (Amberlyst A15 resin) strong acid cation exchange resin at 100° C. under nitrogen atmosphere for 3 hours with minimal separation (extraction) after distillative removal of water. The treated material is bright yellow. The MW132 acetal was only reduced from 3.2 wt% to 2.6 wt%. The treated material was distilled and successive distillation fractions showed a reduction of MW 132 acetal from 11 wt% to 2 wt%, but the final fraction formed up to 2700 ppm acrylate. Because of the strong acid treatment that liberates 3-hydroxy-propionic acid, excessive acrylate formation can be expected, resulting in substantial ester and eventual acrylate formation. This example illustrates that no significant removal of the MW132 acetal was observed for resin treatments without co-separation (extracti...

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Abstract

The present invention relates to improvements in the production of 1,3-propanediol (PDO), wherein an aqueous solution of 3-hydroxypropionaldehyde (HPA) is formed and the HPA is hydrogenated to produce a crude PDO mixture. A modification of the process involves treating the crude PDO mixture with acidic zeolites, acidic cation exchange resins, or soluble acids to convert the MW176 cyclic acetal to a more volatile species that can be easily separated from PDO by distillation. Another improvement involves removing water from the crude 1,3-propanediol mixture and contacting the resulting mixture with a solid acid purifying agent at a temperature of about 50-250°C to convert the MW132 cyclic acetal to the more volatile The cyclic acetal, and the separation of the more volatile cyclic acetal from the 1,3-propanediol by distillation or stripping.

Description

technical field [0001] The present invention relates to a process for the preparation of 1,3-propanediol (PDO), wherein an aqueous solution of 3-hydroxypropanal (HPA) is formed, and the neutralized HPA is hydrogenated to produce a PDO mixture which is then distilled to prepare purified The PDO. Background technique [0002] Several companies have developed the technology to prepare PDO starting from ethylene oxide as the main raw material. Ethylene oxide reacts with synthesis gas, a mixture of carbon monoxide and hydrogen, which can be produced by steam reforming of natural gas or partial oxidation of hydrocarbons. The idealized reaction between ethylene oxide (EO) and syngas to produce PDO can be expressed as follows: [0003] <chemistry num="001"> <chem file="200380102354_cml001.xml" / > < / chemistry> [0004] US 4,873,378, US 4,873,379 and US 5,053,562 to Hoechst Celanese describe a single-step reaction using 2:1 (mole) synthesis gas at 110-120°C and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/141C07C29/80C07C29/88
CPCC07C29/141C07C29/80C07C29/88C07C31/205
Inventor R·L·布莱克本S·E·布鲁尔Z·迪亚兹G·C·康普林J·B·鲍威尔P·R·韦德
Owner SHELL INT RES MAATSCHAPPIJ BV
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