Continuous preparation device of small molecular weight amine-terminated polyether and preparation method

Abstract

The invention discloses a continuous preparation device of small molecular weight amine-terminated polyether and a preparation method. The continuous preparation device of small molecular weight amine-terminated polyether comprises a hydrogen storage device, a liquid ammonia storage tank, a polyether polyol storage tank, a mixing preheater, a fixed bed reactor I, a fixed bed reactor II, a primarygas-liquid separator, an intermediate drying tower, a secondary gas-liquid separator, a circulating hydrogen compressor, a flash ammonia stripping tower, a pressurized liquefaction plant, a dehydrating tower, a wastewater pool and a product storage tank. The preparation method comprises the following steps: by taking small molecular weight polyether polyol, H2 and liquid NH3 as raw materials, respectively carrying out 'two-step' hydrogen present ammonolysis reactions in the presence of a catalyst in a manner of connecting the two fixed bed reactors in series, thereby obtaining the small molecular weight amine-terminated polyether. The operation process is continuous, the product quality is stable and controllable, and the reaction conditions are mild; recycling of the H2 and liquid NH3 isrealized, and the device is environmentally friendly and economical; and the reaction conversion rate is more than or equal to 99.0%, and the primary amine selectivity is more than or equal to 98.5%.

Description

technical field

[0001] The invention relates to a continuous preparation device and method for small-molecular-weight amino-terminated polyethers, belonging to the field of preparation of amino-terminated polyethers. Background technique

[0002] Amine-Terminated Polyether (ATPE), also known as polyether amine, is a kind of polyoxyalkylene compound, the main chain of which is a polyether skeleton, but the end is blocked by an amino group. According to the number of substituted H atoms in the amino group, it can be divided into primary amino group and secondary amino group terminated amino polyether. At present, the production of domestic amino-terminated polyether products is mostly batch method, with incomplete product types and unstable quality, and the production capacity cannot meet market demand at all.

[0003] At present, the synthesis of amino-terminated polyether in foreign companies is mainly a continuous gas, liquid, and solid three-phase fixed-bed hydrogenation ...

Examples

Embodiment 1

[0053] 100mL supported nickel-based catalyst (containing Ni 92%, Cr 7.8%, Fe 0.2%) and 100mL Raney-type nickel-based catalyst (particle size 20 mesh, activity 1ml H 2 / min. g) Fill in fixed-bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume about 350ml) (catalyst volume to fixed bed volume ratio is 0.29:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 12L / h 2 , the volume space velocity is 2.0h -1 NH 3 and a volumetric space velocity of 1.0h -1 , molecular weight 230, low molecular weight polyether (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 8:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 0.6:1); fully mixed and preheated at 60°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 180°C and 2.5MPa Ammonification reaction: the product is separated from gas and liq...

Embodiment 2

[0056] 35mL supported nickel-based catalyst (containing Ni 95%, Cr 3%, Fe 2%) and 35mL Raney-type nickel-based catalyst (particle size 40 mesh, activity 5ml H 2 / min. g) Fill in fixed bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume 350ml) (catalyst volume to fixed bed volume ratio is 0.2:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 8L / h 2 , the volume space velocity is 4.0h -1 NH 3 and a volumetric space velocity of 2.0h -1 , molecular weight 400, low molecular weight polyether (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 15:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 1:1); fully mixed and preheated at 50°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 140°C and 1.5MPa Ammonification reaction: the product is separated from gas and liquid at 160°C by...

Embodiment 3

[0059] 155mL supported nickel-based catalyst (containing Ni 90%, Cr 8%, Fe 2%) and 155mL Raney-type nickel-based catalyst (particle size 30 mesh, activity 3ml H 2 / min. g) Fill in fixed bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume 350ml) (the ratio of catalyst volume to fixed bed volume is 0.44:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 20L / h 2 , the volume space velocity is 1.0h -1 NH 3 and a volumetric space velocity of 2.0h -1 , a molecular weight of 600, a small molecular weight polyether with a functionality of 2 (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 5:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 0.9:1); fully mixed and preheated at 100°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 160°C and 2.0MPa Ammonification reaction: the prod...

technical field

[0001] The invention relates to a continuous preparation device and method for small-molecular-weight amino-terminated polyethers, belonging to the field of preparation of amino-terminated polyethers. Background technique

[0002] Amine-Terminated Polyether (ATPE), also known as polyether amine, is a kind of polyoxyalkylene compound, the main chain of which is a polyether skeleton, but the end is blocked by an amino group. According to the number of substituted H atoms in the amino group, it can be divided into primary amino group and secondary amino group terminated amino polyether. At present, the production of domestic amino-terminated polyether products is mostly batch method, with incomplete product types and unstable quality, and the production capacity cannot meet market demand at all.

[0003] At present, the synthesis of amino-terminated polyether in foreign companies is mainly a continuous gas, liquid, and solid three-phase fixed-bed hydrogenation ...

Examples

Embodiment 1

[0053] 100mL supported nickel-based catalyst (containing Ni 92%, Cr 7.8%, Fe 0.2%) and 100mL Raney-type nickel-based catalyst (particle size 20 mesh, activity 1ml H 2 / min. g) Fill in fixed-bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume about 350ml) (catalyst volume to fixed bed volume ratio is 0.29:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 12L / h 2 , the volume space velocity is 2.0h -1 NH 3 and a volumetric space velocity of 1.0h -1 , molecular weight 230, low molecular weight polyether (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 8:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 0.6:1); fully mixed and preheated at 60°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 180°C and 2.5MPa Ammonification reaction: the product is separated from gas and liq...

Embodiment 2

[0056] 35mL supported nickel-based catalyst (containing Ni 95%, Cr 3%, Fe 2%) and 35mL Raney-type nickel-based catalyst (particle size 40 mesh, activity 5ml H 2 / min. g) Fill in fixed bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume 350ml) (catalyst volume to fixed bed volume ratio is 0.2:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 8L / h 2 , the volume space velocity is 4.0h -1 NH 3 and a volumetric space velocity of 2.0h -1 , molecular weight 400, low molecular weight polyether (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 15:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 1:1); fully mixed and preheated at 50°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 140°C and 1.5MPa Ammonification reaction: the product is separated from gas and liquid at 160°C by...

Embodiment 3

[0059] 155mL supported nickel-based catalyst (containing Ni 90%, Cr 8%, Fe 2%) and 155mL Raney-type nickel-based catalyst (particle size 30 mesh, activity 3ml H 2 / min. g) Fill in fixed bed reactors I and II of φ25×720mm (diameter 25mm, height 720mm, volume 350ml) (the ratio of catalyst volume to fixed bed volume is 0.44:1), heat up and feed H 2 Activate and dry. After completion, press H into the mixing preheater at a flow rate of 20L / h 2 , the volume space velocity is 1.0h -1 NH 3 and a volumetric space velocity of 2.0h -1 , a molecular weight of 600, a small molecular weight polyether with a functionality of 2 (NH 3 The molar ratio to the hydroxyl group in the polyether polyol molecule is 5:1; H 2 The molar ratio to the hydroxyl group in the polyether polyol molecule is about 0.9:1); fully mixed and preheated at 100°C, and then enters the fixed bed reactor I from the top, and the first step of hydrogenation occurs at 160°C and 2.0MPa Ammonification reaction: the prod...

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