阅读说明：本技术 一种降低聚醚多元醇挥发性有机物含量的方法 (Method for reducing content of volatile organic compounds in polyether polyol ) 是由 张莹 刘沂 郭辉 李晓 张涛 高铭 于 2019-11-22 设计创作，主要内容包括：本发明属于化工合成技术领域,具体涉及一种降低聚醚多元醇挥发性有机物含量的方法。将待处理聚醚多元醇加入反应釜中,氮气置换,搅拌升温,氮气保护下,向反应釜内加入除醛剂,加入完毕,氮气置换,继续搅拌10～120分钟后,分别加入纯水和精制吸附剂并进行搅拌,干燥,过滤,即得成品；其中,除醛剂由除醛剂A、除醛剂B及助剂C组成,除醛剂的加入量为待处理聚醚多元醇质量的0.01～0.5‰,除醛剂A、除醛剂B与助剂C的质量比为1：1：1～1：5：50。本发明通过化学反应的方法将待处理聚醚多元醇中的醛酮类物质直接氧化分解成小分子物质或通过酯化反应去除,并通过氮气鼓泡蒸发提纯及物理吸附的方式可将挥发性有机物有效去除。(The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for reducing the content of volatile organic compounds in polyether polyol. Adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a finished product; the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50. according to the invention, aldehyde ketone substances in polyether polyol to be treated are directly oxidized and decomposed into small molecular substances by a chemical reaction method or removed by an esterification reaction, and volatile organic compounds can be effectively removed by nitrogen bubbling evaporation purification and physical adsorption.)

1. A method for reducing the content of volatile organic compounds in polyether polyol is characterized by comprising the following steps: the method comprises the following steps:

adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a polyether polyol finished product;

the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50;

the aldehyde removing agent A is one or a mixture of more of ethanol, propanol, n-butanol, n-pentanol, hexanol, heptanol, octanol, nonanol, decanol, 3-methyl-2-butanol, tert-butanol, 2-methyl-2-butanol, propylene glycol, ethylene glycol, diethylene glycol, isobutanol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol or glycerol;

the aldehyde removing agent B is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hypochlorous acid, sulfurous acid, acetic acid, trifluoroacetic acid, propionic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid or tert-valeric acid;

the auxiliary agent C is one or a mixture of two of polyether polyol with the functionality of 2 and the number average molecular weight of 400-12000 or polyether polyol with the functionality of 3 and the number average molecular weight of 400-12000.

2. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: stirring and heating to 50-130 ℃, and adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen.

3. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the adding amount of the pure water is 1-10% of the mass of the polyether polyol to be treated.

4. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the refined adsorbent is one or more of magnesium silicate, aluminum silicate or magnesium aluminum silicate.

5. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: the addition amount of the refined adsorbent is 1-10 per mill of the mass of the polyether polyol to be treated.

6. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: respectively adding pure water and the refined adsorbent and stirring the mixture specifically: firstly, adding pure water and stirring for 10-120 minutes, then adding the refined adsorbent and stirring for 10-120 minutes.

7. A process for reducing the volatile organic content of polyether polyols according to claim 1, wherein: replacing nitrogen until the oxygen content in the reaction kettle is less than or equal to 100 ppm.

Technical Field

The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for reducing the content of volatile organic compounds in polyether polyol.

Background

Along with the living standard of peopleThe continuous improvement of the technology, the ecological livable and healthy trip problems cause wide attention of the whole society. The state improves and revises the standards of passenger cars, and releases national standard' air quality evaluation guide in passenger cars (revision GB _ T27630-2011). According to this standard, it is required that the formaldehyde content does not exceed 0.1mg/m³The content of acetaldehyde is not more than 0.2mg/m³The content of acrolein is not more than 0.05mg/m³. The high-end automobile seat transnational production enterprises develop the purchasing standard of the main raw material polyether polyol according to the standard, and the content of formaldehyde, acetaldehyde and acrolein in the polyether polyol product is required to be not higher than 1.0 mg/g. After the standard is issued, the trialdehyde content of most domestic polyether polyol production enterprises cannot meet the standard, the acetaldehyde content of foreign polyether polyol products cannot meet the standard, and automobile seat manufacturers can only reduce the content of aldehyde and ketone substances in polyether polyol by adding an aldehyde removing agent. Therefore, there is an increasing interest in reducing the content of volatile organic compounds in polyether polyols.

Chinese patent CN109096479A discloses a method for reducing propionaldehyde in polyether polyol, which adopts specific peroxide and specific catalyst to convert propionaldehyde in polyether polyol into propionic acid, then reacts with solid alkaline substance, and reduces the propionaldehyde content in polyether in a filtering manner, specifically as follows: the specific peroxide is hydrogen peroxide, the using amount of the specific peroxide is 0.02-0.2% of the mass of the polyether polyol, the specific catalyst is a cobalt metal complex catalyst, and the using amount of the specific catalyst is 0.0005-0.002% of the mass of the polyether polyol; the solid alkaline substance is porous magnesium silicate, and the using amount of the solid alkaline substance is 0.1-1% of the mass of the polyether polyol. The method effectively reduces the content of propionaldehyde in the polyether, is safe and reliable, and saves the cost. However, this method requires a specific catalyst to remove propionaldehyde from polyether polyol, which increases production cost.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, can completely remove all aldehyde and ketone substances in the polyether polyol to be treated without specific catalytic treatment, saves the production cost and improves the production efficiency.

The method for reducing the content of the volatile organic compounds in the polyether polyol comprises the following steps:

adding polyether polyol to be treated into a reaction kettle, performing nitrogen replacement, stirring and heating, adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen, performing nitrogen replacement after the addition is finished, continuously stirring for 10-120 minutes, adding pure water and a refined adsorbent respectively, stirring, drying, and filtering to obtain a polyether polyol finished product;

the aldehyde removing agent comprises an aldehyde removing agent A, an aldehyde removing agent B and an auxiliary agent C, the adding amount of the aldehyde removing agent is 0.01-0.5 per mill of the mass of the polyether polyol to be treated, and the mass ratio of the aldehyde removing agent A to the aldehyde removing agent B to the auxiliary agent C is 1: 1: 1-1: 5: 50, preferably 1: 1: 1-1: 5: 10;

the aldehyde removing agent A is one or a mixture of more of ethanol, propanol, n-butanol, n-pentanol, hexanol, heptanol, octanol, nonanol, decanol, 3-methyl-2-butanol, tert-butanol, 2-methyl-2-butanol, propylene glycol, ethylene glycol, diethylene glycol, isobutanol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol or glycerol, and preferably ethanol or propanol;

the aldehyde removing agent B is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hypochlorous acid, sulfurous acid, acetic acid, trifluoroacetic acid, propionic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid or tert-valeric acid, preferably hydrochloric acid or phosphoric acid;

the assistant C is polyether polyol with 2 functionality, 400-12000 number average molecular weight or polyether polyol with 3 functionality, 400-12000 number average molecular weight, or the mixture of two of the two, preferably polyether polyol with 3 functionality, 5000-6000 number average molecular weight.

The aldehyde removing agent A and the aldehyde removing agent B are uniformly dispersed and dissolved in the auxiliary agent C, and the aldehyde removing agent A and the aldehyde removing agent B can oxidize and decompose aldehyde ketone substances in the polyether to be treated or remove the aldehyde ketone substances through esterification reaction under the synergistic chemical action.

Wherein:

stirring and heating to 50-130 ℃, and adding an aldehyde removing agent into the reaction kettle under the protection of nitrogen.

The adding amount of the pure water is 1-10% of the mass of the polyether polyol to be treated.

The refined adsorbent is one or a mixture of magnesium silicate, aluminum silicate or magnesium aluminum silicate.

The addition amount of the refined adsorbent is 1-10 per mill of the mass of the polyether polyol to be treated.

The step of respectively adding pure water and the refined adsorbent and stirring specifically comprises the following steps: firstly, adding pure water and stirring for 10-120 minutes, then adding the refined adsorbent and stirring for 10-120 minutes.

And replacing the nitrogen until the oxygen content in the reaction kettle is less than or equal to 100 ppm.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the invention, the aldehyde removing agent is added into the polyether polyol to be treated, the aldehyde and ketone substances in the polyether polyol to be treated are directly oxidized and decomposed into small molecular substances by a chemical reaction method or are removed by an esterification reaction, and the volatile organic compounds can be effectively removed by a subsequent nitrogen bubbling evaporation purification and physical adsorption mode.

2. The method disclosed by the invention can effectively reduce the content of volatile organic compounds (formaldehyde, acetaldehyde, acrolein, acetone and propionaldehyde) in the polyether polyol, reduce the concentration of harmful gas, meet the requirements of related environmental protection indexes, improve the downstream application quality of the polyether polyol and meet the use requirements of preparing high-end polyurethane products.

3. According to the method, all aldehyde and ketone substances in the polyether polyol to be treated can be completely removed without specific catalytic treatment, so that the production cost is saved, and the production efficiency is improved.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.