阅读说明：本技术 一种固体催化剂催化1,4-丁二醇脱水制备四氢呋喃的方法 (Method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under catalysis of solid catalyst ) 是由 唐元 周代红 丁陶 郎永福 于 2019-10-16 设计创作，主要内容包括：一种固体催化剂催化1,4-丁二醇脱水制备四氢呋喃的方法,采用制备的固体酸性皂土做为脱水催化剂,在温度160-210℃,常压条件下,加入1%-10%酸性皂土,催化1,4-丁二醇脱水制备四氢呋喃。将1,4-丁二醇加入装入搅拌器的反应器中,向反应器内加入制备的酸性皂土催化剂,在120℃-220℃之间常压下进行反应,同时将反应产生的THF蒸馏出去。本发明采用价格低廉、容易制备的固体酸性皂土催化剂,使得BDO脱水制备THF反应在不锈钢反应器中即可进行,反应产生的焦油量少,反应分离容易,催化剂在使用后可以采用简单焙烧的方法再生,避免产生大量的危险废物,具有广阔的工业化前景。(A method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol with a solid catalyst comprises the steps of taking prepared solid acid bentonite as a dehydration catalyst, adding 1-10% of acid bentonite at the temperature of 160-210 ℃ under normal pressure, and catalyzing 1, 4-butanediol to dehydrate to prepare tetrahydrofuran. Adding 1, 4-butanediol into a reactor filled with a stirrer, adding the prepared acidic bentonite catalyst into the reactor, reacting at 120-220 ℃ under normal pressure, and distilling out THF generated in the reaction. The method adopts the solid acid bentonite catalyst which is low in price and easy to prepare, so that the reaction for preparing the THF by BDO dehydration can be carried out in a stainless steel reactor, the amount of the tar generated by the reaction is small, the reaction separation is easy, the catalyst can be regenerated by a simple roasting method after being used, a large amount of dangerous wastes are avoided, and the method has wide industrial prospect.)

1. A method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under the catalysis of a solid catalyst is characterized by comprising the following steps: the prepared solid acid bentonite is used as a dehydration catalyst, and 1-10% of acid bentonite is added under the conditions of temperature 160-. Adding 1, 4-butanediol into a reactor filled with a stirrer, adding the prepared acidic bentonite catalyst into the reactor, reacting at 120-220 ℃ under normal pressure, and distilling out THF generated in the reaction.

2. The method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under the catalysis of the acid bentonite catalyst according to claim 1, wherein the acid bentonite catalyst comprises the following components in percentage by weight: the regeneration method of the acid bentonite catalyst can adopt a high-temperature roasting method for regeneration, and also can adopt sulfuric acid, hydrochloric acid and nitric acid aqueous solution for regeneration.

3. The method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under the catalysis of the acid bentonite catalyst according to claim 1, wherein the acid bentonite catalyst comprises the following components in percentage by weight: the prepared acidic bentonite is adopted to prepare the bentonite, the bentonite is acidified by aqueous solutions of sulfuric acid, nitric acid, hydrochloric acid and the like, anions on the bentonite are washed by distilled water after acidification and filtration, then the bentonite is dried at the temperature of more than 100 ℃, and then the bentonite is roasted by a high-temperature muffle furnace to prepare the acidic bentonite catalyst.

4. The method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under the catalysis of the acid bentonite catalyst according to claim 1, wherein the acid bentonite catalyst comprises the following components in percentage by weight: the method adopts the prepared acid bentonite as the dehydration catalyst, the reactor can be made of stainless steel, glass lining and other materials, and the matched equipment, pipelines and valves are made of stainless steel materials.

Technical Field

The invention belongs to the field of downstream fine chemical industry in coal chemical industry, and particularly relates to a method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol under catalysis of a solid catalyst.

Background

Tetrahydrofuran (THF for short) is the largest derivative of 1, 4-butanediol, is colorless, transparent, volatile and pungent liquid at normal temperature and pressure, is an excellent organic solvent and fine chemical intermediate, and is mainly used for producing polytetrahydrofuran. The dehydration of 1, 4-butanediol is the most direct and important process for the production of tetrahydrofuran. The basic principle is that 1, 4-butanediol is dehydrated to generate tetrahydrofuran in the presence of an acid catalyst, and the commonly used catalyst comprises inorganic acids such as sulfuric acid, phosphoric acid and the like, and other inorganic acids such as heteropoly acid, alumina, ZSM-5 molecular sieve, ion exchange resin and the like. The industrial production of tetrahydrofuran mostly uses sulfuric acid and ion exchange resins as catalysts.

The tetrahydrofuran is prepared by dehydrating the 1, 4-butanediol by adopting inorganic acids such as traditional sulfuric acid and the like as catalysts, the reactor and matched equipment need to adopt Hastelloy materials with high price, the manufacturing cost is high, meanwhile, a large amount of tar is generated by a sulfuric acid method, and the tar contains about 50 percent of BDO, so that the cost for treating the tar is increased, and a large amount of BDO is wasted; the prior art that the ion exchange resin is adopted as the catalyst has the defects of complex catalyst preparation process, high price, harsh reaction conditions, difficult regeneration of the used catalyst and the like, and the application and popularization of the technology are limited.

Disclosure of Invention

The invention aims to solve the problems of tetrahydrofuran prepared by the traditional sulfuric acid method, and provides a method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol by using a solid catalyst which is low in price, easy to prepare, simple in regeneration method and capable of keeping activity in a water phase.

The technical scheme of the invention is as follows: a method for preparing tetrahydrofuran by dehydrating 1, 4-butanediol with a solid catalyst comprises the steps of taking prepared solid acid bentonite as a dehydration catalyst, adding 1-10% of acid bentonite at the temperature of 160-210 ℃ under normal pressure, and catalyzing 1, 4-butanediol to dehydrate to prepare tetrahydrofuran. Adding 1, 4-butanediol into a reactor filled with a stirrer, adding the prepared acidic bentonite catalyst into the reactor, reacting at 120-220 ℃ under normal pressure, and distilling out THF generated in the reaction. The regeneration method of the acid bentonite catalyst can adopt a high-temperature roasting method for regeneration, and also can adopt sulfuric acid, hydrochloric acid and nitric acid aqueous solution for regeneration.

Preferably, the prepared acidic bentonite is used for preparing the acidic bentonite, the bentonite is acidified by aqueous solutions of sulfuric acid, nitric acid, hydrochloric acid and the like, anions on the bentonite are washed by distilled water after acidification and filtration, then the bentonite is dried at the temperature of more than 100 ℃, and then the bentonite is roasted by a high-temperature muffle furnace to finally prepare the acidic bentonite catalyst.

Preferably, the prepared acid bentonite is used as a dehydration catalyst, the reactor can be made of stainless steel, glass lining and the like, and the supporting equipment, pipelines and valves are made of stainless steel.

The invention has the following remarkable effects:

the method adopts the solid acid bentonite catalyst which is low in price and easy to prepare, so that the reaction for preparing THF by BDO dehydration can be carried out in a common stainless steel reactor, the amount of tar generated by the reaction is very small, the reaction separation is very easy, the catalyst can be regenerated by a simple roasting method after being used, a large amount of dangerous waste is avoided, and the method for preparing tetrahydrofuran by adopting the catalyst has wide industrial prospect.

Detailed Description

The invention is further illustrated by the following examples: