CN-117551010-B - Method for recycling hydrogen sulfide by using surfactant-induced modified zeolite

Abstract

The invention discloses a method for recycling hydrogen sulfide by using surfactant-induced modified zeolite, which adopts surfactant-induced modified zeolite to catalyze butene and hydrogen sulfide to synthesize butanethiol, wherein the surfactant-induced modified zeolite is prepared by dissolving 0.3-0.4g of hexadecyl tripropyl ammonium bromide in 0.06-0.1mol/L NaOH aqueous solution, then adding 1-1.2g of FAU type zeolite, stirring for 1-2h at room temperature, transferring the mixture into a high-pressure reaction kettle, heating for 30-90h at 150-170 ℃, separating solid from liquid, roasting the solid at 500-700 ℃ for 3-5h, and then adopting an isovolumetric impregnation method, placing the roasted solid in a molybdate-containing solution, standing and drying.

Inventors

• LUO YONGMING
• Pei Zehao
• LU JICHANG
• ZHU SONGSHAN
• SONG DI

Assignees

• 昆明理工大学

Dates

Publication Date

20260512

Application Date

20231107

Claims (4)

1. 1. A method for recycling hydrogen sulfide by using surfactant-induced modified zeolite is characterized in that the surfactant-induced modified zeolite is used for catalyzing butene and hydrogen sulfide to synthesize butanethiol; The surfactant-induced modified zeolite is prepared by dissolving 0.3-0.4g of hexadecyl tripropyl ammonium bromide in 0.06-0.1mol/L NaOH aqueous solution, then adding 1-1.2g of FAU type zeolite, stirring for 1-2h at room temperature, transferring the mixture into a high-pressure reaction kettle, heating for 30-90min at 150-170 ℃, carrying out solid-liquid separation after heating, and roasting the solid at 500-700 ℃ for 3-5 h; and (3) placing the roasted solid in a molybdate solution by adopting an isovolumetric impregnation method, standing and drying to obtain the surfactant-induced modified zeolite.
2. 2. The method of claim 1, wherein the Mo loading is 5-15wt%.
3. 3. A process as claimed in claim 1, wherein the gas-phase catalytic reaction for the synthesis of butanethiol is carried out at 290-320℃and 0.2-0.3MPa and at 270-290h -1 .
4. 4. The method of claim 1, wherein the molybdate is ammonium molybdate.

Description

Method for recycling hydrogen sulfide by using surfactant-induced modified zeolite Technical Field The invention belongs to the technical field of catalytic synthesis of butanethiol, and particularly relates to a method for recycling hydrogen sulfide by using surfactant-induced modified zeolite. Background Hydrogen sulfide is a typical toxic malodorous gas which not only endangers the atmosphere, but also creates a great threat to human health. The main disadvantage of the current mainstream hydrogen sulfide treatment mode is the claus process is that the added value is low and the treatment effect is not ideal, and the butanethiol synthesis opens up a more attractive path for hydrogen sulfide recycling. Butyl mercaptan is slightly soluble in water, is easily soluble in ethanol, diethyl ether and the like, is mainly used as a solvent and an organic synthesis intermediate, and is an important chemical raw material. At present, the research on preparing butanethiol on an industrial scale is still quite blank, the existing synthetic method is mainly obtained by reacting bromobutane with thiourea, or the existing synthetic method is obtained by catalyzing reaction of butene and hydrogen sulfide, the latter has larger application potential, however, the development of a catalyst for the reaction is a great obstacle, and the efficiency of the catalytic reaction is determined by the good or bad of the catalyst, so that the catalyst for efficiently synthesizing butanethiol from butene and hydrogen sulfide has larger research and development values. The zeolite is widely applied to industries, agriculture, science and technology, plastics, fillers, feeds, fertilizers, rubber, electronics and other departments, the annual output of the natural zeolite in the world is about 400 ten thousand tons currently, and the quantity of the natural zeolite is increased along with the development of industry, wherein the zeolite is also commonly used for preparing a catalyst in the chemical industry because of low price and easy availability, and the modification of the natural zeolite for catalytic reaction has been greatly studied, and if the zeolite can be modified for the catalytic reaction of butene and hydrogen sulfide by utilizing the property of the zeolite, the catalyst with great application potential in the field is obtained. Disclosure of Invention The invention provides a method for recycling hydrogen sulfide by using surfactant-induced modified zeolite, which adopts the surfactant-induced modified zeolite to catalyze butene and hydrogen sulfide to synthesize butanethiol at 290-320 ℃, 0.2-0.3MPa and 270-290h -1 in air space time; wherein the surfactant-induced modified zeolite is prepared by dissolving 0.3-0.4g of hexadecyl tripropyl ammonium bromide in 0.06-0.1mol/L NaOH aqueous solution, then adding 1-1.2 g of FAU type zeolite, stirring at room temperature for 1-2h, transferring the mixture into a high-pressure reaction kettle, heating at 150-170 ℃ for 30-90h, and roasting at 500-700 ℃ for 3-5 h; The surfactant-induced modified zeolite can also be prepared by placing the above baked solid in ammonium molybdate solution by an isovolumetric impregnation method, standing for 24-36h, and drying at 70-80deg.C. The loading of the molybdenum is 5-15 wt%; the catalyst has the advantages of improved catalyst activity, prolonged service life, easy preparation of raw materials, good stability, good sulfur resistance and high selectivity, and the service life of the catalyst is greatly improved. Drawings FIG. 1 is a graph showing the effect of different hydrothermal times on butanethiol synthesis reaction in example 1; FIG. 2 is a graph showing the effect of varying Mo loadings on butanethiol synthesis reaction in example 2; FIG. 3 is the effect on butanethiol selectivity after Mo loading in example 2. Detailed Description The invention is further illustrated by the following examples, but the scope of the invention is not limited to the description. Example 1 preparation of surfactant-induced modified Zeolite and its use in the Synthesis of butanethiol 1. Dissolving 0.3g of hexadecyl tripropyl ammonium bromide in 0.08mol/L NaOH aqueous solution, adding 1g of FAU type zeolite, stirring at room temperature for 1h, transferring the mixture into a high-pressure reaction kettle, respectively heating at 150 ℃ for 30h, 60h and 90h, and roasting at 550 ℃ for 5h to prepare surfactant-induced modified zeolite; 2. And (2) respectively placing 0.4g of the catalyst and 0.4g of the FAU type zeolite prepared in the step (1) under different hydrothermal time in a tubular furnace reactor, introducing a mixed gas of butene and hydrogen sulfide (volume ratio of 1:8) into the tubular furnace reactor, synthesizing butanethiol at the temperature of 300 ℃, the pressure of 0.3MPa and the gas-air time of 280 h -1 at the flow rate of 10mL/min, and preparing modified zeolite with the catalytic performance superior to that of the FAU type natural zeolit