CN105148958A

CN105148958A - Synthetic method of sulfur-doped iron phosphide hydrodesulfurization catalyst

Info

Publication number: CN105148958A
Application number: CN201510615250.0A
Authority: CN
Inventors: 宋立民; 李彤彤; 安彦强
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2015-09-21
Filing date: 2015-09-21
Publication date: 2015-12-16

Abstract

The invention relates to an in-situ synthesis method of sulfur-doped iron phosphide, and belongs to the technical field of inorganic material preparation technologies. According to the in-situ synthesis method of the sulfur-doped iron phosphide, a mechanical mixture of iron sulfide and sodium hypophosphite serves as a precursor, iron phosphide is formed by utilizing the reaction of iron ions and phosphine, and meanwhile generated hydrogen sulfide can build an active phase of FePS on the surface of nickel phosphide to form the sulfur-doped iron phosphide. The method is easy to operate, good in process repeatability, stable in product quality and suitable for large scale production.

Description

A kind of synthetic method of sulfur doping iron phosphide Hydrobon catalyst

Technical field

The invention belongs to inorganic material preparation process technical field, relate to the preparation method of inorganic material, specifically the preparation method of high activity sulfur doping iron phosphide, can be applicable to the aspects such as hydrodesulfurization catalytic material.

Background technology

Transition metal phosphide has been found to have outstanding hydrodesulfurization performance.Such as nickel phosphide, iron phosphide, phosphatization cobalt, tungsten phosphide and phosphating sludge etc.But the activity of transition metal phosphide in hydrodesulfurization reaction studies the study hotspot remaining this field mutually.Scholars studied and found that these mesophase spherule species of MPS were active phases of desulphurization reaction in hydrodesulfurization reaction in recent years, therefore, if in this active phase of phosphide surface construction, can significantly certainly will can improve the activity of the hydrodesulfurization of phosphide.In this patent, we take iron sulfide as raw material, and synthesized the iron phosphide of sulfur doping by low temperature phosphor, the hydrodesulfurization activity of this catalyst is significantly improved.

Summary of the invention

Meaning of the present invention is the synthetic method providing a kind of high activity sulfur doping iron phosphide, and this method while formation iron phosphide, can build the active phase of FePS at its surface in situ, thus significantly improve the activity of the hydrodesulfurization of iron phosphide.And have simple to operate, the reaction time is of short duration, and reaction temperature is lower, good process repeatability, the advantage of constant product quality.

Unsupported sulfur doping iron phosphide synthesis step is as follows:

Vulcanized sodium and ferrous sulfate are dissolved in respectively in a certain amount of deionized water, are more dropwise joined in ferrous ions soln by vulcanized sodium, what obtain is precipitated as ferrous sulfide, for subsequent use after centrifugal, washing is dry.By a certain amount of iron sulfide powder and sodium hypophosphite mixing, after then said mixture being warmed up to 250-550 DEG C under inert gas shielding, heat treatment 1-2h.After completion of the reaction furnace is down to room temperature, with nitrogen inerting 1 hour containing 1% oxygen, the catalyst obtained was for subsequent use.

The synthesis step of support type sulfur doping iron phosphide is as follows:

Be dissolved in by a certain amount of ferrous sulfate in a certain amount of water, then add a certain amount of carrier, impregnated carrier is after 3 hours, add a certain amount of vulcanized sodium, then continue stirring after 1 hour, the precipitation obtained is filtered, dry, grind, finally obtain the iron sulfide powder of load.Then the synthesis step of iron phosphide is repeated.Carrier is nano silicon, molecular sieve, macropore alundum (Al2O3) etc.

Specific embodiments

Embodiment 1

After 0.5 gram of iron sulfide and the mixing of 0.34g sodium hypophosphite, put into tube furnace, be directly warmed up to 300 DEG C, keep after 60 minutes, drop to room temperature, with nitrogen inerting 1 hour containing 1% oxygen, the catalyst obtained was for subsequent use.

Embodiment 2

Reaction temperature is become 250 DEG C, other condition is constant.

Embodiment 3

To become 120 minutes the reaction time, other condition is constant.

Embodiment 4

By 0.5gFeS/SiO ₂with the mixing of 0.55g sodium hypophosphite, put into tube furnace, be directly warmed up to 350 DEG C, keep after 90 minutes, drop to room temperature, with nitrogen inerting 1 hour containing 1% oxygen, the catalyst obtained was for subsequent use.

Claims

1. prepare the method for high activity sulfur doping iron phosphide based on iron sulfide, it is characterized in that comprising the steps:

Vulcanized sodium and ferrous sulfate are dissolved in a certain amount of deionized water respectively, are more dropwise joined in ferrous ions soln by vulcanized sodium, and what obtain is precipitated as ferrous sulfide, centrifugal, washing, dry after for subsequent use; By a certain amount of iron sulfide powder and sodium hypophosphite mixing, after then said mixture being warmed up to 250-550 DEG C under inert gas shielding, heat treatment 1-2h.After completion of the reaction furnace is down to room temperature, with nitrogen inerting 1 hour containing 1% oxygen, the catalyst obtained was for subsequent use; If iron sulfide to be replaced to the iron sulfide of support type, the sulfur doping iron phosphide of support type can be obtained.