CN1386569A

CN1386569A - Heterogenetic catalytic desulfurizing and heterogenetic catalytic oxidizing process for regenerating desulfurizing liquid

Info

Publication number: CN1386569A
Application number: CN 01119574
Authority: CN
Inventors: 熊育丰
Original assignee: Individual
Current assignee: Individual
Priority date: 2001-05-20
Filing date: 2001-05-20
Publication date: 2002-12-25

Abstract

A process for heterogeneous catalytic desulfurization and regenerating the desulfurizing liquid by heterogeneous catalytic oxidization is disclosed. The metal compound, oxygen carrier and assistant are used. Said metal compound as desulfurizing catalyst and the oxygen carrier, assistant, H2S and organic sulfide in the alkaline desulfurizing liquid can form the suspended transition substance. It is characterized by the production of complex solid sulfide to increase the desulfurizing efficiency (lower than 1 ppm).

Description

The heterogeneous catalytic oxidation regeneration techniques of heterogeneous catalysis desulfurization and doctor solution

The present invention relates to the heterogeneous catalytic oxidation regeneration techniques of a kind of heterogeneous catalysis desulfurization and doctor solution.

The discharging of sulfur-bearing industrial waste gas, environment is caused severe contamination, therefore industrial waste gas must carry out desulfurization and handles before discharging, and the existing commonsense method that industrial gasses are carried out desulfurization is a wet oxidation process, and the General Principle of wet oxidation process desulfurization is: with alkaline solution with the H in the gas ₂S absorbs in the solution, with contained catalyst in the solution is oxygen carrier, make it be oxidized to elemental sulfur, absorption liquid obtains regeneration, remove sulphur then outside system, solution recycles, and according to the difference of the desulfurization regeneration that is adopted with catalyst (oxygen carrier), the wet oxidation process desulfurization can be divided into ammoniacal liquor liquid catalytic, tannin extract method, MSQ method, ADA method etc.Some wet oxidation process can also organic sulfide removal and hydrogen cyanide.All articles of at home and abroad publishing on the publication up to now about the wet oxidation process desulfurization, confirm bar none that all wet oxidation process is the method for a kind of homogeneous catalysis desulfurization and homogeneous catalysis oxidation regeneration, it does not allow to have in the solution insoluble precipitability material (as metal oxide, carbonate and sulfide etc.) generate, or look the improper phenomenon in the production of appearing as of this class precipitability material.

Then with the solid phase of precipitability material as catalytic desulfurization and oxidation regeneration, solid phase and liquid-phase catalyst exist jointly in the present invention, carry out the heterogeneous catalytic oxidation regeneration of heterogeneous catalysis desulfurization and doctor solution.

The present invention is achieved like this, the catalyst that is used as the regeneration of heterogeneous catalysis desulfurization and heterogeneous catalytic oxidation is by metallic compound, oxygen carrier, three kinds of components of auxiliary agent are made into, make the metallic compound that desulfurization catalysis uses and (comprise vanadium, copper, zinc, manganese, cobalt, the oxide of iron, hydroxide or salt) in alkaline desulfuration solution, usually solubility property is all very poor, the sulfide that generates with hydrogen sulfide and organic sulfur reaction is sediment, in doctor solution, be suspended state, both can in solution, flow, the rerum natura that keeps solid phase again, material as oxygen carrier comprises the organic quinones that plays catalyst action in the oxidation regeneration of wet desulphurization liquid, hydroquinones, polyhydric phenols (Tea Polyphenols, tannin extract) and E ° of other standard electrode potential greater than 0.2 volt, oxygen carrier less than 0.75 volt, auxiliary agent of the present invention mainly is the organic complexing agent of used metal, has reached anticorrosion and other material promoting catalysis.

The present invention increases the absorption to sulfurous gas greatly because the generation of the complicated sulfide of solid phase is arranged, and inorganic sulfur in the gas and organic sulfur can be stablized remove below 1PPm, and this is that wet desulphurization can not be stablized the effect that reaches; The generation of the complicated sulfide of solid phase can also make the sulfur capacity of identical PH solution increase, and need not to change existing wet oxidation method desulphurization plant, as long as use heterogeneous desulfurization and regenerated catalyst instead, just can increase the desulphurization plant ability; Alkalescence to solution requires to reduce relatively, can reduce alkali consumption, reduces cost; Auxiliary agent not only plays the complexing agent effect, also can play antisepsis.

Below in conjunction with embodiment the present invention is further described below.

Embodiment:

Heterogeneous desulfurization and oxidation regeneration catalyst are by V ₂O ₅, ADA (anthraquinone disulphonate), potassium sodium tartrate, salicylic acid is ferrous and tri-iron tetroxide is formed.

(contain Na in alkalescence ₂CO ₃) in the doctor solution, vanadic anhydride generates sodium metavanadate, the doctor solution that is made into consists of:

NaVO ₃2g/L; ADA 1g/L; Potassium sodium tartrate 1g/L; The ferrous 2g/L of salicylic acid; Fe ₃O ₄3g/L.

Be used for desulfurization of synthesis ammonia plant wet oxidation process and reclaim equiment, under normal production conditions, can contain H advancing desulfurizing tower ₂S 0.1--4g/Nm ³Gas, purify to the H that goes out in the desulfurizing tower gas ₂S content is reduced to below the 1-5PPm.

Use that contained suspended material (referring to the suspended material except that sulphur) remains at the volume ratio more than 5% in the doctor solution of this kind desulphurization catalyst.

Claims

1, the heterogeneous catalytic oxidation regeneration techniques of a kind of heterogeneous catalysis desulfurization and doctor solution, catalyst is made into by metallic compound, oxygen carrier, three kinds of components of auxiliary agent, it is characterized in that doing desulphurization catalyst metallic compound (oxide that comprises vanadium, copper, zinc, manganese, cobalt, iron, hydroxide or salt) can with oxygen carrier, auxiliary agent, the H in the alkaline doctor solution ₂S and organic sulfur form the transitional material of suspended state, as the oxygen carrier (comprising organic quinones and aldehydes matter) of doctor solution oxidation regeneration catalyst are for electrode potential E °: 0.2 volt＜E °＜0.7 volt.