RU2644779C2 - Catalyst for liquid phase oxidation of sodium sulfide - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for liquid-phase oxidation of sodium sulfide in an aqueous medium and can be used in gas, oil refining, petroleum, chemical, leather, and other industries in the disposal of waste water containing inorganic sulfides. The catalyst is a hydrocarbon solution of spatial-substituted stilbenquinone (1) and/or diphenoquinone (2) when the volume ratio of hydrocarbon solution of the catalyst to the oxidizable aqueous medium with sulfide compounds is preferably 1:(2-3). Herewith diesel and/or kerosene, and/or diesel fraction is used as a hydrocarbon solvent, with the following content of components, wt %: spatial-substituted stilbenquinone and/or diphenoquinone: 1÷25.0; hydrocarbon solvent - the rest

,

, where R_1-4 is tert-butyl.

EFFECT: catalyst has a longer service life and does not pollute the oxidized wastewater.

1 tbl, 1 ex

Description

The present invention relates to the production of catalysts for the liquid phase oxidation of sodium sulfide. The invention can be used in gas, oil refining, oil, chemical, leather and other industries for the disposal of wastewater containing inorganic sulfides.

Known catalysts for the oxidation of sulfur compounds based on clay media with various active additives. For example, a catalyst for the oxidation of sulfur compounds containing, as a catalytically active component, a pyrite cinder (33-37% wt.) Introduced into the clay mass [1], or a catalyst containing a pyrite cinder composition (10-15 wt. ) with chromium oxide (VI) 3-5; copper oxide 5-10; vanadium (V) oxide 3-5; petroleum coke 7-10; zinc oxide 5-10 on a clay carrier [2].

The disadvantage of these catalysts is their low stability due to the use of clay as a carrier, subject to alkaline hydrolysis in the process of desulfurization of gases and liquid petroleum products flowing in alkaline environments.

A known catalyst for the oxidation of sulfur compounds containing, as an active component, oxides and / or hydroxides and / or spinels of metals of variable valency on a polymer carrier - polyethylene, polypropylene, polystyrene or other polymer, characterized in that it contains an additional modifying additive - an organic base, and / or heteropoly acids and / or carbon-containing material with the following components: active component (15-50%), modifying additive (0.5-20%), carrier - the rest [3].

The disadvantages of this catalyst include an inefficient form of their execution - in the form of spherical granules, which significantly reduces the geometric surface and free volume of the catalyst, i.e. the proportion of the reaction solution in a unit volume of the reactor, causing an increase in the volume of treatment facilities and the size of capital and operating costs for cleaning. It has a low activity and selectivity.

There is also known a method of liquid-phase oxidation of sulfur compounds in the presence of iron sulfate as a catalyst [4]. A common disadvantage of the proposed method is the limitation of its scope only for dilute solutions, low efficiency and complexity of separating the catalyst precipitate (iron sulfide and hydroxide) after the oxidative treatment of the runoff.

Closest to the claimed is a homogeneous phthalocyanine-based catalyst with cationic ammoniomethyl substituents choln-PcM and pymn-PcM, obtained by chloromethylation of cobalt phthalocyanine or iron phthalocyanine α, α'-dichloromethyl ether, followed by the reaction of chloromethylmethyl-2-methane-methyl-substituted-di-methyl-substituted-substituted-methyl-2-methyl-substituted-substituted respectively [5].

The disadvantage of this catalyst is the scarcity and high cost of its catalytically active component, the complexity of the synthesis of the catalyst and its continuous consumption in the process of oxidation of sulfide-hydrosulfide compounds in effluents due to its solubility in an aqueous medium.

The purpose of the invention is the creation of a catalyst, eliminating its continuous consumption during the oxidation of sodium sulfide in an aqueous medium.

According to the invention, the goal is achieved in that a hydrocarbon solution of catalytically active components — spatially substituted stilbenquinone (1) and / or diphenoquinone (2), insoluble in an aqueous medium, is used as a catalyst for the oxidation of sodium sulfide in an aqueous medium.

where R _1-4 is tert-butyl.

A distinctive feature of the proposed catalyst from the prototype is its composition, namely: the use of a hydrocarbon solution of catalytically active catalyst components, which are used as spatially substituted stilbenquinone and / or diphenoquinone in an amount of from 1 to 25.0% by mass, insoluble in an aqueous medium and gasoline, kerosene or diesel fractions are used as the hydrocarbon solvent of the catalyst.

The specified distinctive feature of the proposed catalyst determines its novelty and inventive step in comparison with known catalysts, since the use of a hydrocarbon solution of spatially substituted stilbenquinone and / or diphenoquinone as a catalyst for the oxidation of sulfide-hydrosulfide compounds in an aqueous medium is not described in the literature and allows one to obtain an oxidation catalyst sulfide compounds with a longer life, not polluting oxidizable wastewater with a catalyst - salt and metals with variable valency.

The volume ratio of the hydrocarbon solution of the catalyst to the oxidizable aqueous medium with sulfide compounds is 1/1 ÷ 10.

The proposed catalyst, soluble in the hydrocarbon phase, does not dissolve in the aqueous medium and is completely separated from the oxidized runoff upon sedimentation. The product of the oxidation of sulfide compounds in an aqueous medium in the presence of the proposed catalyst is thiosulfate.

The investigated catalyst was obtained and tested in laboratory conditions. Below are examples and results of experiments.

Example 1

A certain volume of an aqueous solution of sodium sulfide and hydrocarbon fraction is placed in a heated batch glass reactor with a volume of 75 ml and heated to a predetermined temperature. Then, a certain sample of the catalyst is placed here - spatially substituted stilbenquinone and / or diphenoquinone, and the mixture is intensively mixed on a magnetic stirrer in an oxygen atmosphere. The activity of the catalysts is judged by the change in the residual content of sulfide sulfur over time by potentiometric titration of an oxidizable aqueous solution of sodium sulfide according to GOST 22985-90. The conditions for testing the catalysts: temperature - 90 ° C, oxidation time - 60 min, the initial concentration of sulfide sulfur in an oxidizable aqueous solution of sodium sulfide - 2.0% wt.

From the above table. 1 data shows that the proposed catalysts - spatially substituted stilbenquinone and / or diphenoquinone, are highly active in the oxidation reaction of sulfide sulfur when their content in the hydrocarbon is from 1 to 25% of the mass.

It has been found that the volume ratio of the hydrocarbon solution of the catalyst to the oxidizable effluent is 1: (2-3). (tab. 1, op. 9).

It is shown that gasoline, kerosene or diesel fractions can be used as a hydrocarbon solvent for the catalyst.

The possibility of repeated use of the proposed catalyst (table. 1, op. 13) in the process of oxidation of an aqueous solution of sodium sulfide, confirming the absence of its continuous consumption in the process of wastewater treatment, has been established.

*) the catalyst from experiment No. 9 after its 10-fold repeated use for the oxidation of sodium sulfide

Literature

1. Pat. 2089287 Russian Federation, INC 7 B01J 23/78, B01J 23/86, B01D 53/78, B01J 23/86, B01J 101: 64. Catalyst for the oxidation of sulfur compounds / Kochetkova R.P., Kochetkov A.Yu., Panfilova I.V., Kovalenko N.A., Borovsky V.M., Kuimov SV., Babikov A.F., Yaskin V.P. , An E.D., Glazyrin V.V., Zaykova PM, Semiletko S.V., Shapkin S.V., Tikhonov G.P., applicant and patentee Private individual research and production enterprise "Catalysis". - No. 95113808/04. - Declared. 08/01/1995, publ. 09/10/1997.

2. Pat. 2059428 Russian Federation, INC ⁷ B01J 23/86, B01J 103: 40, B01J 103: 20. Catalyst for the oxidation of sulfur compounds / Kochetkova R.P., Kochetkov A.Yu., Kovalenko N.A., Borovsky V.M., Kuimov S.V., Glazyrin V.V., Zaykova PM, Babikov A.F., Yaskin V.P., Applicant and Patent Owner Private Individual Research and Production Enterprise “Catalysis”. - No. 93029900/04. - Declared. 06/17/1993, publ. 05/10/1996.

3. Pat. 2255805 Russian Federation, INC ⁷ B01J 23/70, B01J 23/94, B01D 53/86. A heterogeneous catalyst for the oxidation of inorganic and / or organic compounds on a polymer carrier / Kochetkova RP, Kochetkov A.Yu., Kovalenko NA, patent holder Kochetkov A.Yu. - No. 2003105374/04. - Declared. 02/25/2003, publ. 07/10/2005.

4. Pat. 2425798 (Russian Federation. MKP C01B 17/98, C01D 13/00. Method for the liquid-phase oxidation of an aqueous solution of sodium hydrosulfite / Anatoly Ivanov, Ekaterina Ageeva; Patent holder (s): State Educational Institution of Higher Professional Education "Kursk State Technical University" ( Kursk State Technical University) - No. 2009144412/05, Declared Nov 30, 2009, published Oct 10, 2011.

5. Pat. 2381066 (Russian Federation, MKP B01J 23/745, B01J 23/75, C07D 487/22, C10G 27/10, С09В 47/00. Catalyst and method for the oxidation of sodium sulfide / Vorozhtsov G.N., Egorova. O.Yu., Kaliya O.L., Lukyanets E.A. Patent holder (s): State Research Center Scientific Research Institute of Organic Intermediates and Dyes (Federal State Unitary Enterprise Scientific Center "NIOPIK"). - No. 2008141392/04. Declared. 21.10.2008 published on 02/10/2010.

Claims (5)

The catalyst for the liquid-phase oxidation of sodium sulfide in an aqueous medium, which is a hydrocarbon solution of spatially substituted stilbenquinone (1) and / or diphenoquinone (2) with a volume ratio of the hydrocarbon solution of the catalyst to the oxidizable aqueous medium with sulfide compounds, preferably 1: (2-3), where as a hydrocarbon solvent, gasoline and / or kerosene and / or diesel fractions are used,

where R _1-4 - tert-butyl, with the following content of components, mass. %: spatially substituted stilbenquinone and / or diphenoquinone: 1 ÷ 25.0; hydrocarbon solvent - the rest.