CN1202013C - Process for united producing barium hydroxide and manganese sulfate - Google Patents

Abstract

The invention relates to a process _{for preparing barium hydroxide (Ba(OH) 2 )} and manganese sulfate (MnSO ₄ ) from manganese dioxide (MnO 2 ) and barium sulfide (BaS). The present invention dissolves barium sulfide in water to obtain an aqueous barium sulfide solution with a concentration of 1.1 mol/L; through its hydrolysis and redox reaction with _MnO2 , barium hydroxide and manganese sulfate are obtained. The invention has easy-to-obtain raw materials, simple process, high yield and no pollution, and has great economic benefits, environmental protection benefits and social benefits.

Description

Process for joint production of barium hydroxide and manganese sulfate

technical field

The present invention relates to the preparation of barium hydroxide and manganese sulfate.

Background technique

Barium hydroxide and manganese sulfate are basic chemical raw materials and are in great demand in society. The industrial production of manganese sulfate requires the reaction of MnO and H ₂ SO ₄ , but the preparation of MnO requires the reduction of MnO ₂ with carbon at high temperature, which produces a large amount of CO and causes serious pollution. There are many traditional production methods for producing barium hydroxide, such as: ion exchange method, barium oxide method, barium chloride method, barium silicate method, caustic soda method, zinc oxide and barium sulfide double decomposition method, manganese dioxide oxide barium sulfide method wait. At present, most of the production methods are eliminated due to the complicated process, large consumption and high cost. Although the manganese dioxide oxidized barium sulfide method is feasible to prepare barium hydroxide, there are two major disadvantages: 1) the aqueous solution maximum concentration of barium sulfide is no more than 69 grams per liter, and the barium sulfide concentration reacted with manganese dioxide is low, generating barium hydroxide Finally, a large amount of water needs to be evaporated to crystallize the product; 2) In a strong alkaline solution, the molar ratio of manganese dioxide to barium sulfide reaction is as high as 2.4 to 4, which consumes a large amount of manganese dioxide and cannot be recovered.

Contents of the invention

The purpose of this invention is to provide a kind of processing method of producing barium hydroxide and manganese sulfate, can overcome the shortcoming of prior art. The invention adopts the reaction of manganese dioxide and barium sulfide to obtain barium hydroxide and manganese sulfate at the same time. The raw materials are easy to obtain, the process is simple, the yield is high, no pollution, and has great economic, environmental and social benefits.

The present invention comprises the following steps:

(1) Dissolve solid barium sulfide in water at a temperature of 60-85°C to obtain an aqueous barium sulfide solution, then cool to obtain a mixture of barium hydroxide and barium sulfide crystals, filter to obtain the product barium hydroxide crystals, wash with water 1-3 times The barium sulfide is removed, and the washing solution is returned to use.

(2) Add manganese dioxide to the filtrate to react with Ba(HS) ₂ and BaS in the solution to generate MnO precipitate.

(3) Filtrate to obtain MnO and wash it with water for 1-3 times to remove Ba ²⁺ , HS ^- , S ^2- ions, then dissolve MnO into sulfuric acid; remove S by filtration to obtain manganese sulfate solution; the sulfuric acid is 6mol/L .

(4) Concentrate the manganese sulfate solution, cool and crystallize to obtain manganese sulfate crystals.

(5) The filtrate of (3) is concentrated, cooled and crystallized to obtain barium hydroxide crystals.

The above-mentioned barium sulfide aqueous solution has a concentration of 1.1mol/L; it is cooled at a temperature of 12-18°C. It is best to cool at a temperature of 15°C. The molar ratio of manganese dioxide to ^HS- and ^S2- is 1-1.5:1, preferably 1.1:1.

The feature of the present invention is: shilling barium sulfide is cooled and crystallized from the solution at a certain temperature, due to hydrolysis, a part of product barium hydroxide has been obtained in the crystallization of precipitation, due to the precipitation of barium hydroxide, there is a large amount of Ba in the solution ( HS) ₂ and BaS, like this, the Ba(HS) ₂ and BaS concentration that reacts with manganese dioxide can be up to 120 g/liter; On the other hand, because the precipitation of barium hydroxide, the alkalinity of solution reduces, manganese dioxide and The molar ratio of Ba(HS) ₂ and BaS reaction can be reduced to 1.1, so that the utilization rate of manganese dioxide is greatly improved and the consumption is greatly reduced. Because the washing solution containing barium ions can be recycled in the reaction system, the utilization rate of barium ions in the solution can reach 100%.

Detailed ways

The substantive features and effects of the present invention can be obtained from the following examples, but are not limitations of the present invention.

Example 1

According to steps (1), (2), put 46.5 grams of barium sulfide solids and 250 ml of water in a 500 ml container with temperature control, after reacting for 2 hours, cool and crystallize at 18 ° C, and then wash to remove barium sulfide to obtain 10.86 grams of Ba(OH) ₂ ·8H ₂ O crystals.

Example 2

According to Example 1, cooling and crystallization at 16°C, washing to remove barium sulfide, yielded 12.91 g of Ba(OH) ₂ ·8H ₂ O crystals.

Example 3

According to Example 1, cooling and crystallization at 12°C, washing to remove barium sulfide, yielded 12.28 g of Ba(OH) ₂ ·8H ₂ O crystals.

Example 4

According to Example 1, cooling and crystallization at 15°C, washing to remove barium sulfide, yielded 14.45 g of Ba(OH) ₂ ·8H ₂ O crystals.

Example 5

Under the conditions of Example 4, add 15.66 grams of manganese dioxide in the solution after the crystallization is separated in step (1) according to step (3), the solid phase product after the reaction is dissolved into the sulfuric acid of 6mol/L, obtains product sulfuric acid manganese and crystallized to obtain 28.85 g of MnSO ₄ ·H ₂ O crystals. Yield: 94.84%.

Example 6

Under the conditions of Example 4, 16.44 grams of manganese dioxide was added to the solution, and the solid phase product after the reaction was dissolved in 6mol/L sulfuric acid to obtain the product manganese sulfate and make it crystallize to obtain 30.54 grams of MnSO ₄ ·H ₂ O crystals. Yield: 95.61%.

Example 7

Under the conditions of Example 4, 17.22 grams of manganese dioxide was added to the solution, and the solid phase product after the reaction was dissolved in sulfuric acid to obtain the product manganese sulfate and crystallize it to obtain 32.83 grams of MnSO ₄ ·H ₂ O crystals. Yield: 98.12%.

Example 8

Under the conditions of Example 4, 18.79 grams of manganese dioxide was added to the solution, and the reacted solid-phase product was dissolved in sulfuric acid to obtain the product manganese sulfate and crystallize it to obtain 35.21 grams of MnSO ₄ ·H ₂ O crystals. Yield: 96.46%.

Example 9

Under the conditions of Example 4, 18.01 g of manganese dioxide was added to the solution, and the reacted solid-phase product was dissolved in sulfuric acid to obtain the product manganese sulfate and crystallize it to obtain 33.34 g of MnSO ₄ ·H ₂ O crystals. Yield: 95.31%.

Example 10

Under the conditions of Example 7, after obtaining the product manganese sulfate and crystallizing it, and filtering it, the filtrate is concentrated together with the washing liquid containing barium ions recovered according to steps (1) and (3), cooled and crystallized to obtain Barium crystal 72.00 grams, together with the barium hydroxide crystal that embodiment 4 obtains is 86.45 grams in total. Yield: 99.79%.

Claims (7)

1, a kind of processing method of producing hydrated barta and manganous sulfate is a raw material with Manganse Dioxide and barium sulphide solid, it is characterized in that it comprises the following steps:

(1) with solid barium sulphide water-soluble barium sulfide solution that obtains under 60-85 ℃ of temperature, cooling obtains hydrated barta and barium sulphide crystalline mixture then, filters, and gets product hydrated barta crystal, washes the flush away barium sulphide 1-3 time, and washings returns use;

(2) add Manganse Dioxide in the filtrate, make Ba (HS) in itself and the solution ₂Reaction generates the MnO precipitation with BaS;

(3) filter, obtain MnO washing 1-3 time, remove Ba ²⁺, HS ^-, S ^2-Behind the ion, MnO dissolves in sulfuric acid again; Remove by filter S, obtain manganese sulfate solution;

(4) concentrated vitriol manganese solution, cooling, crystallization obtain manganous sulfate;

(5) with the filtrate of (3), concentrate, crystallisation by cooling obtains the hydrated barta crystal.

2,, it is characterized in that described step (1) barium sulfide solution concentration is 1.1mol/L according to the processing method of described production hydrated barta of claim 1 and manganous sulfate.

3,, it is characterized in that described step (1) barium sulfide solution is to cool off under the 12-18 ℃ of temperature according to the processing method of described production hydrated barta of claim 1 and manganous sulfate.

4. according to the processing method of described production hydrated barta of claim 3 and manganous sulfate, it is characterized in that described barium sulfide solution is to cool off under 15 ℃ of temperature.

5, according to the processing method of described production hydrated barta of claim 1 and manganous sulfate, it is characterized in that described step (2) Manganse Dioxide and HS ^-And S ^2-The molar ratio of sum is 1～1.5: 1.

6, according to the processing method of described production hydrated barta of claim 1 and manganous sulfate, it is characterized in that described step (2) Manganse Dioxide and HS ^-And S ^2-The molar ratio of sum is 1.1: 1.

7,, it is characterized in that described step (3) sulfuric acid is 6mol/L according to the processing method of described production hydrated barta of claim 1 and manganous sulfate.