CN101774622A

CN101774622A - Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3

Info

Publication number: CN101774622A
Application number: CN200910161725A
Authority: CN
Inventors: 姜志光; 华东
Original assignee: BEIJING WANKUN JIAHONG SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
Current assignee: BEIJING WANKUN JIAHONG SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd; Guizhou Redstar Developing Co Ltd
Priority date: 2009-08-04
Filing date: 2009-08-04
Publication date: 2010-07-14
Anticipated expiration: 2029-08-04
Also published as: CN101774622B

Abstract

The invention relates to a method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3, which comprises the following steps: rising the temperature for boiling 0.4 to 0.85 mol/L Ba(NH3)2 solution; stopping heating; adding 2 to 3.5 mol/L (NH4)2CO3 under the agitation for reaction; carrying out solid and liquid separation; carrying out hot washing on obtained filter cake by deionized water; then, carrying out solid and liquid separation; obtaining BaCO3 products after baking the solid; evaporating and concentrating the obtained mother liquid to 400 to 500 g/L; then, carrying out heating reaction for the mother liquid and the BaCO3 in a sealed container; controlling the reaction temperature in a range between 70 and 118 DEG C; introducing NH3 and CO2 released in the reaction in the step C into an absorption device to be absorbed; detecting the concentration of CO3<2-> and NH<4+> in absorption liquid; and supplementing a proper amount of lime-kiln gas for synthesizing (NH4)2CO3. The invention can cyclically utilize the NH4CO3 for preparing BaCO3 products with low strontium content and low calcium magnesium content.

Description

A kind of recycling (NH 4) 2CO 3Produce BaCO 3Method

Technical field

The present invention relates to prepare BaCO ₃Method, particularly recycling (NH ₄) ₂CO ₃Produce BaCO ₃Method.

Background technology

High-pruity barium carbonate is the main crystal phase material of electronics sensitive ceramic, mainly contains two kinds of operational paths of bariumchloride and nitrate of baryta at present, bariumchloride route chlorion washing difficulty, and energy consumption is big; The nitrate of baryta route need separate to reduce Ca, Mg, Sr impurity, high impurity mother liquor difficult treatment raw material nitrate of baryta recrystallization.

CN1425613 discloses a kind of Manganse Dioxide (MnO that utilizes ₂) and barium sulphide (BaS) be feedstock production hydrated barta (Ba (OH) ₂) and the processing method of manganous sulfate (MnSO4), the chemical reaction that relates generally among this preparation method is exactly that barium sulphide and Manganse Dioxide reaction generate manganese monoxide and barium polysulfide, barium polysulfide does not have to produce the economic benefit of utilizing fully as liquid waste disposal.

Also narrated the method for dioxide ore for manganese and barium sulphide prepared in reaction manganous sulfate in inventor's patent application 200910157921.8 formerly, mainly be to utilize the manganese monoxide that generates in the reaction, so utilize the barium polysulfide that generates to enrich product line as low-cost raw material.

The inventor also narrated the method for utilizing barium polysulfide solution to prepare nitrate of baryta in formerly the patent application 200910150195.7.It mainly is with the kiln gas carbonization of barium polysulfide solution, and carbonization produces BaCO ₃Separate with sulphur mixing solutions suction strainer, mother liquor returns the leaching operation, and filter cake heat is washed back suction strainer separation, and filter cake is pulled an oar and and HNO with small amount of deionized water ₃Reaction generates the filter cake recovery sulphur, and the filtrate evaporative crystallization makes BaNO ₃

Summary of the invention

The present invention is exactly the Ba (NO that utilizes above-mentioned preparation ₃) ₂Prepare low strontium low calcium and magnesium BaCO ₃Product and NH ₄CO ₃The recovery technology of subdivision recycle.Main chemical reactions of the present invention is as follows:

Ba(NO ₃) ₂+(NH ₄) ₂CO ₃→BaCO ₃+2NH ₄NO ₃

2NH ₄NO ₃+BaCO ₃→Ba(NO ₃) ₂+2NH ₃↑+CO ₂↑

2NH ₃↑+CO ₂↑+H ₂O→(NH ₄) ₂CO ₃

Main technique schema of the present invention as shown in Figure 1.Technical scheme of the present invention is:

Placing a certain amount of concentration in reactor is 0.4～0.85mol/L, is preferably the Ba (NO of 0.7～0.85mol/L ₃) ₂Solution, intensification is boiled, and stops heating, stirs to add 2～3.5mol/L (NH down ₄) ₂CO ₃Synthesize, solid-liquid separation, mother liquid evaporation concentrates back and BaCO ₃Prepared in reaction Ba (NO ₃) ₂And recovery (NH ₄) ₂NO ₃Make compound agent, after filter cake is washed with deionized water heat, solid-liquid separation, the solid drying obtains BaCO ₃Product.For (NH ₄) ₂CO ₃The feeding quantity of solution is not particularly limited, and is generally 1～3L/ hour.

The material-water ratio that described heat is washed can be 1: 5, and it is 80-100 ℃ that heat is washed temperature, and the heat time of washing is 1～2 hour.For hot washing process, those skilled in the art know the various parameters that heat is washed, and each parameter is not strict the qualification, more than listed parameter generally be applicable to hot washing process.

Lay special stress on of the present invention NH ₄NO ₃The recycling method, Ba (NO ₃) ₂With (NH ₄) ₂CO ₃Mother liquor after synthetic contains certain density (NH ₄) ₂NO ₃, earlier with this solution with three-effect evaporation and condensation to 400～500g/L, then with BaCO ₃Be reflected at the reaction of encloses container internal heating, control reaction temperature is at 70～118 ℃ of scopes, the NH that discharges ₃And CO ₂The feeding absorption unit absorbs, and gets absorption liquid.The reactant gases absorption unit is fairly simple, is multipurpose plant, and the injection that deionized water is housed absorbs container exactly.Above-mentioned generated reactive gas is measured CO in the absorption liquid after absorbing then ₃ ^2-And NH ₄ ⁺Concentration, in room temperature～65 ℃, be preferably and mend an amount of limestone kiln gas (carbonic acid gas) under 40～60 ℃ of conditions, make it synthetic (NH ₄) ₂CO ₃

With existing bariumchloride prepared BaCO ₃Compare, handicraft product washing of the present invention is comparatively simple, and energy consumption is low, compares with existing nitrate of baryta technology, and the present invention need not to carry out Ba (NO ₃) ₂Recrystallization just can obtain the low high-purity BaCO of strontium low calcium and magnesium ₃Product.

Description of drawings

Fig. 1 is a process flow sheet of the present invention.

Embodiment

Embodiment 1

With [Ba ²⁺] 0.85mol/L nitrate of baryta solution 3000ml places the 5000ml beaker, heated and boiled stops heating, stirs to add 3.0mol/L (NH down ₄) ₂CO ₃900ml added speed control about 1.5L/ hour.

Above-mentioned synthetic material suction strainer is separated, and with the drip washing of small amount of thermal deionized water, merging filtrate enters recovery system, filter cake is washed suction strainer separation after 1 hour by 100 ℃ of heat of 1: 5 material-water ratio, places 180 ℃ of drying in oven acquisition in 16 hours BaCO ₃Sample 1 ^#

Embodiment 2

With [Ba ²⁺] 0.83mol/L nitrate of baryta solution 3000ml places the 5000ml beaker, heated and boiled stops heating, stirs to add 2.15mol/L (NH down ₄) ₂CO ₃1220ml, control adding speed is about 2.0L/ hour.

Above-mentioned synthetic material suction strainer is separated, and with the drip washing of small amount of thermal deionized water, merging filtrate enters recovery system, filter cake washes by 100 ℃ of heat of 1: 5 material-water ratio that suction strainer separates after 1 hour, places 180 ℃ of baking ovens to dry 16 hours acquisition BaCO ₃Sample 2 ^#

Embodiment 3

With [Ba ²⁺] 0.40mol/L nitrate of baryta solution 3000ml places the 5000ml beaker, heated and boiled stops heating, stirs to add 2.0mol/L (NH down ₄) ₂CO ₃630ml, control adding speed is about 2.0L/ hour.

Above-mentioned synthetic material suction strainer is separated, and with the drip washing of small amount of thermal deionized water, merging filtrate enters recovery system, filter cake washes by 100 ℃ of heat of 1: 5 material-water ratio that suction strainer separates after 1 hour, places 180 ℃ of baking ovens to dry 16 hours acquisition BaCO ₃Sample 3 ^#

Embodiment 4

With [Ba ²⁺] 0.7mol/L nitrate of baryta solution 3000ml places the 5000ml beaker, heated and boiled stops heating, stirs to add 3.5mol/L (NH down ₄) ₂CO ₃630ml, control adding speed is about 2.0L/ hour.

Above-mentioned synthetic material suction strainer is separated, and with the drip washing of small amount of thermal deionized water, merging filtrate enters recovery system, filter cake washes by 100 ℃ of heat of 1: 5 material-water ratio that suction strainer separates after 1 hour, places 180 ℃ of baking ovens to dry 16 hours acquisition BaCO ₃Sample 4 ^#

Embodiment 5

Mother liquor behind embodiment 1 or the 2 building-up reactions suction strainers is carried out evaporation concentration, with (NH wherein ₄) ₂NO ₃Concentration is controlled at 400～420g/L scope, according to (NH ₄) ₂NO ₃: BaCO ₃The ratio that is 2.2: 1 adds BaCO ₃, reaction beaker covers with film, and emulsion tube is connected to the absorption bottle in the ice-water bath, adds an amount of water in the absorption bottle, opens vacuum pump and form little negative pressure in absorption bottle.The reacting by heating beaker is until the nearly 118 ℃ of stopped reaction of temperature, and the gas of generation feeds sponge oil unit.Measure CO in the absorption liquid ₃ ^2-And NH ₄ ⁺Concentration be respectively 2.14mol/L and 4.71mol/L, mend the (NH that limestone kiln gas generates 2.30mol/L ₄) ₂CO ₃Solution is modulated into suitable concentration recycle with it.

Embodiment 6

Mother liquor behind embodiment 1 or the 2 building-up reactions suction strainers is carried out evaporation concentration, with (NH wherein ₄) ₂NO ₃Concentration is controlled at 480～500g/L scope, according to (NH ₄) ₂NO ₃: BaCO ₃The ratio that is 2.2: 1 adds BaCO ₃, reaction beaker covers with film, and emulsion tube is connected to the absorption bottle in the ice-water bath, adds an amount of water in the absorption bottle, opens vacuum pump and form little negative pressure in absorption bottle.The reacting by heating beaker is until the nearly 70 ℃ of stopped reaction of temperature, and the gas of generation feeds sponge oil unit.Measure CO in the absorption liquid ₃ ^2-And NH ₄ ⁺Concentration be respectively 1.97mol/L and 4.24mol/L, mend the (NH that limestone kiln gas generates 2.05mol/L ₄) ₂CO ₃Solution is modulated into suitable concentration recycle with it.

Embodiment 7

Mother liquor behind embodiment 1 or the 2 building-up reactions suction strainers is carried out evaporation concentration, with (NH wherein ₄) ₂NO ₃Concentration is controlled at 440～460g/L scope, according to (NH ₄) ₂NO ₃: BaCO ₃The ratio that is 2.2: 1 adds BaCO ₃, reaction beaker covers with film, and emulsion tube is connected to the absorption bottle in the ice-water bath, adds an amount of water in the absorption bottle, opens vacuum pump and form little negative pressure in absorption bottle.The reacting by heating beaker is until the nearly 90 ℃ of stopped reaction of temperature, and the gas of generation feeds sponge oil unit.Measure CO in the absorption liquid ₃ ^2-And NH ₄ ⁺Concentration be respectively 3.02mol/L and 6.40mol/L, mend the (NH that limestone kiln gas generates 3.15mol/L ₄) ₂CO ₃Solution is modulated into suitable concentration recycle with it.

The BaCO of the various embodiments described above 1,2,3 and 4 preparations ₃Each parameter of sample such as following table:

Content	??1 ^#	??2 ^#	??3 ^#	??4 ^#
Content	??1 ^#	??2 ^#	??3 ^#	??4 ^#	??BaCO ₃(weight %)	??99.92	??99.95	??99.87	??99.90
??Sr	??54ppm	??57ppm	??62ppm	??47ppm	??BaCO ₃(weight %)	??99.92	??99.95	??99.87	??99.90
??Sr	??54ppm	??57ppm	??62ppm	??47ppm	??Ca	??＜50ppm	??＜50ppm	??＜50ppm	??＜50ppm
??Mg	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm	??Ca	??＜50ppm	??＜50ppm	??＜50ppm	??＜50ppm
??Mg	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm	??Na	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm
??K	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm	??Na	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm
??K	??＜10ppm	??＜10ppm	??＜10ppm	??＜10ppm	??Fe	??＜5ppm	??＜5ppm	??＜10ppm	??＜10ppm
??D ₅₀um	??0.67	??0.78	??0.66	??0.81	??Fe	??＜5ppm	??＜5ppm	??＜10ppm	??＜10ppm

Claims

1. recycling (NH ₄) ₂CO ₃Produce BaCO ₃Method, it comprises step:

A is with the Ba (NO of 0.4～0.85mol/L ₃) ₂Solution heats up and boils, and stops heating, stirs to add 2～3.5mol/L (NH down ₄) ₂CO ₃React, solid-liquid separation gets mother liquor and filter cake;

B washes filter cake with deionized water heat after, solid-liquid separation, the solid drying obtains BaCO ₃Product;

C is with mother liquid obtained evaporation concentration to 400～500g/L, then with BaCO ₃Be reflected at the reaction of encloses container internal heating, control reaction temperature is 70～118 ℃ of scopes;

The NH that D discharges reaction among the step C ₃And CO ₂The feeding absorption unit absorbs, and gets absorption liquid;

E measures CO in the absorption liquid ₃ ^2-And NH ₄ ⁺Concentration, under ℃ condition of room temperature～65, mend an amount of limestone kiln gas, make it synthetic (NH ₄) ₂CO ₃

2. recycling (NH according to claim 1 ₄) ₂CO ₃Produce BaCO ₃Method, used Ba (NO in the steps A wherein ₃) ₂The concentration of solution is 0.7～0.85mol/L.

3. recycling (NH according to claim 1 ₄) ₂CO ₃Produce BaCO ₃Method, wherein among the step B heat to wash material-water ratio be 1: 5.

4. recycling (NH according to claim 1 ₄) ₂CO ₃Produce BaCO ₃Method, wherein among the step B heat to wash temperature be 80-100 ℃.

5. recycling (NH according to claim 1 ₄) ₂CO ₃Produce BaCO ₃Method, wherein the heat time of washing is 1～2 hour among the step B.

6. recycling (NH according to claim 1 ₄) ₂CO ₃Produce BaCO ₃Method, wherein in the step e, under 40～60 ℃ of conditions, mend limestone kiln gas.