CN101774622B - Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3 - Google Patents
Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3 Download PDFInfo
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- CN101774622B CN101774622B CN2009101617258A CN200910161725A CN101774622B CN 101774622 B CN101774622 B CN 101774622B CN 2009101617258 A CN2009101617258 A CN 2009101617258A CN 200910161725 A CN200910161725 A CN 200910161725A CN 101774622 B CN101774622 B CN 101774622B
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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
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 cl ions 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 process 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, and barium polysulfide not have to produce the economic benefit of utilization 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 patented claim 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 patented claim 200910150195.7.It mainly is that barium polysulfide solution is used the kiln gas carbonization, 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 with small amount of deionized water making beating and and HNO
3Reaction generates the filter cake recovery sulier, and the filtrating 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 dividing recycle again.Main chemical reactions of the present invention is following:
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 is as shown in Figure 1.Technical scheme of the present invention is:
In reactor, placing a certain amount of concentration 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 cakes with deionized water heat is washed, solid-liquid separation, solid obtains BaCO through oven dry
3Product.For (NH
4)
2CO
3The not special restriction of the feeding quantity of solution was generally 1～3L/ hour.
The material-water ratio that said 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 gets into 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
#
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 gets into 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 gets into 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 gets into 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, and the open vacuum pump forms 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, and the open vacuum pump forms 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, and the open vacuum pump forms 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 above-mentioned each embodiment 1,2,3 and 4 preparations
3Each parameter of sample such as following table:
| Content | 1 # | 2 # | 3 # | 4 # |
| 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 |
| 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 |
Claims (6)
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;
After B washes cakes with deionized water heat, solid-liquid separation, solid obtains BaCO through oven dry
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101617258A CN101774622B (en) | 2009-08-04 | 2009-08-04 | Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101617258A CN101774622B (en) | 2009-08-04 | 2009-08-04 | Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101774622A CN101774622A (en) | 2010-07-14 |
| CN101774622B true CN101774622B (en) | 2012-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101617258A Active CN101774622B (en) | 2009-08-04 | 2009-08-04 | Method for producing BaCO3 through cyclically recovering and reusing (NH4)2CO3 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849772B (en) * | 2012-09-19 | 2014-06-11 | 中国核动力研究设计院 | Ba<14>CO3 preparation method |
| CN102923750B (en) * | 2012-11-26 | 2014-09-24 | 贵州红星发展股份有限公司 | High-purity barium carbonate prepared by multi-decomposed method and preparation method of high-purity barium carbonate |
| CN103435083B (en) * | 2013-08-29 | 2015-02-11 | 贵州红星发展股份有限公司 | Narrowly distributed subsphaeroidal low-sulfur barium carbonate and preparation method thereof |
| CN103738995B (en) * | 2013-12-13 | 2015-07-08 | 绵阳市远达新材料有限公司 | Method for preparing high purity barium carbonate by using barium nitrate and ammonium bicarbonate |
| CN117085610B (en) * | 2023-08-25 | 2024-06-14 | 贵州红星发展股份有限公司 | System for producing barium carbonate |
| CN117088394A (en) * | 2023-08-25 | 2023-11-21 | 贵州红星发展股份有限公司 | High-purity barium carbonate and production method thereof |
| CN117088395A (en) * | 2023-08-25 | 2023-11-21 | 贵州红星发展股份有限公司 | Production method for synchronously producing barium carbonate of different grades |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043483A (en) * | 1988-12-22 | 1990-07-04 | 化工部天津化工研究院 | The method for making of barium carbonate |
| CN1058199A (en) * | 1990-07-14 | 1992-01-29 | 化学工业部天津化工研究院 | The manufacture method of high-pruity barium carbonate |
| CN1062886A (en) * | 1990-12-27 | 1992-07-22 | 天津市无机化学工业研究所 | Hydrated barta and barium carbonate associating manufacture method |
| CN1150125A (en) * | 1995-11-02 | 1997-05-21 | 于惠生 | Process for preparing calcium carbonate |
| CN1244497A (en) * | 1999-09-08 | 2000-02-16 | 化学工业部天津化工研究设计院 | Preparation of barium carbonate |
| CN101486481A (en) * | 2009-03-02 | 2009-07-22 | 多氟多化工股份有限公司 | Method for coproduction of ammonia sulfate and superfine light calcium carbonate from fluorgypsum |
| CN101492178A (en) * | 2009-03-06 | 2009-07-29 | 瓮福（集团）有限责任公司 | Method for joint production of ammonium sulphate and calcium carbonate with phosphogypsum |
-
2009
- 2009-08-04 CN CN2009101617258A patent/CN101774622B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043483A (en) * | 1988-12-22 | 1990-07-04 | 化工部天津化工研究院 | The method for making of barium carbonate |
| CN1058199A (en) * | 1990-07-14 | 1992-01-29 | 化学工业部天津化工研究院 | The manufacture method of high-pruity barium carbonate |
| CN1062886A (en) * | 1990-12-27 | 1992-07-22 | 天津市无机化学工业研究所 | Hydrated barta and barium carbonate associating manufacture method |
| CN1150125A (en) * | 1995-11-02 | 1997-05-21 | 于惠生 | Process for preparing calcium carbonate |
| CN1244497A (en) * | 1999-09-08 | 2000-02-16 | 化学工业部天津化工研究设计院 | Preparation of barium carbonate |
| CN101486481A (en) * | 2009-03-02 | 2009-07-22 | 多氟多化工股份有限公司 | Method for coproduction of ammonia sulfate and superfine light calcium carbonate from fluorgypsum |
| CN101492178A (en) * | 2009-03-06 | 2009-07-29 | 瓮福（集团）有限责任公司 | Method for joint production of ammonium sulphate and calcium carbonate with phosphogypsum |
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|---|---|
| CN101774622A (en) | 2010-07-14 |
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