CN101559967A - Method for preparing barium nitrate, calcium nitrate, calcium sulfate and sodium nitrate by utilizing middle and low grade barium carbonate ore - Google Patents
Method for preparing barium nitrate, calcium nitrate, calcium sulfate and sodium nitrate by utilizing middle and low grade barium carbonate ore Download PDFInfo
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- CN101559967A CN101559967A CNA200910059462XA CN200910059462A CN101559967A CN 101559967 A CN101559967 A CN 101559967A CN A200910059462X A CNA200910059462X A CN A200910059462XA CN 200910059462 A CN200910059462 A CN 200910059462A CN 101559967 A CN101559967 A CN 101559967A
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Abstract
The invention discloses a method for preparing barium nitrate, calcium nitrate, calcium sulfate and sodium nitrate by utilizing a middle and low grade barium carbonate ore, which is characterized in that the middle and low grade ore of BaCo3 with the content of between 30 and 72 weight percent and CaCO3 with the content of between 15 and 45 weight percent and nitric acid react to prepare the barium nitrate and the calcium nitrate; or the middle and low grade ore and the nitric acid react to prepare the barium nitrate, the double decomposition reaction of a residual mother solution (a calcium nitrate solution) and sodium sulfate are performed to prepare the calcium sulfate and the sodium nitrate, and a small amount of acid undissolved substance is used for cement additive. The method achieves the comprehensive utilization of raw materials, has no discharge of three wastes, and has the advantages of cleanliness, environmental protection, high product quality, and low cost.
Description
Technical field
The present invention relates to the low-grade witherite method that is equipped with nitrate of baryta, nitrocalcite, calcium sulfate and SODIUMNITRATE made of stones in a kind of the utilization, belong to inorganic field of fine chemical.
Background technology
Barium carbonate ore popular name " toxicity stone " belongs to world's rare ore.Have only Mexico and Britain to find this ore deposit in the world, now exploited coda.China finds unique super-huge barium ore deposit, industrial reserve (BaCO
3〉=68%) about 3,800 ten thousand ton.Now formed year 300000 tons of abilities of exploitation, and BaCO
3%=30~60% is about 4~600,000,000 tons, fails so far to exploit and utilizes.
At present, the production method of technical grade nitrate of baryta has both at home and abroad:
1, technical grade barium carbonate (98%) is produced with technical grade nitric acid (98%) reaction;
2, technical grade bariumchloride and SODIUMNITRATE (or ammonium) replacement(metathesis)reaction production;
3, barium sulphide and the production of technical grade nitric acid (98%) direct reaction.
More than the shortcoming of three kinds of methods be: purity is relatively poor, generally reaches 99.0% (international one-level), rare 99.3% (the international top grade) that reach, this purity can not satisfy other industrial requirements; Production cost is higher; While method 3 also has waste residue and poisonous gas (H
2S) discharging, contaminate environment.
At present, the production method of industrial or agricultural level nitrocalcite has both at home and abroad:
1, neutralisation: generate nitrocalcite with nitric acid and calcium carbonate reaction;
2, absorption process: absorb nitric acid tail gas with milk of lime and generate nitrocalcite;
3, by product method: by product when producing nitro phosphor complex with nitric acid decomposing phosphate rock stone obtains Ca (NO through being refrigerated to-10~0 ℃
3)
24H
2O.
Its shortcoming is: product purity is poor, resource-constrained, and bring environmental pollution.
At present, the production method of technical grade SODIUMNITRATE has both at home and abroad:
1, the reaction of caustic soda or soda ash and technical grade nitric acid (98%) is produced;
2, nitric acid, lime and sodium sulfate reaction are produced.
Its shortcoming is: method 1 cost is higher; Method 2 waste residues also do not utilize.
Summary of the invention
The objective of the invention is provides the low-grade witherite method that is equipped with nitrate of baryta, nitrocalcite, calcium sulfate and SODIUMNITRATE made of stones in a kind of the utilization at the deficiencies in the prior art, is characterized in content being the BaCO of 30~72wt%
3CaCO with 15~45wt%
3Middle low grade ore and nitric acid reaction prepare nitrate of baryta and nitrocalcite, perhaps prepare nitrate of baryta with low level ore in above-mentioned and nitric acid reaction, remaining mother liquor (ca nitrate soln) prepares calcium sulfate and SODIUMNITRATE with the sodium sulfate replacement(metathesis)reaction, a little acid non-soluble substance is used for cement additire, reached the starting material comprehensive utilization, three-waste free discharge has clean environment firendly, quality product height, the advantage that cost is low.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The low-grade witherite method that is equipped with nitrate of baryta and nitrocalcite made of stones in the utilization, the chemical equation of this method is as follows:
BaCO
3+2HNO
3→Ba(NO
3)
2+CO
2↑+H
2O
CaCO
3+2HNO
3→Ca(NO
3)
2+CO
2↑+H
2O
And by the preparation of following processing step and processing parameter:
1, the preparation of nitrate of baryta
The adding of concentration 20~40wt% circulating mother liquor 140~166 weight parts is had in the reactor of agitator and thermometer, stir to add down and contain 30~72wt%BaCO
3With 15~45wt%CaCO
3Middle low grade ore breeze 50 weight parts and nitric acid 30~45 weight parts after pulverizing, in 20~60 ℃ of stirring reaction 10~120min of temperature, be cooled to room temperature, when pH=5.0~7.0 remove by filter thin slag, obtain crude product Ba (NO simultaneously
3)
2Crystal and filtrate 191~228 weight parts, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, and the filtrate crystallisation by cooling separates: the solid oven dry, obtain nitrate of baryta product 19~27 weight parts, and yield is 97~~98%, purity reaches 99.7~99.8%; Parting liquid returns and transfers to the lysate use again;
2, the preparation of nitrocalcite
Filtrate part 140~166 weight parts in the step (1) are used as the next round circulating mother liquor, remainder 51~62 weight parts are through evaporation, cooling, crystallization, separation: obtain nitrocalcite product 15.2~48 weight parts, yield is 96~97%, and purity reaches 96~98.2wt%; Parting liquid returns evaporization process and uses;
The low-grade witherite method that is equipped with nitrate of baryta, calcium sulfate and SODIUMNITRATE made of stones in the utilization, the chemical equation of this method is as follows:
BaCO
3+2HNO
3→Ba(NO
3)
2+CO
2↑+H
2O
CaCO
3+2HNO
3→Ca(NO
3)
2·4H
2O+CO
2↑+H
2O
Ca(NO
3)
2·4H
2O+Na
2SO
4→CaSO
4·2H
2O+2NaNO
3+2H
2O
And by following processing step and processing parameter preparation
1, the preparation of nitrate of baryta
To contain the adding of concentration 20~40wt% circulating mother liquor 140~166 weight parts and have in the reactor of agitator and thermometer, and stir to add down and contain 30~72wt%BaCO
3With 15~45wt%CaCO
3Middle low grade ore breeze 50 weight parts and nitric acid 30~45 weight parts after pulverizing, in 20~60 ℃ of stirring reaction 10~120min of temperature, be cooled to room temperature, when pH=5.0~7.0 remove by filter thin slag, obtain crude product Ba (NO simultaneously
3)
2Crystal and filtrate 191~228 weight parts, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation: the solid oven dry, obtain nitrate of baryta product 19~27 weight parts, and yield is 97~98%, purity reaches 99.7~99.8wt%; Parting liquid returns and transfers to the lysate use again;
2, the preparation of calcium sulfate
Filtrate part 140~166 weight parts in the step (1) are used as the next round circulating mother liquor, remainder mother liquor 51~62 weight parts, with sodium sulfate 8.91~43.2 weight parts, add in the reactor that has agitator and thermometer and carry out replacement(metathesis)reaction, in 60~80 ℃ of stirring reactions of temperature 5~30 minutes, separate: obtain terra alba product 10~34 weight parts, yield is 97%, and purity reaches 97.4~98.2wt%; Parting liquid send subsequent processing;
3, the preparation of SODIUMNITRATE
Parting liquid in the step (2) all is heated to 80~100 ℃, and with pH=11~13 of alkali regulator solution, filter and remove residue, filtrate evaporation concentration, crystallisation by cooling obtains SODIUMNITRATE product 10~33 weight parts, and yield is 96~97%, and purity is 98.2~98.7%.
Description of drawings
Fig. 1 be with in the low-grade witherite schema that is equipped with nitrate of baryta and nitrocalcite made of stones.
Fig. 2 be with in the low-grade witherite schema that is equipped with nitrate of baryta, calcium sulfate and SODIUMNITRATE made of stones.
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
1, the preparation of nitrate of baryta
With concentration 20.5wt% circulating mother liquor 140g, adding has in the reactor of agitator and thermometer, stirs to add down to contain 35.5wt%BaCO
3And 58.3wt%CaCO
3In low-grade barium carbonate breeze 50g weight part and concentration be the nitric acid 88g weight part of 51.0wt%, dissolve 15min under the room temperature, be warming up to 60 ℃, stirring reaction 10min is cooled to room temperature, works as pH=5.0, removes by filter thin slag, obtains crude product Ba (NO simultaneously
3)
2Crystal and filtrate 201g, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation: the solid oven dry, obtain nitrate of baryta product 30g, and yield is 97%, purity reaches 99.70wt%; Parting liquid is back to and transfers to the lysate use again.
2, the preparation of nitrocalcite
Filtrate in the step (1) part 140g is made circulating mother liquor use, remainder 61g is heated to 98 ℃, and cooling then, crystallization, separation obtain four water-calcium nitrate product 48g, and yield is 97%, purity 98.2%.
Embodiment 2
1, the preparation of nitrate of baryta
With concentration 40wt% circulating mother liquor 174.5g, adding has in the reactor of agitator and thermometer, stirs to add down to contain 66.5wt%BaCO
3And 18.4wt%CaCO
3In low-grade barium carbonate breeze 50g, with concentration be the nitric acid 60g of 51.0wt%, dissolve 25min under the room temperature, be warming up to 39 ℃, stirring reaction 110min is cooled to room temperature, works as pH=5.5, removes by filter thin slag, obtains crude product Ba (NO simultaneously
3)
2Crystal and filtrate 202g, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation: the solid oven dry, obtain nitrate of baryta product 43.2g, and yield is 98%, purity reaches 99.8wt%; Parting liquid is back to and transfers to the lysate use again.
2, the preparation of nitrocalcite
Filtrate in the step (1) part 174.5g is made circulating mother liquor use, remain a part of 27.5g and be heated to 100 ℃, cooling then, crystallization, separation obtain four water-calcium nitrate product 15.2g, and yield is 96%, purity 98.7%.
Embodiment 3
1, the preparation of nitrate of baryta
With concentration 38wt% circulating mother liquor 160g, adding has in the reactor of agitator and thermometer, stirs to add down to contain 45.1wt%BaCO
3And 39.8wt%CaCO
3In low-grade barium ore breeze 50g and the concentration nitric acid 86.5g that is 46.1wt% after pulverizing, dissolve 25min under the room temperature, be warming up to 50 ℃, stirring reaction 10min is cooled to room temperature, works as pH=6.0, removes by filter thin slag, obtains crude product Ba (NO simultaneously
3)
2Crystal and filtrate 199.8g, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation: the solid oven dry, obtain nitrate of baryta product 29.0g weight part, and yield is 98%, purity reaches 99.78wt%; Parting liquid is back to and transfers to the lysate use again.
2, the preparation of calcium sulfate
160g uses as the next round circulating mother liquor with the part of the filtrate in the step (1), remainder mother liquor 39.8g is heated to 60 ℃, adding concentration is 32wt% sodium sulfate 89g, reaction 5min, filtering separation: solid is through washing, obtain terra alba 34g, yield is 97%, and purity reaches 97.40wt%; Filtrate send subsequent processing to use.
3, the preparation of SODIUMNITRATE
Parting liquid in the step (2) all is heated to 80 ℃, uses Na
2CO
3The pH=11.0 of regulator solution, filter and remove residue, the filtrate evaporation concentration, crystallisation by cooling obtains SODIUMNITRATE product 33 weight parts, and yield is 96~97%, and purity is 98.2~98.7%.
Embodiment 4
1, the preparation of nitrate of baryta
With concentration 58wt% circulating mother liquor 161g, adding has in the reactor of agitator and thermometer, stirs to add down to contain 72.0wt%BaCO
3And 12.4wt%CaCO
3Middle low grade ore breeze 50g and the concentration nitric acid 55g that is 58.0wt% after pulverizing, dissolve 25min under the room temperature, be warming up to 37 ℃, stirring reaction 120min is cooled to room temperature, works as pH=7.0, removes by filter thin slag, obtains crude product Ba (NO simultaneously
3)
2Crystal and filtrate 208g, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation: the solid oven dry, obtain nitrate of baryta product 47g, and yield is 98%, purity reaches 99.8wt%; Parting liquid is back to and transfers to the lysate use again.
2, the preparation of calcium sulfate
Filtrate in the step (1) part 161g is made circulating mother liquor use, remainder 47g is heated to 80 ℃, and adding concentration is 32wt% sodium sulfate 27g, reaction 30min, filtering separation: solid obtains terra alba 10.3g through washing, yield is 97%, purity 98.2%; Parting liquid send subsequent processing to use.
3, the preparation of SODIUMNITRATE
Above-mentioned parting liquid in the step (2) all is heated to 100 ℃, with NaOH regulator solution pH=13.0, filter and remove residue, the filtrate evaporation concentration, crystallisation by cooling obtains SODIUMNITRATE product 10.4g, and yield is 97%, purity 99.76%.
Claims (4)
1, the low-grade witherite method that is equipped with nitrate of baryta and nitrocalcite made of stones in the utilization is characterized in that the chemical equation of this method is as follows:
BaCO
3+2HNO
3→Ba(NO
3)
2+CO
2↑+H
2O
CaCO
3+2HNO
3→Ca(NO
3)
2+CO
2↑+H
2O
2, utilize according to claim 1 in the low-grade witherite method that is equipped with nitrate of baryta and nitrocalcite made of stones, it is characterized in that this method may further comprise the steps:
(1) preparation of nitrate of baryta
The adding of concentration 20~40wt% circulating mother liquor 140~166 weight parts is had in the reactor of agitator and thermometer, stir to add down and contain 30~72wt%BaCO
3With 15~45wt%CaCO
3Middle low grade ore breeze 50 weight parts and nitric acid 30~45 weight parts after pulverizing, in 20~60 ℃ of stirring reaction 10~120min of temperature, be cooled to room temperature, when pH=5.0~7.0 remove by filter thin slag, obtain crude product Ba (NO simultaneously
3)
2Crystal and filtrate 191~228 weight parts, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, and the filtrate crystallisation by cooling separates: the solid oven dry, obtain nitrate of baryta product 19~27 weight parts, and yield is 97~~98%, purity reaches 99.7~99.8wt%; Parting liquid returns and transfers to the lysate use again;
(2) preparation of nitrocalcite
Filtrate part 140~166 weight parts in the step (1) are used as the next round circulating mother liquor, remainder 51~62 weight parts, be heated to 98~100 ℃, cooling then, crystallization, separation, obtain nitrocalcite product 15.2~48 weight parts, yield is 96~97%, and purity reaches 96~98.2wt%, and parting liquid returns evaporization process and uses
3, the low-grade witherite method that is equipped with nitrate of baryta, calcium sulfate and SODIUMNITRATE made of stones in a kind of the utilization is characterized in that the chemical equation of this method is as follows:
BaCO
3+2HNO
3→Ba(NO
3)
2+CO
2↑+H
2O
CaCO
3+2HNO
3→Ca(NO
3)
2·4H
2O+CO
2↑+H
2O
Ca(NO
3)
2·4H
2O+Na
2SO
4→CaSO
4·2H
2O+2NaNO
3+2H
2O
4, as the low-grade witherite method that is equipped with nitrate of baryta, calcium sulfate and SODIUMNITRATE made of stones in as described in the claim 3, it is characterized in that this method may further comprise the steps:
(1) preparation of nitrate of baryta
To contain the adding of concentration 20~40wt% circulating mother liquor 140~166 weight parts and have in the reactor of agitator and thermometer, and stir to add down and contain 30~72wt%BaCO
3With 15~45wt%CaCO
3Middle low grade ore breeze 50 weight parts and nitric acid 30~45 weight parts after pulverizing, in 20~60 ℃ of stirring reaction 10~120min of temperature, be cooled to room temperature, when pH=5.0~7.0 remove by filter thin slag, obtain crude product Ba (NO simultaneously
3)
2Crystal and filtrate 191~228 weight parts, crude product Ba (NO
3)
2Crystal dissolves through multiple the commentaries on classics, removes by filter rough slag, filtrate cooling, crystallization, separation, and the solid oven dry obtains nitrate of baryta product 19~27 weight parts, and yield is 97~98%, and purity reaches 99.7~99.8wt%; Parting liquid returns and transfers to the lysate use again;
(2) preparation of calcium sulfate
Filtrate part 140~166 weight parts in the step (1) are used as the next round circulating mother liquor, remainder mother liquor 51~62 weight parts, with sodium sulfate 8.91~43.2 weight parts, add in the reactor that has agitator and thermometer and carry out replacement(metathesis)reaction, in 60~80 ℃ of stirring reactions of temperature 5~30 minutes, separate: obtain terra alba product 10~34 weight parts, yield is 97%, and purity reaches 97.4~98.2wt%; Parting liquid send subsequent processing;
(3) preparation of SODIUMNITRATE
Parting liquid in the step (2) all is heated to 80~100 ℃, and with pH=11~13 of alkali regulator solution, filter and remove residue, filtrate evaporation concentration, crystallisation by cooling obtains SODIUMNITRATE product 10~33 weight parts, and yield is 96~97%, and purity is 98.2~98.7%.
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Cited By (6)
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CN103303954A (en) * | 2012-03-09 | 2013-09-18 | 黄家鹄 | Method of preparing barium carbonate and/or precipitated calcium carbonate by using raw materials containing barium carbonate and calcium carbonate |
CN104030333A (en) * | 2014-06-27 | 2014-09-10 | 重庆邮电大学 | Method for joint production of strontium nitrate and barium nitrate from high-calcium strontianite and witherite |
CN104829442A (en) * | 2015-01-02 | 2015-08-12 | 赤峰瑞阳化工有限公司 | Method of producing calcium formate with sodium formate as raw material |
CN107500572A (en) * | 2017-10-12 | 2017-12-22 | 广西广厦环保科技有限公司 | Discard the method and system of artificial hilllock lime made of stones |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103303954A (en) * | 2012-03-09 | 2013-09-18 | 黄家鹄 | Method of preparing barium carbonate and/or precipitated calcium carbonate by using raw materials containing barium carbonate and calcium carbonate |
CN102583489A (en) * | 2012-03-30 | 2012-07-18 | 贵州红星发展股份有限公司 | Low-strontium and high-purity nitrate barium and preparation method thereof |
CN102583489B (en) * | 2012-03-30 | 2014-02-26 | 贵州红星发展股份有限公司 | Low-strontium and high-purity nitrate barium and preparation method thereof |
CN104030333A (en) * | 2014-06-27 | 2014-09-10 | 重庆邮电大学 | Method for joint production of strontium nitrate and barium nitrate from high-calcium strontianite and witherite |
CN104030333B (en) * | 2014-06-27 | 2015-07-22 | 重庆邮电大学 | Method for joint production of strontium nitrate and barium nitrate from high-calcium strontianite and witherite |
CN104829442A (en) * | 2015-01-02 | 2015-08-12 | 赤峰瑞阳化工有限公司 | Method of producing calcium formate with sodium formate as raw material |
CN107500572A (en) * | 2017-10-12 | 2017-12-22 | 广西广厦环保科技有限公司 | Discard the method and system of artificial hilllock lime made of stones |
CN115259199A (en) * | 2021-04-29 | 2022-11-01 | 中国科学院过程工程研究所 | Preparation method of defluorinating agent and resource utilization method of fluorine-containing solution |
CN115259199B (en) * | 2021-04-29 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method of defluorinating agent and resource utilization method of fluorine-containing solution |
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