CN102976406A - Process for producing bismuth subnitrate by coarse bismuth oxide - Google Patents
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Abstract
The invention relates to a process for producing bismuth subnitrate by coarse bismuth oxide. The process comprises the following steps: firstly, adding nitric acid to remove chemical impurities to prepare a novel component containing substances unsolvable in nitric acid; then removing the substances unsolvable in nitric acid; introducing an acid soluble filtrate into a hydrolytic tank; and adding deionized water, and hydrolyzing to obtain bismuth subnitrate and a bismuth nitrate mother liquid. With the adoption of the process provided by the invention to prepare bismuth subnitrate products by deep extraction of coarse bismuth oxide, compared with pyrogenic attack, the preparation and calcination of a precursor are canceled. Consumption of chemical reagents is less and the cost of chemical reagents is about 1/2, and compared with other wet treatments, a lot of chemical reagent accessories are saved, the process flow is simplified, and the cost is reduced to a great extent. Meanwhile, the treatment cost of wastewater and exhaust is lowered, so that the process is more environment-friendly.
Description
Technical field
The present invention relates to a kind of production method of bismuth-series chemical product, especially relate to the technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate.
Background technology
Bismuth subnitrate, Chinese another name: Vikaline.Be mainly used in the industry such as medicine, veterinary drug, electronics, ceramic glaze, metal finishing, makeup, also be used for bismuth salt processed.
The raw material of producing bismuth subnitrate generally has 2 kinds, and a kind of is smart bismuth, prepares bismuth oxide by smart bismuth first, makes Bismuth trinitrate again, and the Bismuth trinitrate hydrolysis makes the bismuth subnitrate Chemicals at last.Such as on January 20th, 2010, Chinese invention patent application publication number CNl01628735A, the preparation method of disclosed a kind of bismuth-series chemical product.The method requires high to the smart bismuth of raw materials for production, cause production cost high.Another kind is directly to make Bismuth trinitrate with bismuth oxide, also can be hydrolyzed to make the bismuth subnitrate series chemical product.But desired bismuth oxide purity is quite high, and the bismuth oxide of my company comes from a kind of electric arc furnace settling pocket material, and is impure many.Main manifestations for contain Pb, Cu,, the impurity atom such as As, Na, Ag, Fe, Ni, Ca, K, Si, Sb, also contain the carbon class physical impurity that is insoluble to nitric acid.Be called as thick bismuth oxide on this class bismuth oxide industry.Obviously, this thick bismuth oxide can not reach and produce bismuth subnitrate raw material Application standard.The conventional process pattern adopts and should return the smeltery by thick bismuth oxide, and fire reduction, removal of impurities, the smart bismuth of ingot casting re-use again; Also having the means of processing is the hydrometallurgies that it fully dissolved with the employing acid adding.More than any method all exist processing cost too high, namely to consume a large amount of chemical reagent and discharge a large amount of waste water.
Summary of the invention
Order of the present invention is the problem for described existence, and a kind of usefulness technique that thick bismuth oxide is produced bismuth subnitrate is provided, and solves simultaneously the problem that traditional technology will consume a large amount of chemical reagent and discharge a large amount of waste water.Production cost is significantly reduced, and technical process is brief.
Solution of the present invention is: the technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate, and it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb7-12, Cu 25-30, As 1.5-3, Na 0.5-3, Ag 4-7, Fe 100-125, Ni 1-3, Ca 500-600, K 1-4, Si 60-70, Sb 3-5 is insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; The concrete technology step is as follows:
1. take by weighing thick bismuth oxide-60 order 〉=95% that sieve, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; To restrain/to restrain as unit, liquid-solid mass ratio is 2-20: 1; Nitric acid and thick bismuth oxide raw materials quality are than 1-1.5: 1, temperature of reaction 0-200 ℃ (preferred 85 ℃), reaction times 1-48h (preferred 4 hours) carries out chemical subtraction, control supernatant liquor pH0.5-1.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 0.5-5: 1, temperature 0-100 ℃; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
Above-mentioned thick bismuth oxide raw material comes from a kind of electric arc furnace settling pocket material.
Above-mentioned new compound mainly is bismuth subnitrate.
The above-mentioned carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
The main component of above-mentioned sour lixiviation liquid is Bismuth trinitrate.
Innovative point of the present invention has been to break in the processing step the conventional thinking of utilizing nitric acid to remove to dissolve bismuth, in thick bismuth oxide raw material, add conditionally nitric acid dissolve contain Pb, Cu,, the impurity atoies such as As, Na, Ag, Fe, Ni, Ca, K, Si, Sb.The key problem in technology that the present invention breaks through is, utilizes reaction conditions control nitric acid, allows bismuth generate a kind of bismuth subnitrate compound of insoluble in water, separates with bismuth so that impurity atom becomes filtrate.
The present invention has positive economic benefit and social benefit, and economic benefit shows:
Adopt deep processing of the present invention to prepare the bismuth subnitrate product, compare pyrogenic attack and do again the bismuth subnitrate product, omitted presoma preparation and calcination; Chemical reagent consumption is few, and cost is about 1/2 only, compares other wet processings, has also saved a large amount of chemical reagent auxiliary materials, brief technical process, and cost has also obtained reducing greatly; Compare equally the discharging that CNl01628735A technique also greatly reduces waste water, waste gas, reduced simultaneously waste water, off gas treatment cost, environment is more friendly.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The below is with embodiment and describe by reference to the accompanying drawings the present invention in detail.
Embodiment 1
The technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate, it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb 9, and Cu 30, As 1.5, Na 3, and Ag 4, and Fe 100, Ni 3, Ca 500, and K 2, and Si 70, Sb 5, are insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; The concrete technology step is as follows:
1. take by weighing thick bismuth oxide 50g 96% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 50g; To restrain/to restrain as unit, liquid-solid mass ratio is 2: 1; Nitric acid and thick bismuth oxide raw materials quality be than 1: 1,85 ℃ of temperature of reaction, and 4 hours reaction times was carried out chemical subtraction, control supernatant liquor pH0.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 1: 1,85 ℃ of temperature; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 3, K-, Si 2, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
Embodiment 2
The technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate, it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb 7, and Cu 28, As 2, Na 0.5, and Ag 6, and Fe 125, Ni 2, Ca 560, and K 3, and Si 64, Sb 3, are insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; The concrete technology step is as follows:
1. take by weighing thick bismuth oxide 50g 98% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; To restrain/to restrain as unit, liquid-solid mass ratio is 20: 1; Nitric acid and thick bismuth oxide raw materials quality be than 1.5: 1,0 ℃ of temperature of reaction, and 48 hours reaction times was carried out chemical subtraction, control supernatant liquor pH1; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 5: 1, temperature 50 C; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 4, K-, Si 2, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
Embodiment 3
The technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate, it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb 10, and Cu 25, As 3, Na 3, and Ag 7, and Fe 110, Ni 3, Ca 540, and K 1, and Si 60, Sb 4, are insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; The concrete technology step is as follows:
1. take by weighing thick bismuth oxide 50g-60 orders that sieve and account for 95% of total mass, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 60g; To restrain/to restrain as unit, liquid-solid mass ratio is 4: 1; Nitric acid and thick bismuth oxide raw materials quality be than 1.2: 1,200 ℃ of temperature of reaction, and 1 hour reaction times was carried out chemical subtraction, control supernatant liquor pH1.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 0.5: 1,100 ℃ of temperature; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 3, K-, Si 3, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
Embodiment 4
The technique that the thick bismuth oxide of a kind of usefulness is produced bismuth subnitrate, it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb 12, and Cu 26, As 2, Na 0.5, and Ag 5, and Fe 117, Ni 1, Ca 600, and K 4, and Si 65, Sb 4, are insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; The concrete technology step is as follows:
1. take by weighing thick bismuth oxide 50g 97% of-60 order total masses of sieving, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; To restrain/to restrain as unit, liquid-solid mass ratio is 10: 1; Nitric acid and thick bismuth oxide raw materials quality be than 1.5: 1,100 ℃ of temperature of reaction, and 24 hours reaction times was carried out chemical subtraction, control supernatant liquor pH1.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 4: 1,0 ℃ of temperature; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 4, K-, Si 3, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
Claims (5)
1. technique of producing bismuth subnitrate with thick bismuth oxide, it is as follows by the PPM densitometer to contain impurity atom in the thick bismuth oxide raw material of use: Pb7-12, Cu 25-30, As 1.5-3, Na 0.5-3, Ag 4-7, Fe 100-125, Ni 1-3, Ca 500-600, K 1-4, Si 60-70, Sb 3-5 is insoluble to the carbon class physical impurity of nitric acid less than 0.52% of raw material total mass; It is characterized in that: the concrete technology step is as follows:
1. take by weighing thick bismuth oxide-60 order 〉=95% that sieve, to the coarse particles of screen overflow after grinding such as ball mill class grinding plant after sieve, mixing;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; To restrain/to restrain as unit, liquid-solid mass ratio is 2-20: 1; Nitric acid and thick bismuth oxide raw materials quality are than 1-1.5: 1, temperature of reaction 0-200 ℃ (preferred 85 ℃), reaction times 1-48h (preferred 4 hours) carries out chemical subtraction, control supernatant liquor pH0.5-1.5; Be prepared into a kind of new compound that contains the nitric acid insolubles; So that the mass percent of bi content is greater than 99% in the new compound, bismuth is less than 1g/L in the reaction soln; Press filtration separates; Contain impurity atom liquid and add the heavy bismuth of alkali with known technology, the bismuth slag returns with thick bismuth oxide raw material and mixes again chemical subtraction, perhaps send conventional pyrometallurgical smelting to do bismuth ingot and reclaims; The heavy bismuth waste liquid that produces discharges through environmental protection treatment again;
3. the filter cake with press filtration adds excessive nitric acid, dissolve complete, and the mass ratio of control nitric acid and filter cake is 0.5-5: 1, temperature 0-100 ℃; Filter, the nitric acid insolubles after the filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid lixiviation liquid imports hydrolytic tank, adds deionized water, through hydrolysis, obtains bismuth subnitrate and Bismuth trinitrate mother liquor; It is as follows that this bismuth subnitrate impurity atom is pressed the PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. the Bismuth trinitrate Recycling Mother Solution is used in the chemical subtraction system.
2. the thick bismuth oxide of a kind of usefulness according to claim 1 is produced the technique of bismuth subnitrate, and be further characterized in that: described thick bismuth oxide raw material comes from a kind of electric arc furnace settling pocket material.
3. the thick bismuth oxide of a kind of usefulness according to claim 1 is produced the technique of bismuth subnitrate, and be further characterized in that: described new compound mainly is bismuth subnitrate.
4. the thick bismuth oxide of a kind of usefulness according to claim 1 is produced the technique of bismuth subnitrate, and be further characterized in that: the described carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
5. the thick bismuth oxide of a kind of usefulness according to claim 1 is produced the technique of bismuth subnitrate, and be further characterized in that: the main component of described sour lixiviation liquid is Bismuth trinitrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150306113A1 (en) * | 2014-04-29 | 2015-10-29 | The Procter & Gamble Company | Bismuth Containing Liquid Pharmaceutical Suspensions |
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| CN101760612A (en) * | 2008-12-24 | 2010-06-30 | 深圳市东江环保股份有限公司 | Method for recovering bismuth from secondary zinc oxide slag |
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Patent Citations (3)
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| GB570565A (en) * | 1940-09-12 | 1945-07-12 | Saint Gobain | Improved process for extracting bismuth from alloys |
| CN101760612A (en) * | 2008-12-24 | 2010-06-30 | 深圳市东江环保股份有限公司 | Method for recovering bismuth from secondary zinc oxide slag |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150306113A1 (en) * | 2014-04-29 | 2015-10-29 | The Procter & Gamble Company | Bismuth Containing Liquid Pharmaceutical Suspensions |
| US9486460B2 (en) * | 2014-04-29 | 2016-11-08 | The Procter & Gamble Company | Bismuth containing liquid pharmaceutical suspensions |
| US20170021027A1 (en) * | 2014-04-29 | 2017-01-26 | The Procter & Gamble Company | Bismuth Containing Liquid Pharmaceutical Suspensions |
| US10039835B2 (en) * | 2014-04-29 | 2018-08-07 | The Procter & Gamble Company | Bismuth containing liquid pharmaceutical suspensions |
| US20180303947A1 (en) * | 2014-04-29 | 2018-10-25 | The Procter & Gamble Company | Bismuth Containing Liquid Pharmaceutical Suspensions |
| US10632200B2 (en) * | 2014-04-29 | 2020-04-28 | The Procter & Gamble Company | Bismuth containing liquid pharmaceutical suspensions |
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