CN102976406B - Process for producing bismuth subnitrate by coarse bismuth oxide - Google Patents
Process for producing bismuth subnitrate by coarse bismuth oxide Download PDFInfo
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- CN102976406B CN102976406B CN201210577281.8A CN201210577281A CN102976406B CN 102976406 B CN102976406 B CN 102976406B CN 201210577281 A CN201210577281 A CN 201210577281A CN 102976406 B CN102976406 B CN 102976406B
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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 use 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 for bismuth salt processed.
The raw material of producing bismuth subnitrate generally has 2 kinds, and one is smart bismuth, first prepares bismuth oxide by smart bismuth, then makes Bismuth trinitrate, and Bismuth trinitrate hydrolysis finally makes bismuth subnitrate Chemicals.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 raw materials for production essence bismuth, cause production cost high.Another kind is directly to make Bismuth trinitrate with bismuth oxide, also can be hydrolyzed and make 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, 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.In this class bismuth oxide industry, be called as thick bismuth oxide.Obviously, this thick bismuth oxide can not reach the bismuth subnitrate raw material use standard of producing.Conventional process pattern adopts returns smeltery by this thick bismuth oxide, and fire reduction, removal of impurities, ingot casting essence bismuth re-use again; Also having the means of processing is the hydrometallurgies that it fully dissolved by employing acid adding.Any method all exists processing cost too high above, will 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 use technique that thick bismuth oxide is produced bismuth subnitrate is provided, and solves the problem that traditional technology will consume a large amount of chemical reagent and discharge a large amount of waste water simultaneously.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 use is produced bismuth subnitrate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: 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, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take 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, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; Taking gram/gram 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 DEG C (preferably 85 DEG C), reaction times 1-48h (preferably 4 hours) carries out chemical subtraction, controls supernatant liquor pH0.5-1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5-5: 1, and temperature 0-100 DEG C; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in 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 is mainly 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 acid-soluble filtrate is Bismuth trinitrate.
Innovative point of the present invention has been to have broken in 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 atom such as As, Na, Ag, Fe, Ni, Ca, K, Si, Sb.The present invention break through key problem in technology be, utilize reaction conditions control nitric acid, allow bismuth generate a kind of bismuth subnitrate compound of insoluble in water, make impurity atom become filtrate and separate with bismuth.
The present invention has positive economic benefit and social benefit, and economic benefit shows:
Adopt deep processing of the present invention to prepare bismuth subnitrate product, compare pyrogenic attack and do again bismuth subnitrate product, omitted presoma preparation and calcination; Chemical reagent consumption is few, and cost is only 1/2 left and right, 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 discharge that CNl01628735A technique also greatly reduces waste water, waste gas, reduced waste water, off gas treatment cost simultaneously, environment is more friendly.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Also describe by reference to the accompanying drawings the present invention in detail by embodiment below.
Embodiment 1
The technique that the thick bismuth oxide of use is produced bismuth subnitrate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 9, Cu 30, As 1.5, Na 3, Ag 4, Fe 100, Ni 3, Ca 500, K 2, Si 70, Sb 5, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take 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, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 50g; Taking gram/gram as unit, liquid-solid mass ratio is 2: 1; Nitric acid with thick bismuth oxide raw materials quality than 1: 1,85 DEG C of temperature of reaction, 4 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH0.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 1: 1,85 DEG C of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 3, K-, Si 2, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 2
The technique that the thick bismuth oxide of use is produced bismuth subnitrate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 7, Cu 28, As 2, Na 0.5, Ag 6, Fe 125, Ni 2, Ca 560, K 3, Si 64, Sb 3, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take 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, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; Taking gram/gram as unit, liquid-solid mass ratio is 20: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,0 DEG C of temperature of reaction, 48 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH1; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 5: 1, temperature 50 C; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1, Ni-, Ca 4, K-, Si 2, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 3
The technique that the thick bismuth oxide of use is produced bismuth subnitrate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 10, Cu 25, As 3, Na 3, Ag 7, Fe 110, Ni 3, Ca 540, K 1, Si 60, Sb 4, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take 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, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 60g; Taking gram/gram as unit, liquid-solid mass ratio is 4: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.2: 1,200 DEG C of temperature of reaction, 1 hour reaction times was carried out chemical subtraction, controlled supernatant liquor pH1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5: 1,100 DEG C of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 3, K-, Si 3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Embodiment 4
The technique that the thick bismuth oxide of use is produced bismuth subnitrate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: Pb 12, Cu 26, As 2, Na 0.5, Ag 5, Fe 117, Ni 1, Ca 600, K 4, Si 65, Sb 4, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; Concrete technology step is as follows:
1. take 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, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid 75g; Taking gram/gram as unit, liquid-solid mass ratio is 10: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,100 DEG C of temperature of reaction, 24 hours reaction times was carried out chemical subtraction, controlled supernatant liquor pH1.5; Be prepared into a kind of new compound containing nitric acid insolubles; Make the mass percent of bi content in new compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 4: 1,0 DEG C of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 PPM densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 2, Ni-, Ca 4, K-, Si 3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
Claims (4)
1. a technique of producing bismuth subnitrate with thick bismuth oxide, contains impurity atom in the thick bismuth oxide raw material of use as follows by ppm densitometer: 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, the carbon class physical impurity that is insoluble to nitric acid is less than 0.52% of raw material total mass; It is characterized in that: concrete technology step is as follows:
1. take thick bismuth oxide-60 order >=95% that sieve, to the coarse particles of screen overflow after ball mill class grinding plant grinds after sieve, mix;
2. get the thick bismuth oxide raw material after sieving, add nitric acid; Taking gram/gram 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, and temperature of reaction 0-200 DEG C, reaction times 1-48h carries out chemical subtraction, controls supernatant liquor pH0.5-1.5; Be prepared into a kind of bismuth subnitrate compound; Make the mass percent of bi content in compound be greater than 99%, in reaction soln, bismuth is less than 1g/L; Press filtration, separates; Add the heavy bismuth of alkali containing impurity atom liquid with known technology, bismuth slag returns with thick bismuth oxide raw material and mixes chemical subtraction again, or send conventional pyrometallurgical smelting to do bismuth ingot and reclaim; The heavy bismuth waste liquid producing is through environmental protection treatment, then discharges;
3. the filter cake of press filtration is added to excessive nitric acid, dissolve completely, the mass ratio of controlling nitric acid and filter cake is 0.5-5: 1, and temperature 0-100 DEG C; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Acid-soluble filtrate 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 ppm densitometer: Pb-, Cu-, As-, Na-, Ag-, Fe 1-2, Ni-, Ca 3-4, K-, Si 2-3, Sb-;
4. Bismuth trinitrate Recycling Mother Solution is used in chemical subtraction system.
2. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced bismuth subnitrate, is further characterized in that: described thick bismuth oxide raw material comes from a kind of electric arc furnace settling pocket material.
3. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced bismuth subnitrate, is further characterized in that: the described carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
4. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced bismuth subnitrate, is further characterized in that: the main component of described acid-soluble filtrate is Bismuth trinitrate.
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Non-Patent Citations (5)
| Title |
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| "复杂铅烟尘湿法处理新工艺研究";郑时路等;《中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑》;20060615(第6期);第24-27页、29页 * |
| "次硝酸铋、次碳酸铋的生产方法";厦门冰醋酸厂;《无机盐工业》;19770331(第2期);第54-56页 * |
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