CN102992401B - Process for producing bismuth aluminate by using crude bismuth oxide - Google Patents
Process for producing bismuth aluminate by using crude bismuth oxide Download PDFInfo
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- CN102992401B CN102992401B CN201210577287.5A CN201210577287A CN102992401B CN 102992401 B CN102992401 B CN 102992401B CN 201210577287 A CN201210577287 A CN 201210577287A CN 102992401 B CN102992401 B CN 102992401B
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Abstract
The invention relates to a process for producing bismuth aluminate by using a crude bismuth oxide. The process comprises the following steps of: firstly, adding nitric acid to remove chemical impurities to prepare a novel compound containing nitric acid insoluble substance, and then removing the nitric acid insoluble substance; and secondly, adding sodium metaaluminate to the acid-soluble filtering solution after being filter to obtain a mother liquor of bismuth aluminate and sodium nitrate. By utilizing the process for extracting and deeply processing the crude bismuth oxide to prepare bismuth aluminate products, compared with the pyrogenic attack, the preparation and calcination of a precursor are omitted, so that the consumption of chemical reagents is small and the cost is only 50%; compared with other wet processes, a great amount of chemical reagent auxiliary materials is also saved, the process flows are shortened and the cost is also greatly reduced; and meanwhile, the cost for treating wastewater and waste gas is reduced, and 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 Aluminate.
Background technology
Bismuth Aluminate is a kind of decahydrate.Utmost point calomel mercurous chloride end, almost water-fast alkaline matter.Generally by sodium aluminate, react and make with Bismuth trinitrate.And the raw material of producing Bismuth trinitrate has 2 kinds, a kind of is smart bismuth, first by smart bismuth, prepares bismuth oxide, then makes Bismuth trinitrate.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 with bismuth oxide, to make Bismuth trinitrate.But desired bismuth oxide purity is quite high, the bismuth oxide of Er Wo 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 oxide 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 to make its hydrometallurgy fully dissolving by employing acid adding, filters physical impurity, by crystallization, adds alkali and prepares new compound or pass through extracting and separating.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 Aluminate 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 Aluminate, 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; With gram/Ke Wei 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 ℃ (preferably 85 ℃), 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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 ℃; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
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 sour lixiviation liquid 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 key problem in technology that the present invention breaks through is, utilizes reaction conditions to control nitric acid, allows bismuth generate a kind of bismuth subnitrate compound of insoluble in water, makes impurity atom become filtrate separated 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 Aluminate product, compare pyrogenic attack, then do Bismuth Aluminate 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.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
By embodiment, also describe by reference to the accompanying drawings the present invention in detail below.
Embodiment 1
The technique that the thick bismuth oxide of use is produced Bismuth Aluminate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: 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, and 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; With gram/Ke Wei unit, liquid-solid mass ratio is 2: 1; Nitric acid with thick bismuth oxide raw materials quality than 1: 1,85 ℃ 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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 ℃ of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
Embodiment 2
The technique that the thick bismuth oxide of use is produced Bismuth Aluminate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: 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, and 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; With gram/Ke Wei unit, liquid-solid mass ratio is 20: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,0 ℃ 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
Embodiment 3
The technique that the thick bismuth oxide of use is produced Bismuth Aluminate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: 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, and 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; With gram/Ke Wei unit, liquid-solid mass ratio is 4: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.2: 1,200 ℃ 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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 ℃ of temperature; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
Embodiment 4
The technique that the thick bismuth oxide of use is produced Bismuth Aluminate, contains impurity atom in the thick bismuth oxide raw material of use as follows by PPM densitometer: 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, and 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; With gram/Ke Wei unit, liquid-solid mass ratio is 10: 1; Nitric acid with thick bismuth oxide raw materials quality than 1.5: 1,100 ℃ 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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 ℃ of temperature; Filter, the nitric acid insolubles after filtering send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
Claims (5)
1. with thick bismuth oxide, produce a technique for Bismuth Aluminate, in the thick bismuth oxide raw material of use, contain impurity atom 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; With gram/Ke Wei 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 ℃, reaction times 1-48h 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, separation; Containing impurity atom liquid, with known technology, add the heavy bismuth of alkali, 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 ℃; Filter, the nitric acid insolubles after filtration send conventional pyrometallurgical smelting to do reductive agent or fuel; Sour lixiviation liquid after filtration adds sodium metaaluminate, obtains Bismuth Aluminate and SODIUMNITRATE mother liquor;
4. SODIUMNITRATE mother liquor concentration and recovery SODIUMNITRATE product.
2. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced Bismuth Aluminate, 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 Aluminate, is further characterized in that: described new compound is mainly bismuth subnitrate.
4. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced Bismuth Aluminate, is further characterized in that: the described carbon class physical impurity that is insoluble to nitric acid exists with solid-state.
5. the technique that the thick bismuth oxide of a kind of use according to claim 1 is produced Bismuth Aluminate, is further characterized in that: the main component of described sour lixiviation liquid is Bismuth trinitrate.
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| CN201210577287.5A CN102992401B (en) | 2012-12-27 | 2012-12-27 | Process for producing bismuth aluminate by using crude bismuth oxide |
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| RU2125020C1 (en) * | 1997-11-11 | 1999-01-20 | Товарищество с ограниченной ответственностью "Цветмет" | Method of bismuth nitrate basic producing |
| CN100528758C (en) * | 2007-03-28 | 2009-08-19 | 湖南金旺实业有限公司 | Method for producing powder in micron order of bismuth oxide |
| CN101987746A (en) * | 2009-08-05 | 2011-03-23 | 天津市化学试剂研究所 | Method for preparing high-purity bismuth oxide |
| CN101774640A (en) * | 2010-01-25 | 2010-07-14 | 云南云铜稀贵新材料有限公司 | Method for synthesizing bismuth subnitrate and bismuth aluminate |
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