WO2006111057A1 - PROCEDE POUR UTILISER TOTALEMENT LA MATIERE PREMIERE DANS UN TRAITEMENT EN MILIEU HUMIDE DE PHOSPHORITE ET PRODUIRE UN NANO-CARBONATE de CALCIUM AVEC UNE GRANDE PURETE ET DE FORME MICROSPHERIQUE EN MEME TEMPS - Google Patents

PROCEDE POUR UTILISER TOTALEMENT LA MATIERE PREMIERE DANS UN TRAITEMENT EN MILIEU HUMIDE DE PHOSPHORITE ET PRODUIRE UN NANO-CARBONATE de CALCIUM AVEC UNE GRANDE PURETE ET DE FORME MICROSPHERIQUE EN MEME TEMPS Download PDF

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Publication number
WO2006111057A1
WO2006111057A1 PCT/CN2005/002346 CN2005002346W WO2006111057A1 WO 2006111057 A1 WO2006111057 A1 WO 2006111057A1 CN 2005002346 W CN2005002346 W CN 2005002346W WO 2006111057 A1 WO2006111057 A1 WO 2006111057A1
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WIPO (PCT)
Prior art keywords
acid
calcium
phosphate rock
water
solution
Prior art date
Application number
PCT/CN2005/002346
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English (en)
Chinese (zh)
Inventor
Shandong Wu
Zheng Wu
Original Assignee
Shandong Wu
Zheng Wu
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Filing date
Publication date
Application filed by Shandong Wu, Zheng Wu filed Critical Shandong Wu
Publication of WO2006111057A1 publication Critical patent/WO2006111057A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/18—Nitrates of ammonium
    • C01C1/185—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present invention relates to the comprehensive utilization of phosphate rock and the acid which decomposes phosphate rock, and more particularly to the separation and extraction of calcium from phosphate rock and the secondary use of used acid. . Background technique .
  • Phosphate rock is a mineral containing calcium, phosphorus and a large amount of impurities, of which about 40-50% of calcium, less than 18% of phosphorus, mainly used as raw materials for the production of phosphorus products, such as phosphoric acid, ammonium phosphate, phosphate fertilizer.
  • phosphorus products such as phosphoric acid, ammonium phosphate, phosphate fertilizer.
  • Ca 5 F(P0 4 )3 + 10HNO 3 5Ca(N0 3 ) 2 + 3H 3 P0 4 + HF t (3)
  • High-efficiency utilization, and the recovery of calcium is very difficult, and the unused raw materials may cause certain harm to the environment.
  • CaCl 2 after extraction of 3 ⁇ 4P0 4 is soluble and can be recovered by adding a suitable precipitant to produce pure calcium compound, but a large amount of water and chloride brought by HC1 brings recovery.
  • CaS0 4 * 2 H 2 0 in formula (2) is a mixture containing a large amount of sediment, CaS0 4 is insoluble and extremely difficult to purify; in formula (3), the acid solution is a calcium, phosphorus mixed system, calcium Phosphorus can only coexist in an ionic state under strong acid conditions.
  • the value is greater than 4
  • CaHP0 4 precipitates, and when the pH is greater than 9, there is almost no calcium phosphate in the acid solution. This is also the reason for decomposing the fluorine-containing calcium salt of the acidity, that is, the phosphate rock, with a strong acid.
  • the object of the present invention is to find a simple and effective method for the secondary comprehensive utilization of waste calcium and used acid in the phosphate rock processing industry, and the use of an acid which must be used for decomposing phosphate rock to change the easily volatile ammonia into fixed ammonium.
  • a variety of products can be obtained by selecting different precipitants; the calcium in the phosphate rock powder is made into a pure compound and the high-purity microsphere nano calcium carbonate is produced in parallel.
  • the surgical solution of the present invention includes the following steps:
  • a precipitant that forms a precipitate of a calcium compound is added to the acid solution.
  • the technical solution adopted by the present invention includes the following steps:
  • the acid is preferably nitric acid, hydrochloric acid, phosphoric acid or any mixture thereof;
  • step (b) Adding the acid hydrolysis solution to the acid solution obtained in step (a); the pH value of the substance, controlling the pH value in the range of 0-12, preferably pH 2-12, obtaining the solidified water-soluble calcium and phosphorus Acid solution;
  • step (c) purifying the acid hydrolysate obtained in the step (b) to obtain an acid hydrolyzate containing water-soluble calcium, and a separated phosphorus-containing cured product;
  • a precipitant which forms a precipitate of a calcium compound is added to the acid-soluble solution containing water-soluble calcium obtained in the step (c) to obtain a precipitate of a calcium compound such as calcium sulfate or calcium carbonate.
  • the obtained calcium compound is treated to obtain high-purity microsphere nano calcium carbonate with a particle size of 20 nm--500.
  • the technical solution for preparing a calcium compound precipitate of the present invention can be cyclically co-produced with a conventional acid hydrolysis phosphate method.
  • the first concept of the present invention was developed from equation (3) to analyze how to obtain pure calcium.
  • the acid hydrolysis solution of the formula (3) is a highly acidic solution in which water-soluble calcium and phosphorus ions coexist, and can be purified by filtration, natural sedimentation, and removal of specific ions by adding a chemical reagent to obtain water-soluble calcium.
  • Purified calcium in the purified acidolysis solution is separated by a precipitant capable of forming a calcium compound precipitate under strong acidic conditions.
  • the added precipitant determines the process product orientation of formula (3).
  • the invention selects a precipitant containing SO/—series, such as H 2 S0 4 , Na 2 S0 4 , K 2 S0 4 , (NH 4 ) 2 S0 4 , etc. containing cations such as H+, Na+, K ⁇ + 4, etc. It is water-soluble, purifiable, and has a single precipitation of CaS0 4 and has good compatibility with the original phosphorus product process.
  • the reaction can obtain both pure CaS0 4 and an acid capable of decomposing phosphate rock, that is, HN0 3 is regenerated, and a cyclic reaction is formed with the formula (3), in which the 3 ⁇ 4P0 4 forms a concomitant. HN0 3 forms a circulating medium.
  • H 3 P0 4 in the separation formula (4) is subjected to extraction.
  • HN0 3 and H 3 P0 4 can enter the compound fertilizer to prepare ammonium phosphate nitrate, but also lose HN0 3 at the same time, while the sulfuric acid method prepares the ammonium, there is neither extraction process nor a large amount of HN0 3 source, 'this takes The separation problem of 3 ⁇ 4P0 4 came.
  • another concept of the present invention is: using different forms of phosphate at different pH values, in the case of containing a large amount of water-soluble Ca 2+ , the calcium salt of each form of phosphoric acid has different solubility characteristics, and the acid is controlled.
  • the phosphate content of the solution is such that the water-soluble phosphorus is limited to a certain range so that it does not affect the purity and quantity of the calcium compound, that is, the phosphorus is left in the solid without being decomposed into water-soluble, and Calcium is decomposed into water-soluble, calcium is first recovered, and high-phosphorus solids that have not been decomposed into water-soluble phosphorus are introduced into the process of producing phosphorus products such as ammonium, calcium, and calcium hydrogen phosphate.
  • this method reduces the amount of calcium recovered, it has obtained two pure substances, especially pure calcium, which can be combined with the current original production process. Therefore, when the pH value is controlled to 4 or more (as long as the phosphate rock powder is excessively controlled, the pH value can be controlled to be greater than 4), there is the following formula:
  • Ca(H 2 P0 4 ) 2 also plays a certain role in media, and has the ability to carry Ca 2+ , but its dissolved enthalpy is too small, under strong acid It is also only about 0.5mol/l. Insufficient use is only an auxiliary function.
  • the dominant role is HN0 3 , and its concentration can be artificially adjusted to within the range of near saturation. In order to obtain a good purification effect and a practical amount of calcium compound precipitation, the acid concentration is adjusted to control Ca 2 . ⁇ in the practical range of 0.5- 8 mol / l, at 2-6 mol / 1 preferred.
  • HN0 3 in the formulae - (8) and (9) may also be replaced by a mixed acid of any ratio of HCl or HN0 3 and HCl.
  • the amount of acid used in this step-by-step decomposition method and the amount of acid used in the one-step decomposition method are equal in both theoretical analysis and actual 'implementation, except that the same amount of acid brings a very different result.
  • a third concept of the invention resides in the value of recovering pure calcium, that is, product orientation and source of raw materials. It can be seen in formula (4), formula (5), formula (6), and formula (7) that different precipitants have significant differences in the orientation of the process and product. In the implementation, it must contribute to the original process, and also solve the problem of sufficient source of precipitant. H 2 S0 4 and Na 2 S0 4 are easily available, and K 2 S0 4 and (N3 ⁇ 4) 2 S04 are relatively difficult to solve, and the recovered pure CaS0 4 is not ideal as the product enters the market, and the price and the sales capacity are not satisfactory.
  • the ammonium salt of carbonate is both purified and industrially supported. Because the ammonia contained therein is easily volatilized and reduces the nitrogen use rate, it can be used to form a mutually supporting cycle process with CaS0 4 , as shown in the following formula:
  • the present invention accomplishes the following overall response:
  • the process equipment for extracting phosphoric acid is not used in the process, and the large amount of HC1 and HN0 3 required for forming water-soluble calcium are not used, and only the stepwise decomposition method can be adopted. .
  • the formula (7) has clearly expressed embodiment recovering pure calcium.
  • the invention has the following help in the process: In the ammonium phosphate, due to the influence of no Ca 2+ , the total nutrient content and the water solubility of phosphorus can be greatly improved, especially the ammonium nitrogen is increased, and the nitrogen fertilizer is adsorbed in the soil. Increase, reduce loss, use better, and eliminate the freezing process.
  • the treatment of phosphate rock by the step-by-step decomposition method has unique advantages for the ammonium phosphate ammonium nitrate process: for the acid hydrolysis solution after decalcification of formula (8), adjusting the ffl value 8-9 to separate CaHP0 4 , CaF 2 and After the iron and aluminum impurities are adjusted, the PH value is 9-12, and Mg(0H) 2 is separated to obtain the calcium hydrogen phosphate fertilizer mainly composed of CaHP0 4 , wherein the effective phosphorus is not easily fixed by iron and aluminum to reduce the fertilizer efficiency. A purer Mg (0H) 2 can be obtained.
  • This method is especially suitable for the development and utilization of high-iron, high-magnesium and low-grade phosphate rock.
  • the purified Ca(N0 3 ) 2 can form a series of high-quality nitrates, which react with K 2 S0 4 , (NH 4 ) 2 S0 4 , Na 2 S0 4 , (N ) 2C0 3 , NH 4 HC 0 3 , respectively.
  • the precipitant containing C0 3 2 - has great advantages, the process is simple, the product is pure, the reactant concentration is high, the investment is small, the effect is quick, and the original process can greatly reduce the load of the freezing process. Or save the freezing process. . 'Benefit effect
  • the beneficial effects of the invention 1. Further utilizing the raw materials used for preparing the phosphorus product of the acid phosphate rock to prepare a plurality of pure products. 2.
  • the invention has good compatibility with the current technology, and not only can co-produce many products, the development scale can be large or small, and the new process is simple and easy. 3.
  • the process steps of the present invention adopt a recycling process, and there is no pollution of three wastes. 4.
  • the invention can produce high-quality calcium carbonate, ammonium sulfate and ammonium nitrate in large quantities, especially to obtain high-purity, micro-sphere, nano-scale calcium carbonate, which not only provides market demand, but also has good economic, social and social benefits. . .
  • Figure 1 is a process flow diagram for preparing decalcified phosphate rock and pure calcium sulfate.
  • Figure 2 is a process flow diagram for the full recovery of calcium, phosphorus and acid from decalcified phosphate rock.
  • Figure 3 is a flow chart showing the process of producing high-purity microsphere nano-calcium carbonate from the separated high-purity calcium sulfate.
  • the clear solution is filtered to clear and transparent into the Ca 2+ clear solution tank.
  • the solid-liquid mixture in the regeneration reaction tank is sent to a solid-liquid separation suction filter tank for filtration, and the filtrate is regenerated acid and sent to the acid hydrolysis tank.
  • step 4 Return to step 4. Return to step 2 when the Ca 2+ containing solution is used up.
  • the solid matter is taken out from the acid hydrolysis tank and filtered to a water content of about 25%.
  • the molar ratio of nitrate nitrogen to 1.2%, Ca046%, . Ca 2+ /P0 4 3- was 1.3.
  • This embodiment has a particularly good effect on the treatment of high-iron and high-magnesium phosphate rock.
  • Most of the iron and magnesium impurities enter the acid hydrolysis solution, and the pH value is mentioned to about 8 with lime milk, and CaHP0 4 and iron can be separated, and then PH The value mentions 12, Mg 2+ will precipitate completely, and the acid solution is pure Ca 2+ containing solution.
  • Example 2 Full recovery of calcium, phosphorus and acid from decalcified phosphate rock
  • the product is transferred into a vacuum suction filter box for solid-liquid separation, and 100 kg of fresh water is added for washing three times. Put The strongly acidic filtrate and washing liquid were combined to about 380 kg, and sent to an evaporation process to be ammoniated and dried.
  • N-P-K ternary compound fertilizer can be obtained.
  • CaC0 3 10kg, powdery, non-caking, purity greater than 98%, whiteness greater than 98%, microsphere type, uniform particle size and less than '100 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Fertilizers (AREA)

Abstract

La présente invention fournit un procédé pour utiliser totalement la matière première dans un traitement en milieu humide de phosphorite et produire un nano-carbonate de calcium avec une grande pureté et de forme microsphérique en même temps, qui résout les problèmes dus au fait que le calcium est abandonné et que l’acide utilisé n'est pas réutilisé dans les procédés existants. Le procédé comprend : la réaction d’un phosphorite avec un acide pour produire une solution contenant un ion Ca2+ hydrosoluble et un phosphate, l’addition d’un matériau à la solution obtenue pour ajuster la valeur du pH ; puis la purification de la solution, et l’addition d’un produit de précipitation dans celle-ci pour entraîner la précipitation d’un composé de calcium unitaire et pur. Chaque étape du procédé est effectuée dans un mode de recyclage, et est bien compatible avec les procédés existants, et peut produire de nombreux types de produits en même temps. Le procédé est simple. Selon le procédé, un nano-carbonate de calcium avec une grande pureté et de forme microsphérique, un sulfate d'ammonium et un nitrate d'ammonium peuvent être produits à grande échelle.
PCT/CN2005/002346 2005-04-18 2006-01-10 PROCEDE POUR UTILISER TOTALEMENT LA MATIERE PREMIERE DANS UN TRAITEMENT EN MILIEU HUMIDE DE PHOSPHORITE ET PRODUIRE UN NANO-CARBONATE de CALCIUM AVEC UNE GRANDE PURETE ET DE FORME MICROSPHERIQUE EN MEME TEMPS WO2006111057A1 (fr)

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CN200510067111.5 2005-04-18
CN200510067111.5A CN1686816B (zh) 2005-04-18 2005-04-18 对酸解磷矿的原料综合利用和联产高纯微球纳米碳酸钙的方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111302376A (zh) * 2020-02-27 2020-06-19 武汉工程大学 利用盐酸酸解高镁磷尾矿制备阻燃剂的方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1962421B (zh) * 2006-11-19 2010-04-14 武善东 酸解磷矿的方法
CN101168852B (zh) * 2007-08-31 2011-10-26 武善东 一种大规模生产硫酸钙晶须的方法
CN101311355B (zh) * 2008-04-24 2012-05-02 云南民族大学 一种磷石膏制备硫酸钙晶须的方法
CN102417169B (zh) * 2011-08-15 2013-11-20 武善东 一种含镁磷矿的酸解方法
CN104150521B (zh) * 2014-08-06 2016-05-11 广东省工业技术研究院(广州有色金属研究院) 一种含稀土磷灰石矿回收磷和钙的方法

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JPS5175696A (ja) * 1974-12-27 1976-06-30 Onoda Chem Ind Co Ltd Rinkosekinobunkaiho
CN1118331A (zh) * 1994-08-07 1996-03-13 张智新 盐酸或硝酸循环法分解磷矿粉
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JPS5175697A (ja) * 1974-12-27 1976-06-30 Onoda Chem Ind Co Ltd Rinkosekinobunkaihoho
JPS5175696A (ja) * 1974-12-27 1976-06-30 Onoda Chem Ind Co Ltd Rinkosekinobunkaiho
CN1118331A (zh) * 1994-08-07 1996-03-13 张智新 盐酸或硝酸循环法分解磷矿粉
CN1285312A (zh) * 1999-08-22 2001-02-28 李怀然 盐酸法制作饲料级磷酸氢钙和付产碳酸钙及氯化铵新工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111302376A (zh) * 2020-02-27 2020-06-19 武汉工程大学 利用盐酸酸解高镁磷尾矿制备阻燃剂的方法

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