WO2008061473A1 - Procédé d'acidolyse de phosphorite - Google Patents

Procédé d'acidolyse de phosphorite Download PDF

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Publication number
WO2008061473A1
WO2008061473A1 PCT/CN2007/071089 CN2007071089W WO2008061473A1 WO 2008061473 A1 WO2008061473 A1 WO 2008061473A1 CN 2007071089 W CN2007071089 W CN 2007071089W WO 2008061473 A1 WO2008061473 A1 WO 2008061473A1
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Prior art keywords
acid
phosphate rock
solution
calcium
phosphate
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PCT/CN2007/071089
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English (en)
Chinese (zh)
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Shandong Wu
Zheng Wu
Jianhua Zhang
Shanbin Wu
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Shandong Wu
Zheng Wu
Jianhua Zhang
Shanbin Wu
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Publication of WO2008061473A1 publication Critical patent/WO2008061473A1/fr

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    • 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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/26—Compounds containing phosphorus
    • 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
    • C01B25/18—Phosphoric acid
    • C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process

Definitions

  • the present invention relates to a method for the acidolysis of phosphate rock, and more particularly to a novel method for fully utilizing the raw material of the acid phosphate rock - Background
  • the technical solution includes four characteristic steps: 1. Phosphate rock The acid hydrolysis solution prepared by reacting with acid to prepare water-soluble calcium and phosphorus; 2. adding a substance which adjusts the pH value of the acid hydrolysis solution, and controlling the pH value in the range of 0-12; 3. purifying the acid hydrolysis solution; 4. in the acid hydrolysis solution A precipitant which forms a precipitate of the calcium compound is added.
  • the method can recover pure calcium compound and used acid root, but the obtained phosphorus product is impure: when the phosphate rock is decomposed with sulfuric acid, it contains Ca(H 2 P0 4 ) 2 ⁇ 2 0, CaHP0 4 ⁇ 2 ⁇ 2 A mixture of 0 and phosphate rock and acid insolubles, which is a mixture of phosphoric acid (or phosphate) and nitric acid (or nitrate) in the ammonium phosphate ammonium nitrate process. Under the premise of ammonium phosphate process or phosphorous product process, impure phosphorus products can be further processed and contribute to these processes. The drawback of this method is that no pure, pure phosphorus product is obtained. Although there are independent and pure phosphorus products in the current phosphorus product processing technology, it has not been able to recover and utilize calcium and used acid roots with high efficiency. Summary of the invention
  • An object of the present invention is to overcome the deficiencies of the above process and to provide a novel method for comprehensive utilization of all raw materials except for acid insolubles in the acid phosphate rock process.
  • the technical solution of the present invention includes the following steps:
  • step a A precipitant is added to the purified acid hydrolyzate to form a calcium compound precipitate, and the calcium compound and the filtrate are separated.
  • the acid described in step a is a mixed acid containing HCL, or HN0 3 , or H 3 P0 4 , or any combination of the three.
  • the HCL includes an HCL solution in which the HCL gas formed by the reaction of H 2 S0 4 with KCL or NaCl is absorbed by the acid hydrolysis solution.
  • the separation described in step b is to separate the solid matter in the acid hydrolysis solution by means of sedimentation separation, and the obtained acid hydrolysis liquid is an acid hydrolysis liquid from which the solid matter is separated;
  • the phosphorus-containing compound includes phosphate rock or phosphoric acid. Hydrogen calcium or any ratio of the two
  • the preferred particle size of the phosphate rock is greater than 1 mm, more preferably 10 to 200 mm.
  • the solid matter described in the step c is a solid matter washed with washing water, and the washing water is derived from the defluorinated acid hydrolyzate, which is washed with the solid matter and returned to the acid hydrolyzate before defluorination.
  • the separated fluorine compound described in the step d is a method of forming a fluorosilicate precipitate, or a method of forming a CaF lake, or a combination of the two methods; and the method for forming a fluorosilicate precipitate is to add a water solution to the acid solution.
  • Potassium or sodium salt such as NaCl, or KC1, or NaN0 3 , or KN0 3 ; the way to form CaF 2 precipitate is to add CaC0 3 , Ca(OH) 2 to the acid solution.
  • step e The purification described in step e is to filter out the solid matter, or to add a chemical reagent to separate various impurities, or a combination of the two.
  • Said step f precipitant containing S04 2 - a water-soluble compounds containing S04 2 - - class or C0 3 2-soluble compound is H 2 S0 4, K 2 S0 4, Na 2 S0 4, (NH 4 ) 2 S0 4 KHS0 4 , NaHS0 4 , water-soluble compounds containing C0 3 2 - are Na 2 C0 3 , NaHC0 3 , (NH 4 ) 2 C0 3 NH 4 HC0 3 , KHC0 3 ;
  • the resulting calcium compound is CaS0 4 ⁇ XH 2 0 or CaC0 3 , X is 0, 1/2 or 2;
  • the filtrate obtained is an acid-containing filtrate or an acid-free filtrate, and the acid-containing filtrate contains HCL, or HN0 3 , or H 3 P0 4 , or a combination of the three in any ratio, returns to the acid phosphate rock step a, and the acid-free filtrate exits the invention and enters other processes.
  • the above methods are not necessarily carried out in the order of 1 to 6, or may be flexibly combined according to actual needs.
  • the acid solution contains a low concentration of phosphoric acid, and the cycle does not dephosphorize; the fluorine content is low. , the cycle does not defluorinate.
  • FIG. 2 is a process flow diagram of the present invention for phosphating phosphate rock.
  • Figure 3 is a process flow diagram of the present invention for producing feed grade calcium hydrogen phosphate and calcium dihydrogen phosphate.
  • Fig. 4 is a flow chart showing the process of acidifying phosphate rock using HC1 and HNO3 as raw materials in the present invention.
  • the dotted arrow in the figure indicates the feasible flow direction.
  • the dotted line in Figure 2 indicates the open solution outlet of the acid solution and enters other processes.
  • Acid-dissolved phosphate rock selects a strong acid such as HCL, HN0 3 , H 3 P0 4 or a mixed acid of any ratio which can form water-soluble calcium to decompose the phosphate rock to obtain an acid solution. Since the decomposition products are mainly water-soluble calcium and phosphoric acid, this reduces the requirement for the particle size of the phosphate rock from the principle of the reaction. From a practical point of view, the mineral material having a particle size of 300 mm or less can be selected as long as the acid solution is immersed in the phosphate rock. In the middle, the acid hydrolysis process can be completed within 1 hour. If the capacity of the acid hydrolysis tank is greater than or equal to twice the volume of the acid hydrolysis solution, the ball milling process can be omitted, and the phosphate rock size can be reduced. Taking the intracellular circulation of the acid solution can speed up the reaction.
  • a strong acid such as HCL, HN0 3 , H 3 P0 4 or a mixed acid of any ratio which can form
  • Sedimentation separation For the acid hydrolysis solution after acid hydrolysis of phosphate rock, it is preferred to separate the solid matter by sedimentation, and after solid precipitation for 1 to 2 hours, more than 99% of the solid matter can be separated. If a flocculant is added, the settling process can be completed quickly.
  • the acid solution containing the solid matter contains 3 ⁇ 4 ?0 4 .
  • the present invention utilizes a phosphorus-containing compound for dephosphorization, i.e., removal of 3 ⁇ 4P0 4 in the acidolysis solution.
  • the phosphorus-containing compound used is mainly phosphate rock, and its reaction with H 3 P0 4 is:
  • the first type, using large-sized massive phosphate rock When the particle size of the phosphate rock is larger than lmm, the density of the phosphate rock is about 3 g/cm 3 , and the difference between the two solid particles and the density can be completely separated by a swirling method; When the particle size of the phosphate rock is 10 - 200 mm, the swirling action can be omitted, and the acid solution can directly take away the crystalline solid to achieve solid-solid separation, and the large-sized massive phosphate rock is preferred. If the practical reaction time is 2-4 hours, this method is preferred. Heating or cycling the acid hydrolysate in the tank accelerates the reaction.
  • the solid matter of Ca(H 2 P0 4 ) 2 ⁇ 3 ⁇ 40 crystal is repeatedly decomposed repeatedly by H 3 P0 4 in the acid solution, since Ca(H 2 P0 4 ) 2 ⁇ 2 0 does not react with H 3 P0 4 Only the phosphate rock reacts with H 3 P0 4 , and the final product is a solid substance mainly composed of Ca(H 2 P0 4 ) 2 ⁇ 3 ⁇ 40 crystal.
  • Removal of H 3 P0 4 from the acidolysis solution also includes the use of CaHP0 4 ⁇ 2 ⁇ 2 0+. ⁇ 2 This phosphorus-containing compound.
  • the fluoride-containing phosphorus-containing compound is derived from the defluorination step of the feed calcium hydrogen phosphate process, and is obtained by neutralizing about 50% of water-soluble phosphorus with CaC0 3 or Ca(OH) 2 together with all the F- in the solution. a mixture that is used as a fertilizer. Although this is not a quality product, it is an ideal defluorination link.
  • CaHP0 4 ⁇ 2H 2 0+CaF 2 can react with H 3 P0 4 in the acid hydrolysis solution, and its reaction rate is much higher than that of phosphate rock.
  • the acid solution entering the dephosphorization step contains water-soluble phosphorus preferably 2 to 4 mol/l.
  • the concentration is low, the yield of Ca(H 2 P0 4 ) 2 * H 2 0 is low; when the concentration is high, the concentration of Ca 2+ ions is also high, and the loss of circulating medium is easily increased for subsequent decalcification.
  • the acid concentration is preferably 3-6 mol/lH + , and the concentration of H 3 P0 4 in the acid hydrolysis solution is mainly increased by the circulation method, and the medium loss in the decalcification process is taken into consideration.
  • the acid is reacted only once with the phosphate rock, preferably at a high concentration of 6-12 mol/l H + , in order to increase the yield of Ca(H 2 P0 4 ) 2 ⁇ H 2 0 as much as possible.
  • defluorination, purification dephosphorization of the acid solution, according to Mg 2+ , Al 3 + and other impurities can have three destinations: First, less impurities, no defluorination, direct purification, get calcium-containing serum and then take off Calcium; Second, the fluorine is high, then enter the defluorination process with NaCl or KC1 (NaN0 3 or KN0 3 ) to form fluorosilicate to Fl to lOg / 1 or less, and then purify to obtain calcium-containing serum, and then Decalcification; Thirdly, there are many impurities such as Mg 2+ and Al 3+ .
  • the acid hydrolysis solution is further purified by the feed hydrogen phosphate process after defluorination, ie: To increase the pH value, add an alkaline substance to the acid solution, such as NH 3 , CaC0 3 , CaCOH ⁇ , etc., and adjust the PH value to 2-4 to obtain the fertilizer dicalcium (CaHP0 4 ⁇ 2H 2 0+CaF 2 ), and then adjust PH value to 8, to feed the calcium dihydrate CaHP0 4 ⁇ 2H 2 0, and then adjust the PH value to 12, remove magnesium to make easy to process Mg (OH) 2; the acid solution after purification is already fluorine-free and pure
  • the calcium-containing serum can be used as washing water for washing Ca(H 2 P0 4 ) 2 * H 2 0. This kind of washing water from the acid hydrolysis system and returned to the original system after washing the product ensures the water balance regardless of the amount.
  • the purification of the acid solution is a pretreatment measure that must be carried out in order to obtain a high-purity calcium compound.
  • the standard of purification is that the calcium compound formed by the reaction of the acid solution and the precipitant has unity, and the purity of purity above 98% can be separated. Calcium compound.
  • the purified acid solution contains water-soluble calcium, which can produce a large number of compounds.
  • the present invention selects two major types of precipitants, namely S04 2 - and C0 3 2 - water-soluble precipitants.
  • Formula (3) constitutes the cyclic acid of the indirect acidolysis of phosphate rock
  • the solution method, HC1, HN0 3 , H3PO4 becomes a circulating medium, and the acid solution of formula (3) is dephosphorized according to formula (1) and then returns to formula (2) to remove pure calcium.
  • Formula (3), formula (1), and formula (2) constitute the dominant acid hydrolysis route of the sulfuric acid phosphate phosphate of the present invention.
  • CaS0 4 ⁇ 2 ⁇ 2 0 in the formula (2) When the concentration of H 2 S0 4 and the reaction temperature are different, CaS0 4 and CaS0 4 ⁇ 1/2H 2 0 can be formed, and CaS0 4 ⁇ 2H 2 0 can be easily filtered and washed.
  • the product CaS0 4 ⁇ ⁇ 2 0 differs depending on the reaction temperature and concentration, and the value of X can be 0, 1/2 or 2, respectively.
  • sulfate has a similar effect as sulfuric acid.
  • the process of adding a by-product HCL (gas) can be carried out in addition to promoting the present invention under the conditions of the original raw material types, and can also use the HCL open-loop acid-smelting phosphate rock in large quantities, and can mass-produce the sulfate required for the process.
  • HCL gas
  • it does not affect the decomposition of phosphate rock and the preparation of potassium and sodium salts of high-concentration high-quality phosphoric acid, and makes the utilization rate of all raw materials all 100% fully comprehensive utilization. This allows the innovation and utility of the present invention to be more fully embodied.
  • Decomposing phosphate rock with sulfuric acid to produce ammonium phosphate and phosphate, adding NaCl or KC1 raw materials and sulfuric acid to produce sulfate or acid sulfate and by-product HC1 (gas) based on raw materials used in the current process, or adding circulating medium HC1 KN0 3 , CaCl 2 , etc., can promote the invention to achieve complete comprehensive utilization of raw materials. Its innovation and practicality are reflected in the quality of high-purity calcium compounds and the quality of the high-purity calcium compounds, regardless of the grade of the phosphate ore and the amount of impurities.
  • the present invention can provide it with concentrated phosphoric acid or phosphate which is not concentrated by evaporation.
  • the HC1 gas is produced by reacting with NaCl+H 2 S0 4 or 2KC1+H 2 S0 4 (high temperature), and is absorbed into the acid hydrolysis tank by the acid hydrolysis solution, if there are raw materials such as HC1, HN0 3 , CaCl 2 , Ca(N0 3 ) 2 and the like. This step can be saved.
  • the part of the particle size of the phosphate rock is 10 to 200 mm, and the lump ore is placed in the dephosphorization tank, and the rest is placed in the acid hydrolysis tank to react with the acid solution for about 1 hour, and the H + ion concentration is preferably 3-6 mol/l.
  • the acid solution is sedimented and purified into a calcium-containing clear liquid pool.
  • the water-soluble calcium in the calcium-containing clear liquid reacts with H 2 S0 4 (or acid sulfate) to obtain 150-250 kg CaSO per cubic meter of acid hydrolysis solution.
  • 4 ⁇ 2 ⁇ 2 0 is the preferred reaction concentration; the particle size distribution of CaS0 4 ⁇ 2H 2 0 is 1-20 ⁇ m, the average particle size is about 10 ⁇ m, the purity of washing can reach 98% or more; CaS0 is separated by solid-liquid separation. 4 ⁇ 2 ⁇ 2 0, the filtrate is returned to the acid hydrolysis tank. This is a main process line for the acidolysis of phosphate rock to produce pure CaS0 4 ⁇ 2H 2 0.
  • the acid solution is cycled once per cycle on this process line. Except for CaS0 4 * 2H 2 0, the concentration of H 3 P0 4 in the acid solution is continuously increased, when free H 3 P0 4 and water-soluble Ca (H 2 P0) 4) 2 H 2 P0 4 _ total of 2- 4mol / l, separated from the acid solution bath acid solutions were dried NATURAL settle for about 1 hour, (flocculant was added quickly detachable suspension), separated The clear liquid enters the dephosphorization tank and reacts with the massive phosphate rock (or CaHP0 4 ⁇ 2 ⁇ 2 0+.& ⁇ 2 ) to form CaCH 2 P0 4 ) 2 ⁇ 2 0 precipitate to remove H 3 P0 4 from the acid solution.
  • the generated Ca(H2P04) 2 ⁇ ⁇ 20 crystal is taken out to realize the solid-solid separation of the ore and Ca(H 2 P0 4 ) 2 ⁇ 3 ⁇ 40, and then the natural sedimentation and filtration are utilized. In other ways, the solid solution separation of the acid solution and Ca(H 2 P0 4 ) 2 * H 2 0 is achieved.
  • Ca(H 2 P0 4 ) 2 ⁇ 3 ⁇ 40 can also be washed with a defluorinated acidolysis solution.
  • the separated Ca(H 2 P0 4 ) 2 ⁇ ⁇ 2 0 has a ⁇ 2 0 5 content of 50-55%.
  • sulfuric acid or sulfate a high concentration of pure phosphoric acid or a series of phosphoric acid or Phosphate products, a major process line for the production of phosphorus products.
  • the defluorination process can be entered.
  • the Na 2 SiF 6 or K 2 SiF 6 precipitate is formed by reacting NaCl or KC1 with H 2 SiF 6 in the acid hydrolyzate, thereby F1 punching to below 10 g/1.
  • the process has two ways to withdraw the acid solution from the circulation system: one is to make a mouth and separation from the feed calcium hydrogen phosphate process.
  • Example 2 The invention is applied to the production of feed grade calcium hydrogen phosphate and calcium dihydrogen phosphate
  • the innovation and practicability of the present invention are embodied in the case of sulfuric acid and phosphate rock as the main raw material, and the acid-digested calcium dihydrogen phosphate is acid-resolved by a closed-loop acid hydrolysis method, and the raw materials are fully integrated.
  • the conversion rate of phosphorus to feed is 100%, and the ratio of feed calcium to calcium is arbitrarily adjustable.
  • the existing feed calcium hydrogen phosphate process is only used to solve the separation impurities in the present invention, and a fluorine-free aqueous solution is prepared for washing the feed-calcium to ensure the system water balance.
  • the ore selected from the phosphate rock with a particle size of 20-200 mm is placed in the dephosphorization tank, and the rest is placed in the acid hydrolysis tank and added with a concentration of 3.6 mol/l of HC1 (HN0 3 ) for acid hydrolysis, and the acid hydrolysis solution is naturally After sedimentation and purification, the acid solution was decalcified with H 2 S0 4 , and the filtrate after CaS0 4 ⁇ 2 ⁇ 2 0 was separated and returned to the acid hydrolysis tank for the next cycle, and the lost HC1 was added.
  • the generated Ca(H 2 P0 4 ) 2 * H 2 0 is subjected to solid-liquid separation in the separation of one calcium step, and is initially washed by the washing water of the washing-calcium step, and the separated solid matter is washed into the washing-calcium step with fluorine-free washing. The water is washed again.
  • Partially pure Ca(H 2 P0 4 ) 2 * H 2 0 is separated by swirling, and the remaining Ca(H 2 P0 4 ) 2 ⁇ H 2 0 containing more impurities enters the acid hydrolysis-calcium process, and then HC1 (HN0 3 , H 2 S0 4 ) is decomposed into H 3 P0 4 and the acid residue is filtered off.
  • the acid residue contains phosphorus and is placed in a settling tank. Precipitated with high quality CaC0 3 or Ca(OH) 2
  • the acid hydrolysis liquid and the washing liquid separated in the separation process of one calcium are incorporated into the acid hydrolysis system from the purification process when the fluorine content is not high; when the fluorine content is 20 to 60 g/l, the fluorine is defluorinated and then incorporated into the solution. Acid hydrolysis system.
  • the present invention separates and supplies wash water with magnesium-based impurity ions by the existing calcium-feeding process.
  • the acid solution after defluorination is first precipitated with CaCO 3 or Ca(OH) 2 to produce fertilizer dicalcium (Ca(H 2 P0 4 ) 2 ⁇ H 2 0+CaF 2 ), and the fluorine-containing dicalcium is added.
  • HN0 3 and HC1 are used as raw materials to dissolve phosphate rock.
  • This embodiment focuses on accepting various processes and products with high economic benefits, low energy consumption and low investment to form a new high-efficiency comprehensive utilization. Process.
  • the main reason for decomposing phosphate rock with HC1 is to:
  • Decomposing phosphate rock with HN0 3 is mainly for obtaining:
  • the acid hydrolysis of phosphate rock with HC1 is a ring-opening acid hydrolysis method.
  • the acid concentration is preferably 6-12 mol/l, preferably at a high concentration; the phosphate rock contains P 2 O 5 30%, (CaO +MgO) About 50%, 10mol/l HCL(HNO 3 ) can obtain an acid hydrolysis solution of 3 mol/l concentration of H 3 P0 4 .
  • the acid phosphorus solution contains saturated Ca(H 2 P0 4 ) 2 .
  • This embodiment is the open-loop acidolysis form of Figure 1, which is used to decalcify and regenerate HC1 (HN0 3 ) in the acid hydrolysis solution by using H 2 S0 4 (or HS0 4 _ ) in the calcium-containing supernatant process or the decalcification process. , return it to the acid hydrolysis pool, which constitutes a closed-loop acid hydrolysis form.
  • the process is open-loop closed-loop freely, and its practicability is: when accepting low concentration HC1 (HN0 3 ), H 2 S0 4 (or HS0 4 — ) can be used as a precipitant for closed-loop acid hydrolysis, and then ring-opening acid solution Liquid (when the impurities are too much) A large amount of low-concentration acid is accepted.
  • This process has good applicability to mixed acids.
  • the Ca(H 2 P0 4 ) 2 .H 2 0 separated by the process contains about 50-55% of P 2 0 5 , can be used as a fertilizer, and can also be used as a feed grade product by using the conditions of the process (see Example 2). Or made into industrial grade, agricultural grade phosphate (see Example 1).
  • the CaC0 3 produced in the decalcification step in the present embodiment has the condition of generating nano-scale CaC0 3 , and belongs to the current technology (see "Calcium Phosphate Industry” 1987 ( 1-2 ), page 96, the inorganic salt information center station of the Ministry of Chemical Industry, calcium carbonate Intelligence Collaboration Group) Compile. Industrial applicability
  • the main idea of the present invention is to make full use of the chemical energy of the acid and the advantages of the current phosphide processing technology, and the phosphate rock can be decomposed by using HCL, HN0 3 , H 3 P0 4 , H 2 S0 4 or mixed acid. It is a pure crystal of Ca(H 2 P0 4 ) 2 ⁇ H 2 0 with high processing value and use value. Calcium becomes a highly pure industrial filler CaS0 4 or CaC0 3 , and fluorine becomes a pure fluorosilicate. The acid used in the acid phosphate rock is completely recycled and turned into a variety of potassium, sodium and ammonium salts with high efficiency. The theoretical utilization rate of the raw materials is 100%, and a new acid-smelting phosphate rock process is formed.
  • the invention also has the characteristics of compatibility and co-production with the current processing processes of ammonium phosphate and phosphorus products, in particular, the theoretical conversion rate of phosphorus when the invention is applied to feed monocalcium and dicalcium is 100%, and there is no effluent wastewater. This is far from being possible with current technology.
  • the invention can be compatible with various current processes in various forms, and its processes and products have broad development prospects.
  • the use of low-concentration hydrochloric acid and by-product hydrochloric acid processes, phosphogypsum ammonium sulfate process, synthetic ammonium process products, etc. the present invention not only accepts the advantages of these processes and products, but also contributes to these processes, and can achieve high raw materials used.
  • the 100% utilization rate under the premise of efficiency fully demonstrates the innovation and practicability of the invention under the premise of high efficiency.

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Abstract

La présente invention concerne un procédé d'acidolyse de phosphorite. Le procédé comprend : la production d'acide phosphoreux et de calcium hydrosoluble par la désintégration de phosphorite avec un acide ; la préparation d'un solide de biphosphate de calcium par la réaction de l'acide phosphoreux résultant avec une phosphorite ; la séparation du liquide d'acidolyse de façon à obtenir un fluorosilicate pur ; la purification du liquide d'acidolyse de façon à obtenir du sulfate de calcium en tant que charge industrielle de grande pureté et du carbonate de calcium nanométrique. La voie du procédé et les formes des produits principaux ne changent pas, quels que soient les acides HCl, HNO3, H2SO4 et les mélanges de ceux-ci utilisés en tant que produit de départ et on ne déverse aucune eau usagée. Le procédé est compatible avec le présent procédé pour produire des composés phosphoreux.
PCT/CN2007/071089 2006-11-19 2007-11-19 Procédé d'acidolyse de phosphorite WO2008061473A1 (fr)

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CN108584897A (zh) * 2018-06-13 2018-09-28 贵阳开磷化肥有限公司 一种使用氯化钙制备重过磷酸钙的方法
CN108502862B (zh) * 2018-06-13 2020-11-20 贵阳开磷化肥有限公司 一种富过磷酸钙制备磷酸氢铵的方法
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