WO2008061473A1 - Phosphorite acidolysis method - Google Patents

Phosphorite acidolysis method 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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French (fr)
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/en

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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

A phosphorite acidolysis method is provided. The method comprises: producing water-soluble calcium and phosphorus acid through disintegrating phosphorite with acid; preparing calcium biphosphate solid by reacting the resulting phosphorus acid with phosphorite; separating acidolysis liquid to obtain pure fluorosilicate; purifying the acidolysis liquid to obtain high-purity industrial filler calcium sulphate and nanometer calcium carbonate. The process route and the forms of main products are not changed, whichever of HCl, HNO3, H2SO4 and mixed acids thereof is used as raw material, and no wastewater is discharged. The method is compatible with present process for producing phosphorous compounds.

Description

技术领域 Technical field
本发明涉及- -种酸解磷矿的方法， 更确切地说涉及对酸解磷矿的原料进行完全综 合利用的新方法- 背景技术  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
本发明人在申请号为 200510067111.5的专利申请， 即 "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 "中， 所述的技术方案包括 4个特征步骤： 1、 磷矿 与酸反应制备水溶性钙和磷的酸解液； 2、 加入调节酸解液 PH值的物质， 控制 PH值 在 0— 12范围内； 3、 净化酸解液； 4、 在酸解液中加入生成钙化合物沉淀的沉淀剂。  In the patent application of the application No. 200510067111.5, that is, the method for comprehensive utilization of raw materials of acid phosphate rock and co-production of high-purity microsphere nano calcium carbonate, 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.
该方法能回收纯净的钙化合物和已用过的酸根， 但得到的磷产品不纯净： 在以硫 酸分解磷矿时是含有 Ca(H2P04)2 ·Η20、 CaHP04 ·2Η20和磷矿粉及酸不溶物的混杂物， 在硝酸磷铵工艺中是磷酸 （或磷酸盐） 与硝酸 （或硝酸盐） 的混合液。 在有磷铵工艺 或有磷产品工艺基础的前提下， 不纯净的磷产品可以获得进一步加工并有助于这些加 工工艺。 这一方法的缺陷在于没有获得独立的纯净的磷产品。 而在现行磷产品加工工 艺中虽有独立纯净的磷产品， 但未能对钙和用过的酸根进行高效益回收、 利用。 发明内容 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 ·Η 2 0, CaHP0 4 ·2Η 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
本发明的目的在于克服以上工艺方法的缺陷， 提供一种对酸解磷矿工艺中除了酸 不溶物以外的全部原料进行综合利用的新方法。 本发明的技术方案包括以下步骤：  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:
a、 用酸与磷矿反应， 生成包含有水溶性钙和磷酸的酸解液；  a. reacting with the phosphate rock to form an acid hydrolyzate containing water-soluble calcium and phosphoric acid;
b、 分离出酸解液， 用含磷的化合物与酸解液中的磷酸反应， 生成包含有  b, separating the acid solution, reacting the phosphorus-containing compound with the phosphoric acid in the acid solution, and generating
Ca(H2P04)2 · H20结晶体的固形物； a solid of Ca(H 2 P0 4 ) 2 · H 2 0 crystal;
c、 分离出包含有 Ca(H2P04)2 · H20结晶体的固形物； c, separating solid matter containing Ca(H 2 P0 4 ) 2 · H 2 0 crystal body;
d、 从酸解液中分离出氟化合物；  d, separating the fluorine compound from the acid hydrolysis solution;
e、 净化酸解液；  e, purifying the acid solution;
f、 向净化后的酸解液加入沉淀剂， 生成钙化合物沉淀， 分离出钙化合物和滤液。 步骤 a所述的酸是含有 HCL、 或 HN03、 或 H3P04、 或三者任意比例组成的混合酸f. 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.
； HCL包括 H2S04与 KCL或 NaCl反应生成的 HCL气体用酸解液吸收的 HCL溶液。 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.
步骤 b所述的分离是用沉降分离的方式分离出酸解液中的固形物，得到的酸解液是 分离了固形物的酸解液； 所述的含磷的化合物包括磷矿、 或磷酸氢钙或两者任意比例 的组合； 磷矿的优选粒度大于 lmm， 更优选的是 10— 200mm。 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.
步骤 c所述的固形物是用洗涤水洗涤的固形物， 洗涤水来自脱氟后的酸解液， 其洗 涤固形物后又返回脱氟之前的酸解液中。  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.
步骤 d所述的分离氟化合物是用生成氟硅酸盐沉淀的方式， 或生成 CaF^ 淀的方 式， 或者两种方式的组合； 生成氟硅酸盐沉淀的方式是向酸解液中加入水溶性钾盐或 钠盐， 如 NaCl， 或 KC1， 或 NaN03， 或 KN03 ; 生成 CaF2沉淀的方式是向酸解液中加 入 CaC03、 Ca(OH)2。 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.
步骤 e所述的净化是滤除固形物， 或加入化学试剂分离各种杂质， 或者两种方式 的组合。  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.
步骤 f所述的沉淀剂是含有 S042—类或 C03 2—类的水溶性化合物， 含有 S042—的水 溶性化合物是 H2S04、 K2S04、 Na2 S04、 (NH4)2S04 KHS04、 NaHS04， 含有 C03 2—的 水溶性化合物是 Na2C03、 NaHC03 、 (NH4)2C03 NH4HC03、 KHC03; 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 ;
生成的钙化合物是 CaS04 · XH20或 CaC03， X为 0、 1/2或 2; 得到的滤液是含酸 滤液或者是无酸滤液， 含酸滤液含有 HCL、 或 HN03、 或 H3P04、 或三者任意比例的 组合， 返回酸解磷矿步骤 a， 无酸滤液则退出本发明， 进入其它工序。 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.
以上所述的方法不一定完全按照 1至 6的顺序进行，也可以根据实际需要灵活组合， 如闭环酸解磷矿时， 酸解液含磷酸浓度低， 则该循环不脱磷； 氟含量低， 则该循环不 脱氟。 附图概述  The above methods are not necessarily carried out in the order of 1 to 6, or may be flexibly combined according to actual needs. For example, when the phosphate acid solution is closed-loop acid-dissolved, 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. BRIEF abstract
图 1是本发明的工艺原理流程示意图。  1 is a schematic flow chart of the process principle of the present invention.
图 2是本发明用硫酸酸解磷矿的工艺流程图。  2 is a process flow diagram of the present invention for phosphating phosphate rock.
图 3是本发明应用于生产饲料级磷酸氢钙和磷酸二氢钙的工艺流程图。  Figure 3 is a process flow diagram of the present invention for producing feed grade calcium hydrogen phosphate and calcium dihydrogen phosphate.
图 4是本发明用 HC1、 HNO3为原料酸解磷矿的工艺流程图。  Fig. 4 is a flow chart showing the process of acidifying phosphate rock using HC1 and HNO3 as raw materials in the present invention.
图中虚线箭头所示的是可行的物流方向， 图 2虚线框内容表示酸解液开环出口， 进入其它工序。 本发明的最佳实施方案  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. BEST MODE FOR CARRYING OUT THE INVENTION
下面对本发明的工艺原理进行详细说明。  The process principle of the present invention will be described in detail below.
其包括的工序、 步骤如下 （参见附图 1 ) ：  The steps and steps involved are as follows (see Figure 1):
1、 酸解磷矿： 本发明选择能生成水溶性钙的强酸如 HCL、 HN03、 H3P04或三者 任意比例组成的混合酸来分解磷矿， 得到酸解液。 由于分解产物主要是水溶性的钙和 磷酸， 这就从反应原理上降低了对磷矿粒度的要求， 从实用角度出发， 可选用粒度在 300mm以下的矿料， 只要酸解液浸没在磷矿中， 1小时内就可完成酸解过程。 而酸解 池的容量只要大于或等于酸解液体积的 2倍， 就可以省去球磨工序， 减小磷矿粒度和 对酸解液采取池内循环， 可加快反应。 1. Acid-dissolved phosphate rock: The present invention 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.
2、 沉降分离： 对于酸解磷矿后的酸解液， 优选用沉降方式分离出固形物， 经 1一 2小时自然沉降后就可分离出 99%以上的固形物。 如果加入絮凝剂， 可快速完成沉降 过程。  2. 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.
3、 脱磷： 分离了固形物的酸解液中含有¾?04。 本发明是用含磷的化合物进行脱 磷， 即脱除酸解液中的 ¾P04。 所用的含磷的化合物主要是磷矿， 其和 H3P04的反应 为： 3. Dephosphorization: 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:
Ca5F(P04)3+7 H3P04=5Ca(H2P04)2+HF 式 （1 ) Ca 5 F(P0 4 ) 3 +7 H 3 P0 4 =5Ca(H 2 P0 4 ) 2 +HF Formula (1)
因 Ca(H2P04)2在纯水中的标准溶解度为 15克， 约 0.6mol/l， 在高浓度 Ca2+存在下 因同离子效应溶解度下降， 约为 0.5mol/l， 其中 H2P04—约为 lmol/l。 当用大于 1.2mol/l 的 H3P04分解磷矿时， 生成的 Ca(H2P04)2因大于其溶解度而以 Ca(H2P04)2 · H20形式 析出结晶， 这是酸解液在该条件下唯一的过饱和产物， （在有游离 ¾?04存在时， 形 不成 CaHP04 · 2Η20沉淀和 CaF2沉淀） ， 其结晶粒度约在 5— 50 μ m， 密度约 2.2g/cm3 这种结晶固体与磷矿固体的分离， 有二种方式可供选择。 第一种， 使用大粒径块 状磷矿： 当磷矿粒度大于 lmm时， 磷矿的密度约为 3 g/cm3， 用旋流方式利用二种固 体粒度和密度的差别可以完全分离；当磷矿的粒度为 10— 200mm时，可省去旋流措施， 酸解液可直接带走结晶固体， 实现固固分离， 优选这种大粒径的块状磷矿。 如取实用 的反应时间为 2— 4小时， 优选这种方式。 加热或对池内酸解液进行循环， 能加快反应 。 第二种用磷矿脱磷的方式是用粒度小于 lmm的磷矿粉与酸解液中的¾?04反应， 其 优点是速度快， 缺点是一次反应不完全， 其实用的方法是对包含有磷矿和 Since the standard solubility of Ca(H 2 P0 4 ) 2 in pure water is 15 g, about 0.6 mol/l, the solubility due to the same ion effect decreases in the presence of high concentration of Ca 2+ , which is about 0.5 mol/l, where H 2 P0 4 - about 1 mol/l. When the phosphate rock is decomposed with H 3 P0 4 of more than 1.2 mol/l, the Ca(H 2 P0 4 ) 2 formed precipitates crystals in the form of Ca(H 2 P0 4 ) 2 · H 2 0 because it is greater than its solubility. It is the only supersaturated product of the acid solution under this condition (in the presence of free 3⁄4 ?0 4 , it does not form CaHP0 4 · 2Η 20 precipitate and CaF 2 precipitate), and its crystal grain size is about 5-50 μm. The density of about 2.2g / cm 3 separation of this crystalline solid and phosphate rock solids, there are two ways to choose. 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. With phosphate dephosphorization second way is to use a particle size of less than rock phosphate with an acid hydrolyzate lmm in ¾? 0 4 reaction, the advantage of speed, a disadvantage is that reaction was not complete, in fact, the method used is Contains phosphate rock and
Ca(H2P04)2 ·¾0结晶的固形物用酸解液中的 H3P04反复多次分解，因 Ca(H2P04)2 ·Η20 与 H3P04不起反应， 只有磷矿和 H3P04起反应， 其终产物是以 Ca(H2P04)2 · ¾0晶体 为主的固形物。 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 ·Η 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.
脱除酸解液中的 H3P04， 还包括使用 CaHP04 · 2Η20+。 Ρ2这种含磷的化合物。 这 种混有氟化物的含磷化合物来自饲料磷酸氢钙工艺的脱氟环节，是用 CaC03或 Ca(OH)2 中和约 50%的水溶性磷连同溶液中全部的 F—而生成的一种混合物， 被用做肥料。 这虽 不是优质产品， 但却是一个理想的脱氟环节。 CaHP04 · 2H20+CaF2能和酸解液中的 H3P04反应， 其反应速度远大于磷矿， 除生成 Ca(H2P04)2 * H20结晶外， 还能让 CaF2 分解成 F―， 实现回收纯净氟化物， 最主要的是通过这个环节可获得无氟的酸解液。 Removal of H 3 P0 4 from the acidolysis solution also includes the use of CaHP0 4 · 2Η 2 0+. Ρ 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. In addition to the formation of Ca(H 2 P0 4 ) 2 * H 2 0 crystal, it can also The decomposition of CaF 2 into F-, to achieve the recovery of pure fluoride, the most important thing is to obtain a fluorine-free acid hydrolysis solution through this link.
因 Ca(H2P04)2饱和时的 H2P04—浓度约在 1一 1.2mol/l，进入脱磷工序的酸解液含水 溶性磷优选 2— 4mol/l。 浓度低， Ca(H2P04)2 * H20得率低； 浓度高， 则 Ca2+离子浓度 也高， 对后续脱钙易造成循环介质损失增大。 为此， 在闭环酸解时优选酸浓度为 3— 6mol/lH+， 主要利用循环方式提高酸解液中 H3P04浓度， 并兼顾脱钙工序的介质损失。 在开环酸解时， 酸与磷矿只反应一次， 优选 6— 12mol/lH+的高浓度， 以尽量提高 Ca(H2P04)2 · H20的得率。 4、 脱氟、 净化： 脱磷后的酸解液， 根据 Mg2+、 Al3+等杂质情况可有三种去向： 一 是杂质少， 不脱氟， 直接净化， 得到含钙清液再脱钙； 二是含氟高， 则进入脱氟工序 用 NaCl或 KC1 (NaN03或 KN03 ) 以生成氟硅酸盐的方式将 Fl拳到 lOg/1以下， 然后 净化得到含钙清液， 再脱钙； 三是 Mg2+、 Al3+等杂质多， 不脱除就要影响产品质量时， 则在脱氟后再用饲料磷酸氢钙工艺方式对酸解液进行深度净化， 即： 用提高 PH值的 方法， 向酸解液加入碱性物质， 如 NH3、 CaC03、 CaCOH^等调 PH值在 2— 4得肥料二 钙 （CaHP04 · 2H20+CaF2) ， 再调 PH值到 8， 得饲料二钙 CaHP04 · 2H20， 再调 PH 值到 12， 脱镁得易于加工的 Mg(OH)2 ; 经这样净化后的酸解液已是无氟而纯净的含钙 清液， 可作为洗涤水用于洗涤 Ca(H2P04)2 * H20。这种来自于酸解液系统又经洗涤了产 品后返回原系统的洗涤水， 无论用量多少， 都能确保水平衡。 Since the concentration of H 2 P0 4 - when Ca(H 2 P0 4 ) 2 is saturated is about 1 to 1.2 mol/l, 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. For this reason, in the closed-loop acid hydrolysis, 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. In the ring-opening acid hydrolysis, 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. 4, 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+ . If the product quality is not removed, 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.
酸解液的净化是为了获得高纯净钙化合物而必须进行的预处理措施， 净化的标准 是酸解液与沉淀剂反应生成的钙化合物具有单一性， 能分离出纯净度达 98%以上的纯 净钙化合物。 为此， 当用 H2S04或含 S04 2—类沉淀剂在酸性条件下与 Ca2+反应时， 因其 沉淀的单一性， 就简化了净化工序， 只要滤除固形物即可， 对某些特定的需回收或必 须除去的离子， 可加入试剂进行分离， 特别是某些有价值的离子， 也可在该环节用各 种现行方式进行有效的回收； 因酸解液中的 C03 2—在 PH<4时分解， 其使用条件是 PH >4， 在该条件下碳酸盐沉淀不具有单一性， 必须预先分离酸解液中各种干扰离子， 用 前述的饲料磷酸氢钙工艺作净化环节， 可以获得优良的净化效果， 净化后的酸解液 PH 大于 8， 既可与 S042—类又可与 C03 2—类水溶性沉淀剂反应。 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. For this reason, when H 2 S0 4 or a S0 4 2 -based precipitant is reacted with Ca 2+ under acidic conditions, the purification process is simplified due to the singularity of precipitation, as long as the solid matter is filtered out, For certain specific ions that need to be recovered or must be removed, reagents can be added for separation, especially some valuable ions, which can also be effectively recovered in various ways in this process; due to C0 in the acid solution 3 2 —Decomposes at pH<4, and its use condition is PH>4. Under this condition, carbonate precipitation does not have unity, and various interfering ions in the acid solution must be separated in advance, and the aforementioned feed calcium hydrogen phosphate is used. The purification process of the process can obtain excellent purification effect, and the pH of the purified acid solution is greater than 8, which can be reacted with the S04 2 type and the C0 3 2 type water-soluble precipitant.
5、 脱钙： 净化后的酸解液含水溶性钙， 能生成众多的化合物， 利用这一特点， 可 根据用酸种类， 磷矿品位和杂质含量， 联产工艺产品主导方向和经济效益， 随时灵活 机动地联产多种产品。  5. Decalcification: The purified acid solution contains water-soluble calcium, which can produce a large number of compounds. With this feature, according to the type of acid used, the grade of phosphate ore and the content of impurities, the leading direction and economic benefits of the joint production process can be used at any time. Flexible and mobile joint production of a variety of products.
本发明选择了二大类沉淀剂， 即 S042—类和 C03 2—类水溶性沉淀剂。 The present invention selects two major types of precipitants, namely S04 2 - and C0 3 2 - water-soluble precipitants.
在酸性条件下， 用 S04 2—类沉淀剂的反应为： Under acidic conditions, the reaction with a S0 4 2 -type precipitant is:
5CaCl2+Ca(H2P04)2 · 2H20+6H2S04=6CaS04 · 2Η20 Ϊ +10HCl+2H3PO4 式 （2 ) 生成物中含有 CaS04 * 2H20， 分离作产品， 滤液可返回酸解池酸解磷矿， 反应如 下： 5CaCl 2 +Ca(H 2 P0 4 ) 2 · 2H 2 0+6H 2 S0 4 =6CaS0 4 · 2Η 2 0 Ϊ +10HCl+2H 3 PO 4 Formula (2) contains CaS0 4 * 2H 2 0, Separated as a product, the filtrate can be returned to the acid hydrolysis pool to dissolve the phosphate rock. The reaction is as follows:
Ca5F(PO4)3+10HCl+2 H3P04=5CaCL2+5H3P04+HF 式 （3 ) 式 （2 ) 、 式 （3 ) 构成了硫酸间接酸解磷矿的循环酸解方法， HC1、 HN03、 H3PO4 成了循环介质， 式 （3 ) 酸解液按式 （1 ) 脱磷后又回到式 （2 ) 脱除纯净钙。 式 （3 ) 、 式（1 )、式（2 )构成了本发明硫酸酸解磷矿的主导酸解工艺路线。式（2 )中的 CaS04 ·2Η20 在 H2S04浓度、 反应温度不同时， 可形成 CaS04、 CaS04 · 1/2H20， 以 CaS04 · 2H20 易于过滤洗涤。 Ca 5 F(PO 4 ) 3 +10HCl+2 H 3 P0 4 =5CaCL 2 +5H 3 P0 4 +HF Formula (3) Formula (2), 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 ·2Η 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.
用 PH大于 8的纯净水溶性钙与 S04 2—类和 C03 2—类沉淀剂在水溶液中的反应为： Ca(N03)2+K2S04==Ca S04 · 2Η20 ϊ +2ΚΝ03 式 （4 ) The reaction of pure water-soluble calcium with a pH greater than 8 with S0 4 2 -type and C0 3 2 -type precipitant in aqueous solution is: Ca(N0 3 ) 2 +K 2 S0 4 ==Ca S0 4 · 2Η 2 0 ϊ +2ΚΝ0 3 (4)
Ca(N03)2+Na2 S04==Ca S04 · 2H20 Ϊ +2 Na N03 式 （ 5 ) Ca(N03)2+(NH4)2S04==CaS04 · 2H20 +2NH4N03 式 （6)Ca(N0 3 ) 2 +Na 2 S0 4 ==Ca S0 4 · 2H 2 0 Ϊ +2 Na N0 3 (5 ) Ca(N0 3 ) 2 +(NH 4 ) 2 S0 4 ==CaS0 4 · 2H 2 0 +2NH 4 N0 3 (6)
Ca(N03)2+2NaHC03==CaC03 (高纯纳米) +2NaN03+C02+H20 式 （7) Ca(N0 3 ) 2 +2NaHC0 3 ==CaC0 3 (high purity nano) +2NaN0 3 +C0 2 +H 2 0 (7)
Ca(N03)2+Na2C03==CaC03 (高纯纳米) +2NaN03 式 （8 ) Ca(N0 3 ) 2 +Na 2 C0 3 ==CaC0 3 (high purity nano) +2NaN0 3 (8)
CaCl2+(NH4)2S04==CaS04 · 2H20 +2NH4C1 式 （9) CaCl 2 +(NH 4 ) 2 S0 4 ==CaS0 4 · 2H 2 0 +2NH 4 C1 Formula (9)
CaCl2+(NH4)2C03==CaC03 (高纯纳米) +2NH4C1 式 （10) CaCl 2 +(NH 4 ) 2 C0 3 ==CaC0 3 (high purity nano) +2NH 4 C1 formula (10)
CaCl2+2KHC03+NH4Cl==CaC03 Ϊ (高纯纳米) +NH4C1+2KC1+C02+H20 CaCl 2 +2KHC0 3 +NH 4 Cl==CaC03 Ϊ (high purity nano) +NH 4 C1+2KC1+C0 2 +H 2 0
式 （11 ) (11)
CaCL2+2NH4HC03==CaC03 (高纯纳米) +2NH4C1+C02+H20 式 （12) 在中性和碱性条件下， 无论是 Ca(N03)2还是 CaCl2， 都能生成两种纯净物， 实现 钙和酸根的全回收。 在此硝酸分解磷矿所得产品的经济效益更高， 充分体现了硝酸原 料的优势。 在用硫酸分解磷矿时， 本发明必须借助 HN03或 HCL这种原料才能获得纯净的钙 化合物。 为了推动本发明得以实施， 本发明除直接使用 HC1或 HN03外， 还结合本发 明的产品特点， 引进了硫酸制 HC1的工艺环节， g卩： CaCL 2 +2NH 4 HC0 3 ==CaC0 3 (high purity nano) +2NH 4 C1+C0 2 +H 2 0 Formula (12) Under neutral and alkaline conditions, whether Ca(N0 3 ) 2 or CaCl 2 , can produce two kinds of pure, to achieve the full recovery of calcium and acid. The economic benefits of the products obtained by decomposing phosphate rock in this nitric acid are higher, which fully demonstrates the advantages of nitric acid raw materials. In the case of decomposing phosphate rock with sulfuric acid, the present invention must utilize a raw material of HNO 3 or HCL to obtain a pure calcium compound. In order to promote the implementation of the present invention, in addition to the direct use of HC1 or HNO 3 , in combination with the characteristics of the product of the present invention, the process of introducing HC1 by sulfuric acid is introduced, g卩:
低温时 KCL(NaCl)+H2S04==KHS04(NaHS04)+HCl (气） 式（13) KCL(NaCl)+H 2 S0 4 ==KHS0 4 (NaHS0 4 )+HCl (gas) at low temperature (13)
高温时 2KCL(2NaCL)+H2S04==K2S04(Na2S04)+2HCl (气） 式（14) 2KCL(2NaCL)+H 2 S0 4 ==K 2 S0 4 (Na 2 S0 4 )+2HCl (gas) at high temperature (14)
这是硫酸制备硫酸盐或酸式硫酸盐并副产 HCL (气)的经典成熟工艺，式 (14)称为曼 海姆工艺。 HCL (气)可用酸解液吸收， 立即与磷矿反应， 无需单独制备盐酸溶液， 随用 随产极为方便。 而硫酸盐与本发明的磷产品有如下反应：  This is a classic mature process for the production of sulfate or acid sulfate by sulfuric acid and by-product HCL (gas), and the formula (14) is called the Mannheim process. HCL (gas) can be absorbed by the acid solution, and immediately reacts with the phosphate rock. It is not necessary to separately prepare a hydrochloric acid solution, which is very convenient to use. The sulfate reacts with the phosphorus product of the present invention as follows:
Ca(H2P04)2 · H20十 KHS04==CaS04 · XH20十 KH2P04+ H3P04 式（15) Ca(H 2 P0 4 ) 2 · H 2 0 十 KHS0 4 ==CaS0 4 · XH 2 0 十KH 2 P0 4 + H 3 P0 4 (15)
Ca(H2P04)2 · H20十 K2S04==CaS04 · XH20十 2KH2P04 式（16) Ca(H 2 P0 4 ) 2 · H 2 0 十 K 2 S0 4 ==CaS0 4 · XH 2 0 十 2KH 2 P0 4 (16)
Ca(H2P04)2 · H20十 NaHS04==CaS04 · XH20十 NaH2P04+ H3P04式（17) Ca(H 2 P0 4 ) 2 · H 2 0 十NaHS0 4 ==CaS0 4 · XH 2 0 十NaH 2 P0 4 + H 3 P0 4 (17)
Ca(H2P04)2 · H20十 Na2S04==CaS04 · XH20十 2NaH2P04 式（18) Ca(H 2 P0 4 ) 2 · H 2 0 十Na 2 S0 4 ==CaS0 4 · XH 2 0 十 2NaH 2 P0 4 (18)
Ca(H2P04)2 · H20十 H2S04== CaS04 · XH20十 2 H3P04 式（19) Ca(H 2 P0 4 ) 2 · H 2 0 十 H 2 S0 4 == CaS0 4 · XH 2 0 十 2 H 3 P0 4 (19)
CaHP04 · 2H20十 KHS04== CaS04 · XH20十 KH2P04 式 (20) CaHP0 4 · 2H 2 0 十 KHS0 4 == CaS0 4 · XH 2 0 十 KH 2 P0 4 (20)
CaHP04 · 2H20十 NaHS04==CaS04 · XH20十 NaH2P04 式 (21) CaHP0 4 · 2H 2 0 十NaHS0 4 ==CaS04 · XH 2 0 十NaH 2 P0 4 (21)
上式中生成物 CaS04 · ΧΗ20因反应温度和浓度不同， X取值可分别是 0、 1/2或 2In the above formula, the product CaS0 4 · ΧΗ 2 0 differs depending on the reaction temperature and concentration, and the value of X can be 0, 1/2 or 2, respectively.
。 由此可见， 在制备磷酸盐时， 硫酸盐与硫酸有相类似的作用。增加一个副产 HCL (气 )的工艺环节，除推动本发明在原有原料种类条件下能得以实施，还可以大量使用 HCL 开环酸解磷矿， 并能大量生产本工艺所需要的硫酸盐， 同时不影响分解磷矿和制取高 浓度优质磷酸的钾、钠盐， 更使所有原料的利用率均提到 100 %的完全综合利用。这使 本发明的创新性和实用性得到了更充分的体现。 . Thus, in the preparation of phosphate, 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. At the same time, 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.
下面结合附图对本发明作进一步的说明。 应理解， 这些实施例仅用于说明本发明 而不用于限制本发明的范围。 下列实施例中未注明具体条件的方法， 通常按照常规条 件。 实施例 1 : 本发明用硫酸酸解磷矿的应用 The invention will now be further described with reference to the accompanying drawings. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The methods in the following examples which do not specify the specific conditions are usually in accordance with conventional conditions. Example 1: Application of the acid phosphate phosphate in the present invention
参见附图 2。  See Figure 2.
用硫酸分解磷矿生产磷铵和磷酸盐， 在现行工艺所用原料基础上增加 NaCl或 KC1 原料和硫酸生产硫酸盐或酸式硫酸盐并副产 HC1 (气）的工艺，或者加入循环介质 HC1、 KN03、 CaCl2等， 就能推动本发明实现对原料的完全综合利用。 其创新性和实用性体 现在无论磷矿品位高低， 杂质含量多少， 均不影响高纯净钙化合物的质量和 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.
Ca(H2P04)2 * H20为主的磷产品质量。 与现行磷铵工艺相结合， 本发明可以向其提供无 需蒸发浓缩的浓磷酸或磷酸盐。 The quality of the phosphorus product dominated by Ca(H 2 P0 4 ) 2 * H 2 0 . In combination with the current ammonium phosphate process, the present invention can provide it with concentrated phosphoric acid or phosphate which is not concentrated by evaporation.
工艺流程说明：  Process description:
用 NaCl+H2S04或 2KC1+H2S04 (高温） 反应产生 HC1气体， 并用酸解液吸收进入 酸解池， 如果有 HC1、 HN03、 CaCl2、 Ca(N03)2等原料可省此步骤。 把磷矿筛分出的部 分粒径在 10— 200mm的块矿放入脱磷池， 其余放入酸解池中与酸解液反应约 1小时， H+离子浓度优选 3— 6mol/l。 酸解液经沉降、 净化放入含钙清液池中， 含钙清液中的水 溶性钙与 H2S04 (或酸式硫酸盐）反应， 以每立方米酸解液得 150— 250kgCaSO4 · 2Η20 为优选反应浓度； 获得 CaS04 · 2H20的粒度分布为 1一 20 μ m， 平均粒度约 10 μ m， 经洗涤纯度可达 98 %以上； 经固液分离分出 CaS04 · 2Η20， 滤液返回酸解池。 这是酸 解磷矿制取纯净 CaS04 · 2H20的的一条主工艺线。 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 · 2Η 2 0 is the preferred reaction concentration; the particle size distribution of CaS0 4 · 2H 2 0 is 1-20 μm, the average particle size is about 10 μ m, the purity of washing can reach 98% or more; CaS0 is separated by solid-liquid separation. 4 · 2Η 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.
酸解液在这条工艺线上每循环一次， 除获得 CaS04 * 2H20外， 酸解液中的 H3P04 浓度不断提高， 当游离 H3P04和水溶性 Ca(H2P04)2中的总 H2P04_达 2— 4mol/l时， 从 酸解池中分离出的酸解液经自然沉降约 1小时， （加入絮凝剂可快速分离悬浮物） ， 分出清液进入脱磷池与块状磷矿（或 CaHP04 ·2Η20+。&Ρ2)反应，生成 CaCH2P04)2 ·Η20 沉淀从而脱除了酸解液中的 H3P04， 并且利用酸解液冲洗磷矿石的方式把生成的 Ca(H2P04)2 · Η20晶体带出， 实现矿石与 Ca(H2P04)2 · ¾0的固固分离， 再利用自然 沉降、 过滤等方式， 实现酸解液与 Ca(H2P04)2 * H20的固液分离， 分离出的 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 ·2Η 2 0+.&Ρ 2 ) to form CaCH 2 P0 4 ) 2 ·Η 2 0 precipitate to remove H 3 P0 4 from the acid solution. And using the acid solution to wash the phosphate rock, 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(H2P04)2 · ¾0也可以用脱氟的酸解液洗涤。 分离出来的 Ca(H2P04)2 · Η20， 其 Ρ205 含量在 50— 55 %之间， 当与硫酸或硫酸盐反应时， 可获得高浓度较纯净的一系列磷酸 或磷酸盐产品， 这是生产磷产品的一条主工艺线。 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 · Η 2 0 has a Ρ 2 0 5 content of 50-55%. When reacted with 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.
当循环酸解液中 F—浓度达到 20— 60g/l时， 可进入脱氟工序。 用 NaCl或 KC1与酸 解液中的 H2SiF6反应生成 Na2SiF6或 K2SiF6沉淀， 从而把 Fl拳到 lOg/1以下。 When the F-concentration in the circulating acid solution reaches 20-60 g/l, 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.
当酸解液中的以镁为主的杂质离子浓度达 1一 1.2mol/l时， 本工艺有两种方式使酸 解液退出循环系统： 一种是从饲料磷酸氢钙工艺作出口， 分离出的肥料二 钙  When the ion concentration of the magnesium-based impurity in the acid solution reaches 1 to 1.2 mol/l, 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. Fertilizer
( CaHP04 · 2H20+CaF2) 用于脱磷或加工磷酸盐， 饲料二钙 CaHP04 · 2H20作产品， Mg(OH)2加工镁肥， 而 CaC03是高纯净产品， 是这一出口的主要产品， 溶液 NH4CL或 NH4N03去蒸发工序。 另一种是磷铵工艺作出口， 酸解液加入 (NH4)2S04脱钙后再加入 NH3 i¾ NH4HC03, 酸解液中的以镁为主的杂质离子与磷酸根反应生成 MgNH4P04类沉 淀， 当 PH值在 3— 5时生成的虽是枸溶性磷， 但简化了工艺， 保留了有益于农作物的 必要养分。 分离出磷酸盐固形物， 溶液进入蒸发工序。 进入蒸发工序的均为易于蒸发 的铵盐。 实施例 2: 本发明应用于生产饲料级磷酸氢钙和磷酸二氢钙 (CaHP0 4 · 2H 2 0+CaF 2 ) For dephosphorization or processing of phosphate, feed dicalcium CaHP0 4 · 2H 2 0 as product, Mg(OH) 2 processing magnesium fertilizer, and CaC0 3 is a high purity product, The main product of this outlet, the solution NH 4 CL or NH 4 N0 3 devaporation process. The other is the ammonium phosphate process to make the mouth, the acid solution is added to the (NH 4 ) 2 S0 4 decalcification and then the NH 3 i3⁄4 NH 4 HC0 3 is added , and the magnesium-based impurity ions in the acid solution react with the phosphate. Generate MgNH 4 P0 4 class sink Ding, when the pH value is 3-5, it is 枸 soluble phosphorus, but it simplifies the process and retains the necessary nutrients beneficial to crops. The phosphate solids are separated and the solution enters the evaporation process. The ammonium salts which are easy to evaporate are all entering the evaporation process. Example 2: The invention is applied to the production of feed grade calcium hydrogen phosphate and calcium dihydrogen phosphate
参见附图 3。  See Figure 3.
在本实施例中，本发明的创新性和实用性体现在以硫酸和磷矿为主原料的条件下， 以闭环酸解方式酸解出饲料级的磷酸二氢钙， 并使原料得到完全综合利用， 磷转化为 饲料的转化率为 100%， 饲料一钙、 二钙比例任意可调。 现有的饲料磷酸氢钙工艺， 在 本发明中只用于解决分离杂质， 并制备无氟水溶液用以洗涤饲料一钙， 使其确保系统 水平衡。  In the present embodiment, 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.
工艺流程说明：  Process description:
将磷矿筛选出的粒径为 20— 200mm的矿石放入脱磷池，其余放入酸解池并加入优 选 3— 6mol/l浓度的 HC1 (HN03 ) 进行酸解， 酸解液经自然沉降、 净化后， 用 H2S04 对酸解液脱钙， 分离出 CaS04 · 2Η20后的滤液返回酸解池进行下一循环， 并补入损失 的 HC1。 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 · 2Η 2 0 was separated and returned to the acid hydrolysis tank for the next cycle, and the lost HC1 was added.
当酸解液中的 ¾P04浓度提高到总 H2P04_在 2— 4mol/l时， 从沉降池中分离出清 液放入脱磷池， 用块状磷矿 （或 CaHP04 * 2H20+CaF2) 对酸解液脱磷， 控制脱磷的酸 解液中保留少量游离 H3P04， 以防 F_沉淀。 生成的 Ca(H2P04)2 * H20在分离一钙工序 进行固液分离， 并用洗涤一钙工序的洗涤水进行初洗， 分离出的固体物进入洗涤一钙 工序用无氟洗涤水进行再洗。 并以旋流方式分离出部分纯净 Ca(H2P04)2 * H20， 其余的 含杂质较多的 Ca(H2P04)2 · H20进入酸解一钙工序， 再用 HC1(HN03、 H2S04)分解成 H3P04并滤出酸渣， 酸渣含磷、 放入沉降池。 用优质 CaC03或 Ca(OH)2沉淀出 When the concentration of 3⁄4P0 4 in the acid solution is increased to the total H 2 P0 4 _ at 2-4 mol/l, the supernatant is separated from the settling tank and placed in the dephosphorization tank, using a massive phosphate rock (or CaHP0 4 * 2H). 2 0+CaF 2 ) Dephosphorization of the acid solution, a small amount of free H 3 P0 4 is retained in the acid solution for controlling dephosphorization to prevent F_precipitation. 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
Ca(H2P04)2 · H20或 CaHP04 · 2H20。 Ca(H 2 P0 4 ) 2 · H 2 0 or CaHP0 4 · 2H 2 0.
在分离一钙工序分离出的酸解液和洗涤液， 当氟含量不高时从净化工序并入酸解 系统； 当氟含量达 20— 60g/l时， 用 NaCl或 KC1脱氟后并入酸解系统。  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.
由于 Ca(H2P04)2 · H20在每立方水中有 150kg的溶解度， 本发明用现有的饲钙工 艺分离出以镁为主体的杂质离子并为其提供洗涤水。为此，将脱氟后的酸解液用 CaC03 或 Ca(OH)2先沉淀出肥料二钙 （Ca(H2P04)2 · H20+CaF2) ， 并将含氟二钙转入脱磷工 序用于脱磷并回收 F―， 脱氟酸解液 （P2O5/F 200) ， 再用 Ca(OH)2调 PH值到 8， 分 离出饲料 CaH2P04 * H20 (也可用作一钙的原料） ， 滤液再用 Ca(OH)2调 PH值到 12， 分离出以 Mg(OH)2为主的各种杂质。 得到的无氟含钙清液调节 PH值在 1一 3， 可用于 洗涤 Ca(H2P04)2 · H20， 洗涤水来自于循环系统， 又返回循环系统， 既不影响水平衡， 也不会造成磷的损失。 每立方洗涤水可洗涤 1一 2吨 Ca(H2P04)2 · H20结晶体。 实施例 3: 本发明用 HC1， 11 03为原料的酸解磷矿工艺 参见附图 4。 Since Ca(H 2 P0 4 ) 2 · H 2 0 has a solubility of 150 kg per cubic water, the present invention separates and supplies wash water with magnesium-based impurity ions by the existing calcium-feeding process. To this end, 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. Transfer to the dephosphorization process for dephosphorization and recovery of F-, defluorination acid solution (P 2 O 5 /F 200), and then adjust the pH value to 8 with Ca(OH) 2 to separate the feed CaH 2 P0 4 * H 2 0 (which can also be used as a raw material for calcium), and the filtrate is adjusted to a pH of 12 by Ca(OH) 2 to separate various impurities mainly composed of Mg(OH) 2 . The obtained fluorine-free calcium-containing serum adjusts the pH value to 1-3, and can be used for washing Ca(H 2 P0 4 ) 2 · H 2 0. The washing water comes from the circulation system and returns to the circulation system, which does not affect the water balance. It will not cause loss of phosphorus. One to two tons of Ca(H 2 P0 4 ) 2 · H 2 0 crystals can be washed per cubic wash water. Example 3: The acid phosphate rock process of the invention using HC1, 11 0 3 as a raw material See Figure 4.
实施目的：  Implementation purpose:
在无磷产品工艺作依托而用 HN03、 HC1为原料酸解磷矿时， 本实施例侧重接纳各 种有高经济效益、 低能耗、 低投资的工艺和产品， 形成一个高效益综合利用新工艺。 In the case of phosphate-free product process, 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.
用 HC1分解磷矿主要是为了：  The main reason for decomposing phosphate rock with HC1 is to:
1、 接纳副产 HC1 (气） 或稀盐酸；  1. Accept by-product HC1 (gas) or dilute hydrochloric acid;
2、 生产 K2S04、 KHS04、 NaS04 NaHS04等硫酸盐； 2. Producing sulfates such as K 2 S0 4 , KHS0 4 , NaS0 4 NaHS0 4 ;
3、 制取有较大加工价值的 Ca(H2P04)2 · H20和饲料一钙、 饲料二钙； 3. Prepare Ca(H 2 P0 4 ) 2 · H 2 0 with a large processing value and feed one calcium, feed dicalcium;
4、 主产作工业填料用的纳米碳酸钙， 副产 NH4CL。 4. The main production of nano-calcium carbonate for industrial fillers, by-product NH 4 CL.
用 HN03分解磷矿主要是为了获得： Decomposing phosphate rock with HN0 3 is mainly for obtaining:
1、 Ca(H2P04)2 · H20和饲料一钙、 饲料二钙； 1. Ca(H 2 P0 4 ) 2 · H 2 0 and feed-calcium, feed dicalcium;
2、 工业填料用 CaS04 · 1/2Η2Ο(10 μ m)和 CaC03 (纳米) ； 2. For industrial packing, CaS0 4 · 1/2Η 2 Ο (10 μ m) and CaC0 3 (nano);
3、 低成本硝酸盐， 如 NaN03、 KN03。 3. Low-cost nitrates such as NaN0 3 and KN0 3 .
用酸浓度：  Acid concentration:
用 HC1 (HN03 )对磷矿进行酸解， 是一种开环酸解方式， 酸浓度优选 6— 12mol/l， 以浓度高为好； 以磷矿含 P2O530 %， （CaO+MgO) 约 50 %计， 10mol/lHCL(HNO3)可 得 3mol/l浓度 H3P04的酸解液，经脱磷后酸磷液中含有饱和的 Ca(H2P04)2， (含 H2P04 —约 lmol/1) ， 可脱去 2mol/lH3P04并以 Ca(H2P04)2 * H20形式析出结晶， 占酸解液中 水溶性磷的 67%， 当盐酸浓度降为 7mol/l (含 HCL23%) 时， 脱磷环节只能分出 50% 的水溶性磷。 The acid hydrolysis of phosphate rock with HC1 (HN0 3 ) 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 . After dephosphorization, the acid phosphorus solution contains saturated Ca(H 2 P0 4 ) 2 . (containing H 2 P0 4 - about 1 mol / 1), can remove 2mol / l H 3 P0 4 and precipitate crystals in the form of Ca (H 2 P0 4 ) 2 * H 2 0, accounting for 67 of water-soluble phosphorus in acid solution %, when the hydrochloric acid concentration is reduced to 7mol/l (including HCL23%), only 50% of water-soluble phosphorus can be separated in the dephosphorization step.
工艺流程说明：  Process description:
用 HCL (HN03 ) 与磷矿在酸解池反应后， 经沉降分出清液进入脱磷池与块磷矿， 或其它磷化合物如 （Ca(H2P04)2.H20+CaF2) 反应， 生成 Ca(H2P04)2 · ¾0沉淀从而脱 除酸解液中的 H3P04，分离出 Ca(H2P04)2 ·Η20结晶后的酸解液含有饱和 Ca(H2P04)2 ， 经净化后进入含钙清液池 （稳定前后环节的贮槽） ， 再用现行的饲钙工艺对含钙、 磷、 氟、 镁的酸解液进行分别回收， 依次用 KCL或 NaCL (用硝酸分解磷矿时， 用 NaN03 或 KN03 ) 脱氟， 将 F—降到 3— 7g/l， 再用 CaC03或 Ca(OH)2进一步脱氟脱磷， 生成的 CaCH2P04;>2 · H20+CaF2可作肥料或用于脱磷， 当酸解液中的 P205/F 200时， 再用 Ca(OH)2调 PH值到 8， 制取饲料 CaHP04 · 2Η20， 然后用 Ca(OH)2 调 PH到 12， 分离 出以 Mg(OH)2为主的杂质， 得纯净的 CaCL2或 Ca(N03)2， 在脱钙工序用 S04 2—或 C03 2 _类沉淀制取纯净 CaS04 ·2Η20或 CaC03 (纳米级），滤液经浓缩精制成 NaN03、 KN03 或丽 4C1。 After HCL (HN0 3 ) is reacted with the phosphate rock in the acid hydrolysis tank, the supernatant is separated into the dephosphorization tank and the phosphate rock, or other phosphorus compounds such as (Ca(H 2 P0 4 ) 2 .H 2 0+ Ca F 2) reacts to form Ca(H 2 P0 4 ) 2 · 3⁄40 precipitate to remove H 3 P0 4 from the acid hydrolysis solution, and separates the acid solution after Ca(H 2 P0 4 ) 2 ·Η 2 0 crystal The liquid contains saturated Ca(H 2 P0 4 ) 2 , which is purified and then enters the calcium-containing clear liquid pool (storage tank before and after stabilization), and then uses the current calcium feeding process to treat the acid solution containing calcium, phosphorus, fluorine and magnesium. Separately recover, use KCL or NaCL (decompose phosphate rock with nitric acid, use NaN0 3 or KN0 3 ) to defluorinate, reduce F- to 3-7g/l, and then take off CaC0 3 or Ca(OH) 2 Fluoride dephosphorization, CaCH 2 P0 4 formed ; > 2 · H 2 0+CaF 2 can be used as fertilizer or for dephosphorization. When P 2 0 5 /F 200 in acid solution, Ca(OH) is used. 2 Adjust the pH to 8, and prepare the feed CaHP0 4 · 2Η 2 0, then adjust the pH to 12 with Ca(OH) 2 to separate the impurity mainly Mg(OH) 2 to obtain pure CaCL 2 or Ca ( N0 3 ) 2 , in the decalcification process, use S0 4 2 — or C0 3 2 _ type precipitation to prepare pure CaS0 4 · 2Η 2 0 or CaC0 3 (nanoscale), the filtrate is concentrated to make NaN0 3 , KN0 3 or 丽4 C1.
本实施例是附图 1的开环酸解形式，在含钙清液工序或脱钙工序用 H2S04(或 HS04 _ ) 进行脱钙并再生酸解液中的 HC1 (HN03 ) ， 使其返回酸解池， 就构成闭环酸解形 式。 因此， 本工艺开环闭环自如， 其实用性在于； 当接纳低浓度 HC1 (HN03 ) 时， 可 用 H2S04 (或 HS04— ) 作沉淀剂进行闭环酸解， 再开环排出酸解液 （杂质多时） ， 尽 量多接纳低浓度酸。 本工艺对用混合酸有良好的适用性。 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. Therefore, 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.
本工艺分离出的 Ca(H2P04)2.H20含 P205约 50— 55%，可作肥料， 也可利用本工艺 的条件制成饲料级的产品 （参见实施例 2 )或制成工业级、 农用级磷酸盐（参见实施例 1 ) 。 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).
本实施例中脱钙工序生成的 CaC03具备生成纳米级 CaC03的条件，属现行技术（参 见 《磷酸钙工业》 1987 ( 1-2 ) 期 96页， 化工部无机盐情报中心站、 碳酸钙情报协作 组） 编译。 工业应用性 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
1、 本发明的主导思想是充分利用酸所具有的化学能和现行磷化物加工工艺的优 点， 无论用 HCL、 HN03、 H3P04、 H2S04或混合酸都能将磷矿分解成较纯净的有很高 加工价值和使用价值的 Ca(H2P04)2 · H20晶体， 钙变成高纯净的工业填料 CaS04或 CaC03 , 氟成为纯净的氟硅酸盐， 酸解磷矿用过的酸完全回收利用， 变成有高效益的 各种钾、 钠、 铵盐， 实现原料理论利用率 100%， 形成了独立的酸解磷矿新工艺。 1. 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.
2、 本发明同时也具有同现行磷铵和磷产品加工工艺兼容和联产的特性， 特别是本 发明应用于饲料一钙和二钙时磷的理论转换率达 100 %，而无外排废水，这是现行技术 远无法实现的。  2. 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.
3、 本发明能以各种形式与现行多种工艺兼容， 其工艺和产品都有广阔的开发前景 。 如使用低浓度盐酸和副产盐酸工艺， 磷石膏制硫铵工艺， 合成铵工艺产品等， 本发 明不但接纳这些工艺和产品的优点， 还对这些工艺提供帮助， 并且均能实现所用原料 在高效益前提下的 100 %利用率，充分显示了本发明建立在高效益前提下的创新性和实 用性。  3. The invention can be compatible with various current processes in various forms, and its processes and products have broad development prospects. For example, 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.
4、 能耗低、 成本低、 效益高、 工艺简单无废水外排， 。  4. Low energy consumption, low cost, high efficiency, simple process and no waste water discharge.
5、 对 Ca(H2P04)2 · Η20二次加工效益高、 成本低， 开拓了一系列优质磷酸盐或磷 酸加工的新途径。 5. The high efficiency and low cost of Ca(H 2 P0 4 ) 2 · Η 2 0 secondary processing has opened up a series of new ways of high quality phosphate or phosphoric acid processing.

Claims

权 利 要 求 Rights request
1、 一种酸解磷矿的新方法， 其特征在于包括以下步骤： A new method for the acidolysis of phosphate rock, characterized by comprising the steps of:
a、 用酸与磷矿反应， 生成包含有水溶性钙和磷酸的酸解液；  a. reacting with the phosphate rock to form an acid hydrolyzate containing water-soluble calcium and phosphoric acid;
b、 分离出酸解液， 用含磷的化合物与酸解液中的磷酸反应， 生成包含有  b, separating the acid solution, reacting the phosphorus-containing compound with the phosphoric acid in the acid solution, and generating
Ca(H2P04)2 · H20结晶体的固形物； a solid of Ca(H 2 P0 4 ) 2 · H 2 0 crystal;
c、 分离出包含有 Ca(H2P04)2 · H20结晶体的固形物； c, separating solid matter containing Ca(H 2 P0 4 ) 2 · H 2 0 crystal body;
d、 从酸解液中分离出氟化合物；  d, separating the fluorine compound from the acid hydrolysis solution;
e、 净化酸解液；  e, purifying the acid solution;
f、 向净化后的酸解液加入沉淀剂， 生成钙化合物沉淀， 分离出钙化合物和滤液。 f. A precipitant is added to the purified acid hydrolyzate to form a calcium compound precipitate, and the calcium compound and the filtrate are separated.
2、 如权利要求 1所述的酸解磷矿的新方法， 其特征在于： 2. A new method of acidolysis of phosphate rock according to claim 1 wherein:
步骤 a所述的酸是含有 HCL、 或 HN03、 或 H3P04、 或三者任意比例组成的混合 酸； 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;
步骤 b所述的分离是用沉降分离的方式分离出酸解液中的固形物， 得到的酸解液 是分离了固形物的酸解液， 所述的含磷的化合物包括磷矿、 或磷酸氢钙或两者任意比 例的组合；  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 solution is an acid solution which separates the solid matter, and the phosphorus-containing compound includes phosphate rock or phosphoric acid. Hydrogen calcium or a combination of any two of them;
步骤 c所述的固形物是用洗涤水洗涤的固形物；  The solid matter described in step c is a solid matter washed with washing water;
步骤 d所述的分离是用生成氟硅酸盐沉淀的方式， 或生成 CaF2沉淀的方式， 或者 两种方式的组合； The separation described in step d is a method of forming a fluorosilicate precipitate, or a method of forming a CaF 2 precipitate, or a combination of the two;
步骤 e所述的净化是滤除固形物， 或加入化学试剂分离各种杂质， 或者两种方式 的组合；  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 methods;
步骤 f所述的沉淀剂是含有 S042—类或 C03 2—类的水溶性化合物， 生成的钙化合物 分别是 CaS04 · XH20或 CaC03， X为 0、 1/2或 2， 得到的滤液是含酸滤液或者是无酸 滤液。 The precipitating agent described in the step f is a water-soluble compound containing a group of S04 2 or C0 3 2 , and the resulting calcium compound is CaS0 4 · XH 2 0 or CaC0 3 , respectively, and X is 0, 1/2 or 2. The filtrate obtained is an acid-containing filtrate or an acid-free filtrate.
3、 如权利要求 2所述的酸解磷矿的新方法， 其特征在于：  3. A new method of acidifying phosphate rock according to claim 2, wherein:
步骤 b所述的磷矿粒度大于 lmm， 优选 10— 200mm;  The particle size of the phosphate rock described in step b is greater than lmm, preferably 10 to 200 mm;
步骤 c所述的洗涤水来自脱氟后的酸解液， 洗涤固形物后又返回脱氟之前的酸解 液中；  The washing water described in step c is derived from the deacidified acid hydrolysate, and after washing the solid matter, it returns to the acid solution before defluorination;
步骤 d所述的生成氟硅酸盐沉淀的方式是向酸解液中加入水溶性钾盐或钠盐  The method for producing a fluorosilicate precipitate described in the step d is to add a water-soluble potassium salt or a sodium salt to the acid hydrolysis solution.
NaCl, 或 KC1， 或 NaN03， 或 KN03， 生成 CaF2沉淀的方式是向酸解液中加入 CaC03、 Ca(OH)2 ; 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 ;
步骤 e所述的化学试剂是 NH3、 或 CaC03、 或 Ca( H)2; 步骤 f所述的含有 S042—的水溶性化合物是 H2S04、 K2S04、 Na2S04 (NH4)2S04 KHS04、 NaHS04， 含有 C03 2—的水溶性化合物是 Na2C03、 NaHC03 、 (NH4)2C03 NH4HC03、 KHCO3 , 含酸滤液含有 HCL、 或 HN03、 或 H3P04、 或三者任意比例的组 合， 无酸滤液含有 Na N03、 KN03、 NH4N03 NH4C1、 KC1。 The chemical reagent described in step e is NH 3 , or CaCO 3 , or Ca(H) 2; The water-soluble compound containing S04 2 - described in the step f is H 2 S0 4 , K 2 S0 4 , Na 2 S0 4 (NH 4 ) 2 S0 4 KHS0 4 , NaHS0 4 , a water-soluble compound containing C0 3 2 — Is Na 2 C0 3 , NaHC0 3 , (NH 4 ) 2 C0 3 NH 4 HC0 3 , KHCO3 , acid-containing filtrate containing HCL, or HN0 3 , or H 3 P0 4 , or a combination of any three, acid-free filtrate Contains Na N0 3 , KN0 3 , NH 4 N0 3 NH 4 C1, KC1.
4、 如权利要求 3所述的酸解磷矿的新方法， 其特征在于： 步骤 f所述的含酸滤液 返回酸解磷矿步骤 a， 无酸滤液则进入其它工序。  4. A new method for the acidolysis of phosphate rock according to claim 3, wherein: the acid-containing filtrate of step f is returned to the acid phosphate rock step a, and the acid-free filtrate is passed to other steps.
5、 如权利要求 2所述的酸解磷矿的新方法， 其特征在于： 步骤 a所述的 HCL包 括 H2S04与 KCL或 NaCl反应生成的 HCL气体用酸解液吸收的 HCL溶液。 5, as claimed in claim 2, the acid phosphate solution new method, wherein: HCL a step of the HCL solution comprises H 2 S0 4 KCL or NaCl reacts with the acid solution with HCL gas was absorbed.
6、 如权利要求 1所述的酸解磷矿的新方法在硫酸酸解磷矿中的应用。  6. The use of a novel method for the acidolysis of phosphate rock according to claim 1 in a phosphate acid phosphate rock.
7、如权利要求 2所述的酸解磷矿的新方法在生产饲料级磷酸氢钙和磷酸二氢钙中 的应用。  7. Use of a novel method of acidolysis of phosphate rock according to claim 2 for the production of feed grade calcium hydrogen phosphate and calcium dihydrogen phosphate.
8、 如权利要求 2所述的酸解磷矿的新方法在 HC1、 HNO3为原料酸解磷矿中的应 用。  8. The novel method of acidifying phosphate rock according to claim 2, wherein HC1 and HNO3 are used as raw material for acidolysis of phosphate rock.
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