WO2018032911A1 - Procédé de préparation d'hydrophosphate de calcium de qualité alimentaire à partir de déchets liquides comprenant de l'acide phosphorique - Google Patents

Procédé de préparation d'hydrophosphate de calcium de qualité alimentaire à partir de déchets liquides comprenant de l'acide phosphorique Download PDF

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WO2018032911A1
WO2018032911A1 PCT/CN2017/092601 CN2017092601W WO2018032911A1 WO 2018032911 A1 WO2018032911 A1 WO 2018032911A1 CN 2017092601 W CN2017092601 W CN 2017092601W WO 2018032911 A1 WO2018032911 A1 WO 2018032911A1
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phosphoric acid
hydrogen phosphate
feed grade
calcium hydrogen
grade calcium
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PCT/CN2017/092601
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Chinese (zh)
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吴文彪
李雯
徐文彬
袁城
李姗婷
佘玲玲
张艳华
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东江环保股份有限公司
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

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  • the present application relates to a method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid.
  • the photovoltaic phosphor etchant in the photovoltaic industry is a kind of strong acid waste liquid (also known as aluminum etching waste liquid in the industry) which is produced in a large amount in the process of thin film transistor liquid crystal display device (TFT-LCD).
  • TFT-LCD thin film transistor liquid crystal display device
  • the TFT-LCD process mainly coats the surface of the glass with a metal film (mainly aluminum), and then removes the portion not covered and protected by the photoresist by a chemical reaction method according to the circuit design requirement. Thereby the purpose of transferring the mask pattern onto the film is completed.
  • the spent phosphoric acid etching solution contains about 55 wt% to 75 wt% phosphoric acid, 5 wt% to 10 wt% acetic acid, 1 wt% to 5 wt% nitric acid, 1 g/L to 5 g/L aluminum, and 1 g/L to 2 g/L molybdenum. .
  • the treatment method for the waste phosphoric acid etching solution is mainly a harmless neutralization method.
  • the method requires a large amount of alkali to be consumed, and a large amount of waste residue is required to be disposed of in a landfill, thereby wasting a large amount of phosphoric acid resources.
  • a method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid comprises the following steps:
  • the phosphoric acid-containing waste liquid is heated to 40° C. to 60° C. under stirring, the stirring speed is controlled to be 100 rpm to 300 rpm, and the solid-liquid ratio is added to the phosphoric acid-containing waste liquid at a rate of 5 mL/min to 20 mL/min. /L ⁇ 250g / L CaCO 3 slurry to a pH of 2.5 ⁇ 3.5, to obtain a first mixed system, the mixing system for 5 min ⁇ 30 min;
  • the stirring speed is controlled to be 100 rpm to 300 rpm, and a Ca(OH) 2 slurry having a solid-liquid ratio of 50 g/L to 200 g/L is added to the first mixed system at a rate of 5 mL/min to 20 mL/min to a pH value. a mixture of 5.0 to 6.5, a second mixing system is obtained, and the second mixing system is maintained for 30 minutes to 60 minutes by controlling the stirring speed from 80 rpm to 120 rpm;
  • the second mixing system that completes the crystal growth is filtered and the filter residue is retained, which is feed grade calcium hydrogen phosphate.
  • the phosphoric acid-containing waste liquid contains 50% to 80% of phosphoric acid by mass percentage.
  • the phosphoric acid-containing waste liquid is a spent phosphoric acid etchant.
  • the CaCO 3 slurry having a solid-liquid ratio of 100 g/L to 250 g/L is added to the phosphoric acid-containing waste liquid at a rate of 5 mL/min to 20 mL/min to a pH of 2.5 to 3.5.
  • the CaCO 3 slurry has a solid-liquid ratio of 200 g/L, and the CaCO 3 slurry has an addition rate of 10 mL/min.
  • the Ca(OH) 2 slurry having a solid-liquid ratio of 50 g/L to 200 g/L is added to the first mixed system at a rate of 5 mL/min to 20 mL/min to a pH value.
  • the solid-liquid ratio of the Ca(OH) 2 slurry was 100 g/L, and the addition rate of the Ca(OH) 2 slurry was 10 mL/min.
  • the controlled agitation speed is from 80 rpm to 120 rpm for the second mixture In the operation of maintaining the crystal for 30 min to 60 min, the stirring speed is 100 rpm.
  • the operation of filtering and retaining the second mixing system that completes the crystal growth further includes the following operations: retaining the filtrate, and using the filtrate for formulating CaCO 3 slurry and Ca
  • the (OH) 2 slurry is subjected to a cyclic reaction to recover the residual phosphoric acid resources in the filtrate.
  • the method further comprises the steps of drying, crushing, sieving, and packaging the feed grade calcium hydrogen phosphate after the feed grade calcium hydrogen phosphate is obtained.
  • the method for preparing feed grade calcium hydrogen phosphate from the phosphoric acid waste liquid comprises treating the phosphorous acid containing waste liquid with a CaCO 3 slurry, and the pH of the end point of the treatment is 2.5 to 3.5, followed by adding the Ca(OH) 2 slurry.
  • the pH of the end point of the second stage treatment is 5.0-6.5, and finally the crystal is crystallized, and the feed grade calcium hydrogen phosphate can be obtained after filtration.
  • the method for preparing feed grade calcium hydrogen phosphate from the phosphoric acid-containing waste liquid can greatly recycle the phosphoric acid resources in the phosphoric acid-containing waste liquid.
  • the method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid requires only about 3 hours for each batch of phosphoric acid-containing waste liquid, and the filtration operation is only one step, and the operation difficulty of the process is low, so that the corresponding production capacity is achieved. Higher.
  • the feed grade calcium hydrogen phosphate prepared by the method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid meets the requirements of the type I product of GB/T 22549-2008 feed grade calcium hydrogen phosphate, and the feed grade calcium hydrogen phosphate The yield is above 95%, and the moisture content of the product can be controlled below 30%, which greatly reduces the subsequent drying energy consumption.
  • FIG. 1 is a flow chart of a method for preparing feed grade calcium hydrogen phosphate from a phosphoric acid-containing waste liquid according to an embodiment.
  • the two-stage neutralization crystallization method is used to treat the phosphoric acid-containing waste liquid to obtain feed grade calcium hydrogen phosphate.
  • the calcium carbonate slurry which is slow to react with phosphoric acid is used to neutralize most of the H + ionized in the phosphoric acid.
  • a method for preparing feed grade calcium hydrogen phosphate from a phosphoric acid-containing waste liquid according to an embodiment shown in FIG. 1 comprises the following steps:
  • step S10 The reaction equation of step S10 is:
  • 3H 3 PO 4 +2CaCO 3 CaHPO 4 ⁇ 2H 2 O ⁇ +Ca(H 2 PO 4 ) 2 +2CO 2 ⁇ .
  • the first mixing system comprises calcium hydrogen phosphate crystals and water soluble calcium dihydrogen phosphate. Since the reaction rate of phosphoric acid and CaCO 3 is slow, the calcium hydrogen phosphate crystal has a better crystal structure, and the CO 2 gas generated in the reaction of the step S10 can perform a certain mixing effect.
  • the phosphoric acid-containing waste liquid contains 50% to 80% of phosphoric acid in terms of mass percentage.
  • the phosphoric acid-containing waste liquid is a waste phosphoric acid etching solution.
  • the phosphoric acid-containing waste liquid is placed in a stirring tank, and the stirring speed is controlled to be 100 rpm to 300 rpm, and the temperature is raised to 40 ° C to 60 ° C (preferably 40 ° C).
  • a CaCO 3 slurry having a solid-liquid ratio of 100 g/L to 250 g/L is added to the phosphoric acid-containing waste liquid at a rate of 5 mL/min to 20 mL/min to a pH of 2.5 to 3.5, and CaCO 3 is used.
  • the solid-liquid ratio of the slurry was 200 g/L
  • the addition rate of the CaCO 3 slurry was 10 mL/min
  • the CaCO 3 slurry was adjusted to a pH of 3.5.
  • the stirring speed is preferably 200 rpm.
  • Step S20 uses the Ca(OH) 2 slurry to neutralize calcium dihydrogen phosphate in the first mixing system of step S10, so that the calcium dihydrogen phosphate in the first mixing system is also converted into calcium hydrogen phosphate crystal. , thereby converting all of the phosphoric acid in the phosphoric acid-containing waste liquid into crystals of calcium hydrogen phosphate, and the specific reaction equation is:
  • step S20 The higher the pH value of the two-stage end point of step S20, the more complete the reaction of the Ca(OH) 2 slurry with calcium dihydrogen phosphate, however, when the Ca(OH) 2 slurry reacts with calcium dihydrogen phosphate, the reaction tends to When complete, it may convert some of the calcium hydrogen phosphate into calcium phosphate, so the pH of the second stage endpoint should not be too high.
  • the selection consideration of the other reaction conditions in step S20 is substantially similar to the step S10, and details are not described herein again.
  • a Ca(OH) 2 slurry having a solid-liquid ratio of 50 g/L to 200 g/L is added to the first mixed system at a rate of 5 mL/min to 20 mL/min to a pH of 5.0 to 6.5.
  • the solid-liquid ratio of the Ca(OH) 2 slurry was 100 g/L, the Ca(OH) 2 slurry was added at a rate of 10 mL/min, and the Ca(OH) 2 slurry was adjusted to a pH of 5.75.
  • the stirring speed is 100 rpm.
  • the method further comprises the steps of: retaining the filtrate, and using the filtrate for preparing a CaCO 3 slurry and a Ca(OH) 2 slurry for recycling reaction to recover Phosphoric acid resources remaining in the filtrate.
  • S30 also includes the operation of drying, crushing, sieving, and packaging the feed grade calcium hydrogen phosphate after obtaining the feed grade calcium hydrogen phosphate.
  • the method for preparing feed grade calcium hydrogen phosphate from the phosphoric acid waste liquid comprises treating the phosphorous acid containing waste liquid with a CaCO 3 slurry, and the pH of the end point of the treatment is 2.5 to 3.5, followed by adding the Ca(OH) 2 slurry.
  • the pH of the end point of the second stage treatment is 5.0-6.5, and finally the crystal is crystallized, and the feed grade calcium hydrogen phosphate can be obtained after filtration.
  • the method for preparing feed grade calcium hydrogen phosphate from the phosphoric acid-containing waste liquid can greatly recycle the phosphoric acid resources in the phosphoric acid-containing waste liquid.
  • the method for preparing feed grade calcium hydrogen phosphate by using phosphoric acid waste liquid is simple in process, easy to control, and stable in product properties
  • the prepared feed grade calcium hydrogen phosphate product is type I product, that is, both are dihydrogen phosphate dihydrate ( CaHPO 4 ⁇ 2H 2 O), calcium dihydrogen phosphate dihydrate is insoluble in water, so the product is relatively stable (the key indicator ⁇ soluble phosphorus content does not change much, and is close to the theoretical value of 18.02%), and Type II or III products also contain a considerable amount of water-soluble phosphorus, calcium dihydrogen phosphate (Ca(H 2 PO 4 ) 2 ), which is liable to cause losses during filtration or washing, resulting in different batches of products. The nature difference will be great.
  • the feed grade calcium hydrogen phosphate product obtained by the method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid can achieve a conversion rate of more than 95%. It is well known that there is a problem of feed/fertilizer ratio in the preparation of calcium hydrogen phosphate, that is, the yield ratio of feed grade calcium hydrogen phosphate and fertilizer grade calcium hydrogen phosphate.
  • the feed/fertilizer ratio of the conventional method for preparing calcium hydrogen phosphate is generally 6: 4, because the value of feed grade calcium hydrogen phosphate is close to 10 times the value of fertilizer grade calcium hydrogen phosphate, so the higher the feed/fertilizer ratio, the better the economic benefit.
  • the existing waste phosphoric acid etching solution for the preparation of feed grade calcium hydrogen phosphate The patented feed/fertilizer ratio is generally around 8:2, and the conversion rate of feed grade calcium hydrogen phosphate prepared by the process of preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid is close to 100% (one conversion rate is 95%). As described above, the remaining 5% of the phosphorus resources are also recycled through the circulation of the filtrate obtained in S30.
  • the second mixed system is crystallized for 30 min to 60 min, and the crystal of calcium hydrogen phosphate having larger particles and better crystal form can be obtained, and the moisture content of the wet base is lowered, thereby reducing the drying energy consumption.
  • the recycling effect of the filtrate obtained in S30 can also reduce the subsequent treatment cost of the wastewater (the conventional method requires a batch of wastewater to be treated for each batch of products because it is not recycled, and the phosphoric acid-containing waste liquid is used to prepare feed grade calcium hydrogen phosphate.
  • the method can be processed every 10 batches or more due to recycling A batch of wastewater).
  • the method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid requires only about 3 hours for each batch of phosphoric acid-containing waste liquid, and the filtration operation is only one step, and the process operation is less difficult and the productivity is high.
  • the feed grade calcium hydrogen phosphate prepared by the method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid meets the requirements of the type I product of GB/T 22549-2008 feed grade calcium hydrogen phosphate, and the feed grade calcium hydrogen phosphate
  • the yield is above 95%, and the moisture content of the product can be controlled below 30%, which greatly reduces the subsequent drying energy consumption.
  • a waste phosphoric acid etching solution from a certain batch of photoelectric enterprises in Shenzhen is provided. Its composition characteristics are phosphoric acid content of 59.02%, acetic acid content of 7.81%, and nitric acid content of 1.73%.
  • the above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm.
  • a CaCO 3 material having a concentration of 200 g/L of water was added to the stirring tank at a rate of 10 mL/min. Slurry, adjust the pH value of the solution to 3.5, and keep it for 0.5 h. Under the same conditions, continue to add Ca(OH) 2 slurry with a concentration of 100 g/L water, adjust the pH of the solution to 5.75, and reduce the stirring speed to 100 rpm. Crystallized for 0.5h, filtered to obtain a feed grade calcium hydrogen phosphate filter cake.
  • the weight was 203.4 g
  • the moisture content of the wet base was 27.82%
  • the yield of the obtained feed grade calcium hydrogen phosphate was 98.12%.
  • the average particle size of the obtained feed grade calcium hydrogen phosphate product is 152 ⁇ m, wherein the mass percentage of each component is as follows: total phosphorus 17.64%, bismuth soluble phosphorus 17.45%, water soluble phosphorus 1.11%, calcium 23.64%, fluorine 0.0072%, arsenic ⁇ 0.000002%, lead ⁇ 0.001%, cadmium ⁇ 0.00006, fineness 100%.
  • a waste phosphoric acid etching solution from a certain batch of photoelectric enterprises in Shenzhen is provided. Its composition characteristics are phosphoric acid content of 59.02%, acetic acid content of 7.81%, and nitric acid content of 1.73%.
  • the above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm.
  • a CaCO 3 material having a concentration of 200 g/L of water was added to the stirring tank at a rate of 10 mL/min. Slurry, adjust the pH value of the solution to 3.5, and keep it for 0.5 h. Under the same conditions, continue to add Ca(OH) 2 slurry with a concentration of 200 g/L water, adjust the pH of the solution to 6.00, and reduce the stirring speed to 100 rpm. Crystallized for 0.5h, filtered to obtain a feed grade calcium hydrogen phosphate filter cake.
  • the weigh was 199.3 g, the moisture content of the wet base was 28.13%, and the yield of the obtained feed grade calcium hydrogen phosphate was 96.14%.
  • the average particle size of the obtained feed grade calcium hydrogen phosphate is 142 ⁇ m, wherein the mass percentage of each component is as follows: total phosphorus 17.68%, bismuth soluble phosphorus 17.47%, water soluble phosphorus 1.17%, calcium 24.09%, fluorine 0.0089 %, arsenic ⁇ 0.000002%, lead ⁇ 0.001%, cadmium ⁇ 0.00006, fineness 100%.
  • a waste phosphoric acid etching solution from a certain batch of photoelectric enterprises in Shenzhen is provided. Its composition characteristics are phosphoric acid content of 59.02%, acetic acid content of 7.81%, and nitric acid content of 1.73%.
  • the above waste phosphoric acid etching solution 200 g was added to the stirring tank to control the stirring speed of 100 rpm.
  • the CaCO 3 material having a concentration of 250 g/L of water was added to the stirring tank at a rate of 10 mL/min.
  • the slurry was adjusted to pH value of 3.5, under the same conditions, the Ca(OH) 2 slurry with a concentration of 100 g/L water was continuously added, the pH of the solution was adjusted to 6.50, the stirring speed was reduced to 100 rpm, and the crystal was raised for 0.5 h. Filtration, that is, feed grade calcium hydrogen phosphate filter cake.
  • the filter cake was dried, it was weighed to 200.5 g, the moisture content of the wet base was 30.94%, and the yield of the obtained feed grade calcium hydrogen phosphate was 96.77%.
  • the average particle size of the obtained feed grade calcium hydrogen phosphate is 128 ⁇ m, wherein the quality of each component
  • the percentage content is as follows: total phosphorus 17.48%, bismuth soluble phosphorus 16.85%, water soluble phosphorus 0.87%, calcium 22.45%, fluorine 0.0093%, arsenic ⁇ 0.000002%, lead ⁇ 0.001%, cadmium ⁇ 0.00006, fineness 100%.
  • a waste phosphoric acid etching solution from a certain batch of photoelectric enterprises in Shenzhen is provided, and its composition characteristics are phosphoric acid content of 61.05%, acetic acid content of 4.03%, and nitric acid content of 1.88%.
  • the above waste phosphoric acid etching solution (200 g) was added to a stirring tank to control the stirring speed of 300 rpm.
  • a CaCO 3 material having a concentration of 200 g/L of water was added to the stirring tank at a rate of 20 mL/min. Slurry, adjust the pH value of the solution to 3.0, and keep it for 0.5 h. Under the same conditions, continue to add Ca(OH) 2 slurry with a concentration of 100 g/L water, adjust the pH value of the solution to 5.5, and reduce the stirring speed to 100 rpm. Crystallized for 0.5h, filtered to obtain a feed grade calcium hydrogen phosphate filter cake.
  • the weight was 209.2 g
  • the moisture content of the wet base was 29.47%
  • the yield of the obtained feed grade calcium hydrogen phosphate was 97.62%.
  • the average particle size of the obtained feed grade calcium hydrogen phosphate is 138 ⁇ m, wherein the mass percentage of each component is as follows: total phosphorus 17.76%, bismuth soluble phosphorus 17.74%, water soluble phosphorus 1.21%, calcium 23.25%, fluorine 0.0077 %, arsenic ⁇ 0.000002%, lead ⁇ 0.001%, cadmium ⁇ 0.00006, fineness 100%.
  • Example 2 The same waste phosphoric acid etching solution as in Example 1 was provided.
  • the above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm.
  • a CaCO 3 material having a concentration of 200 g/L of water was added to the stirring tank at a rate of 10 mL/min. Slurry, adjust the pH value of the solution to 3.5, and keep it for 0.5 h. Under the same conditions, continue to add Ca(OH) 2 slurry with a concentration of 100 g/L water, adjust the pH value of the solution to 5.75, and filter to obtain feed grade hydrogen phosphate. Calcium filter cake.
  • the weigh was 203.3 g, and the moisture content of the wet base was 31.27%.
  • the yield of calcium hydrogen phosphate was 98.07%.
  • the average particle size of the obtained feed grade calcium hydrogen phosphate is 95 ⁇ m, wherein the mass percentage of each component is as follows: total phosphorus 17.63%, bismuth soluble phosphorus 17.42%, water soluble phosphorus 1.10%, calcium 23.60%, fluorine 0.0071 %, arsenic ⁇ 0.000002%, lead ⁇ 0.001%, cadmium ⁇ 0.00006, fineness 100%.
  • Comparative Examples 1 to 4 and Comparative Example 1 the operation of no crystal growth in Comparative Example 1 resulted in a relatively low average particle size of the feed grade calcium hydrogen phosphate filter cake prepared in Comparative Example 1, and a poor crystal form.
  • the water content is high.

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Abstract

L'invention concerne un procédé de préparation d'hydrophosphate de calcium de qualité alimentaire à partir d'un déchet liquide comprenant de l'acide phosphorique, comprenant les étapes suivantes consistant à : chauffer le déchet liquide comprenant de l'acide phosphorique sous agitation, et ajouter une suspension de CaCO3 à une valeur de pH de 2,5 à 3,5 pour obtenir un premier système mélangé et le garder à la température pendant une certaine durée; ajouter une suspension de Ca(OH)2 au premier système mélangé à une valeur de pH de 5,0-6,5, et soumettre un second système mélangé à une croissance cristalline; effectuer une filtration et réserver les résidus, les résidus étant l'hydrophosphate de calcium de qualité alimentaire. Dans le procédé de préparation d'hydrophosphate de calcium de qualité alimentaire à partir du déchet liquide comprenant de l'acide phosphorique, une suspension de CaCO3 est utilisée pour effectuer une première étape de traitement sur le déchet liquide comprenant de l'acide phosphorique, la valeur de pH final de la première étape de traitement étant comprise entre 2,5 et 3,5, puis une suspension de Ca(OH)2 est ajoutée pour effectuer une deuxième étape de traitement, la valeur de pH final de la deuxième étape de traitement étant comprise entre 5,0 et 6,5, enfin, la croissance des cristaux est effectuée, suivie d'une filtration pour obtenir l'hydrophosphate de calcium de qualité alimentaire. Le procédé de préparation de l'hydrophosphate de calcium de qualité alimentaire à partir du déchet liquide comprenant de l'acide phosphorique peut maximiser le recyclage des ressources d'acide phosphorique dans le déchet liquide comprenant de l'acide phosphorique.
PCT/CN2017/092601 2016-08-15 2017-07-12 Procédé de préparation d'hydrophosphate de calcium de qualité alimentaire à partir de déchets liquides comprenant de l'acide phosphorique WO2018032911A1 (fr)

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