WO2018032911A1 - Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid - Google Patents

Method for preparing feed grade calcium hydrophosphate from waste liquid comprising phosphoric acid 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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French (fr)
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

A method for preparing feed grade calcium hydrophosphate from a waste liquid comprising phosphoric acid, comprising the following steps: heating the waste liquid comprising phosphoric acid under stirring, and adding a CaCO3 slurry to a pH value of 2.5-3.5 to obtain a first mixed system and keeping same at the temperature for a period of time; adding a Ca(OH)2 slurry to the first mixed system to a pH value of 5.0-6.5, and subjecting a second mixed system to crystal growth; performing filtration and reserving the residues, and the residues being the feed grade calcium hydrophosphate. In the method for preparing feed grade calcium hydrophosphate from the waste liquid comprising phosphoric acid, a CaCO3 slurry is used to perform first stage treatment on the waste liquid comprising phosphoric acid, the final pH value of the first stage treatment being 2.5-3.5, and then a Ca(OH)2 slurry is added to perform second stage treatment, the final pH value of the second stage treatment being 5.0-6.5, finally, crystal growth is performed, followed by filtration to obtain the feed grade calcium hydrophosphate. The method for preparing the feed grade calcium hydrophosphate from the waste liquid comprising phosphoric acid can maximize the recycling of the phosphoric acid resources in the waste liquid comprising phosphoric acid.

Description

含磷酸废液制备饲料级磷酸氢钙的方法Method for preparing feed grade calcium hydrogen phosphate from phosphoric acid waste liquid
相关申请Related application
本申请要求2016年08月15日申请的，申请号为201610671498.3，名称为“含磷酸废液制备饲料级磷酸氢钙的方法”的中国专利申请的优先权，在此将其全文引入作为参考。This application claims the benefit of priority to the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the present disclosure.
技术领域Technical field
本申请涉及一种含磷酸废液制备饲料级磷酸氢钙的方法。The present application relates to a method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid.
背景技术Background technique
光电行业废磷酸蚀刻液是薄膜晶体管液晶显示器件(TFT-LCD)制程中大量产生的一种强酸性废液(行业内也称为铝蚀刻废液)。一般TFT-LCD制程主要是将玻璃表面镀上一层金属薄膜(主要为铝)，随即依电路设计需求，用酸性蚀刻液将没有被光阻覆盖及保护的部分以化学反应的方式加以去除，从而完成转移光罩图案到薄膜上的目的。废磷酸蚀刻液中约含55wt％～75wt％的磷酸、5wt％～10wt％的醋酸、1wt％～5wt％的硝酸、1g/L～5g/L的铝以及1g/L～2g/L的钼。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). Generally, 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. .
目前针对废磷酸蚀刻液的处理方法主要为无害化中和法，然而该法需要消耗大量的碱，并且产生大量的废渣需要填埋处置，从而浪费了大量的磷酸资源。At present, the treatment method for the waste phosphoric acid etching solution is mainly a harmless neutralization method. However, 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.
发明内容Summary of the invention
基于此，有必要提供一种能够对废磷酸蚀刻液中的磷酸资源进行回收利用的含磷酸废液制备饲料级磷酸氢钙的方法。 Based on this, it is necessary to provide a method for preparing feed grade calcium hydrogen phosphate from a phosphoric acid-containing waste liquid capable of recycling phosphoric acid resources in a spent phosphoric acid etching solution.
一种含磷酸废液制备饲料级磷酸氢钙的方法，包括如下步骤：A method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid comprises the following steps:
将含磷酸废液在搅拌状态下升温至40℃～60℃，控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向所述含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5，得到第一混合体系，对所述混合体系保温停留5min～30min；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;
控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向所述第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5，得到第二混合体系，控制搅拌速度为80rpm～120rpm对所述第二混合体系进行养晶30min～60min；以及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;
将完成养晶的所述第二混合体系进行过滤并保留滤渣，所述滤渣即为饲料级磷酸氢钙。The second mixing system that completes the crystal growth is filtered and the filter residue is retained, which is feed grade calcium hydrogen phosphate.
在一个实施例中，所述含磷酸废液中按照质量百分数含有50％～80％的磷酸。In one embodiment, the phosphoric acid-containing waste liquid contains 50% to 80% of phosphoric acid by mass percentage.
在一个实施例中，所述含磷酸废液为废磷酸蚀刻液。In one embodiment, the phosphoric acid-containing waste liquid is a spent phosphoric acid etchant.
在一个实施例中，所述以5mL/min～20mL/min的速度向所述含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5的操作中，所述CaCO3料浆的固液比为200g/L，所述CaCO3料浆的添加速度为10mL/min。In one embodiment, 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. In the operation, 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.
在一个实施例中，所述以5mL/min～20mL/min的速度向所述第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5的操作中，所述Ca(OH)2料浆的固液比为100g/L，所述Ca(OH)2料浆的添加速度为10mL/min。In one embodiment, 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. In the operation of 5.0 to 6.5, 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.
在一个实施例中，所述控制搅拌速度为80rpm～120rpm对所述第二混合体 系养晶30min～60min的操作中，所述搅拌速度为100rpm。In one embodiment, 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.
在一个实施例中，所述将完成养晶的所述第二混合体系进行过滤并保留滤渣的操作中，还包括如下操作：保留滤液，并将所述滤液用于配制CaCO3料浆和Ca(OH)2料浆进行循环反应，以回收所述滤液中残留的磷酸资源。In one embodiment, 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.
在一个实施例中，还包括在得到所述饲料级磷酸氢钙后，对所述饲料级磷酸氢钙进行干燥、破碎、筛分、包装的操作。In one embodiment, 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.
这种含磷酸废液制备饲料级磷酸氢钙的方法通过采用CaCO3料浆对含磷酸废液进行一段处理，一段处理的终点pH值为2.5～3.5，接着加入Ca(OH)2料浆进行二段处理，二段处理的终点pH值为5.0～6.5，最后养晶，过滤后即可得到饲料级磷酸氢钙。这种含磷酸废液制备饲料级磷酸氢钙的方法能够极大限度的对含磷酸废液中的磷酸资源进行回收利用。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. In the second stage treatment, 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.
此外，这种含磷酸废液制备饲料级磷酸氢钙的方法处理每批含磷酸废液的时间大约只需要3h左右，而且过滤操作仅有1步，工艺的操作难度较低，从而相应的产能较高。这种含磷酸废液制备饲料级磷酸氢钙的方法制备得到的饲料级磷酸氢钙符合《GB/T 22549-2008饲料级磷酸氢钙》中I型产品的指标要求，其饲料级磷酸氢钙的产率在95％以上，而且产品的湿基含水率可控制在30％以下，大幅降低后续干燥能耗。In addition, 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.
附图说明DRAWINGS
为了使本申请的内容更容易被清楚的理解，下面根据本申请的具体实施例并结合附图，对本申请作进一步详细的说明，其中In order to make the content of the present application easier to understand, the present application will be further described in detail below in accordance with the specific embodiments of the present application and the accompanying drawings.
图1为一实施方式的含磷酸废液制备饲料级磷酸氢钙的方法的流程图。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.
具体实施方式detailed description
为使本申请的目的、技术方案和优点更加清楚，下面将结合附图对本申 请实施方式作进一步地详细描述。In order to make the purpose, technical solution and advantages of the present application more clear, the following will be combined with the accompanying drawings. Please describe the implementation method in further detail.
本申请采用二段中和结晶法处理含磷酸废液来得到饲料级磷酸氢钙，具体地，先利用与磷酸反应速度较慢的碳酸钙料浆中和掉磷酸中电离出来的大部分H+，以得到部分晶型好的磷酸氢钙晶体和水溶性的磷酸二氢钙，再用氢氧化钙料浆中和剩余部分的磷酸二氢钙。In the present application, the two-stage neutralization crystallization method is used to treat the phosphoric acid-containing waste liquid to obtain feed grade calcium hydrogen phosphate. Specifically, 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. To obtain a partially crystalline calcium hydrogen phosphate crystal and a water-soluble calcium dihydrogen phosphate, and to neutralize the remaining portion of calcium dihydrogen phosphate with a calcium hydroxide slurry.
如图1所示的一实施方式的含磷酸废液制备饲料级磷酸氢钙的方法，包括如下步骤：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:
S10、将含磷酸废液在搅拌状态下升温至40℃～60℃，控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5，得到第一混合体系，对混合体系保温停留5min～30min。S10, heating the phosphoric acid-containing waste liquid to 40 ° C to 60 ° C under stirring, controlling the stirring speed to be 100 rpm to 300 rpm, and adding a solid-liquid ratio of 100 g 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, the first mixed system is obtained, and the mixed system is kept for 5 min ~ 30 min.
步骤S10的反应方程式为：The reaction equation of step S10 is:
3H3PO4+2CaCO3＝CaHPO4·2H2O↓+Ca(H2PO4)2+2CO2↑。3H 3 PO 4 +2CaCO 3 =CaHPO 4 ·2H 2 O↓+Ca(H 2 PO 4 ) 2 +2CO 2 ↑.
所述第一混合体系包括磷酸氢钙晶体和水溶性的磷酸二氢钙。由于磷酸与CaCO3的反应速度较慢，因此所述磷酸氢钙晶体具有较好的晶型结构，而且在步骤S10的反应过程中产生的CO2气体能起到一定的混匀作用。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.
本实施方式中，含磷酸废液中按照质量百分数含有50％～80％的磷酸。In the present embodiment, the phosphoric acid-containing waste liquid contains 50% to 80% of phosphoric acid in terms of mass percentage.
优选的，含磷酸废液为废磷酸蚀刻液。Preferably, the phosphoric acid-containing waste liquid is a waste phosphoric acid etching solution.
搅拌速度越大，磷酸和所述CaCO3料浆混合越充分，反应越完全，然而，搅拌速度过快会导致生成的所述磷酸氢钙晶体脆断和打碎。加热温度越高，所述磷酸氢钙晶体的含水率越小，所述磷酸氢钙晶体的晶型结构越完美，然而，温度过高，一方面能耗越大，另一方面所得到的磷酸氢钙晶体的颗粒越细，越难过滤，从而大幅延长了后续步骤S3的过滤时间。 The greater the agitation speed, the more sufficient the phosphoric acid and the CaCO 3 slurry are mixed, and the more complete the reaction, however, the too fast agitation speed causes the generated calcium hydrogen phosphate crystal to be brittle and broken. The higher the heating temperature, the smaller the water content of the calcium hydrogen phosphate crystal, the more perfect the crystal structure of the calcium hydrogen phosphate crystal, however, the temperature is too high, on the one hand, the energy consumption is larger, and on the other hand, the obtained phosphoric acid The finer the particles of the calcium hydride crystal, the more difficult it is to filter, thereby greatly extending the filtration time of the subsequent step S3.
优选的，将含磷酸废液置于搅拌槽内，控制搅拌速度为100rpm～300rpm，升温至40℃～60℃(优选为40℃)。Preferably, 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).
所述CaCO3料浆的进料速度越快，所述反应体系的局部过饱和度越高，也即磷酸和所述CaCO3料浆的反应越不充分，所述磷酸氢钙晶体中包覆的杂质越多，其晶型越差，然而，进料速度过低，会使整体反应时长大幅增加，导致产能变低。同理，所述CaCO3料浆的浓度越高，所述反应体系的局部过饱和度越高，所述磷酸氢钙晶体的晶型也越差，然而，所述CaCO3料浆的浓度过低，会使整体反应时长大幅增加，导致产能变低。所述步骤S10的一段终点pH值越高，所述含磷酸废液中的磷酸被中和的越完全，然而，当所述一段终点pH值达到3.5时，会在CaCO3颗粒表面形成不透性的磷酸氢钙结晶薄膜，导致结晶反应无法完全进行，并且由于磷酸氢钙晶体包夹了部分未反应的CaCO3颗粒，会导致其品质下降。The faster the feed rate of the CaCO 3 slurry, the higher the local supersaturation of the reaction system, that is, the less sufficient the reaction of phosphoric acid and the CaCO 3 slurry, the coating of the calcium hydrogen phosphate crystal The more impurities there are, the worse the crystal form is. However, if the feed rate is too low, the overall reaction time will be greatly increased, resulting in lower productivity. Similarly, the higher the concentration of the CaCO 3 slurry, the higher the local supersaturation of the reaction system, the worse the crystal form of the calcium hydrogen phosphate crystal, however, the concentration of the CaCO 3 slurry is too high. Low, the overall reaction time will increase significantly, resulting in lower productivity. The higher the pH value of the end point of the step S10, the more complete the phosphoric acid in the phosphoric acid-containing waste liquid is neutralized, however, when the pH of the end point reaches 3.5, the surface of the CaCO 3 particles is impervious. The crystalline film of calcium hydrogen phosphate causes the crystallization reaction to not proceed completely, and the quality of the calcium phosphate crystals is degraded due to the inclusion of some unreacted CaCO 3 particles.
优选的，以5mL/min～20mL/min的速度向含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5的操作中，CaCO3料浆的固液比为200g/L，CaCO3料浆的添加速度为10mL/min，CaCO3料浆调节pH值为3.5。Preferably, 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, and the CaCO 3 slurry was adjusted to a pH of 3.5.
优选的，S10中，搅拌速度优选为200rpm。Preferably, in S10, the stirring speed is preferably 200 rpm.
S20、控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向S10得到的第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5，得到第二混合体系，控制搅拌速度为80rpm～120rpm对第二混合体系进行养晶30min～60min。S20, controlling the stirring speed to be 100 rpm to 300 rpm, and adding a Ca(OH) 2 slurry having a solid-liquid ratio of 50 g/L to 200 g/L to the first mixed system obtained in S10 at a rate of 5 mL/min to 20 mL/min. To a pH 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.
步骤S20使用所述Ca(OH)2料浆来中和步骤S10所述第一混合体系中的磷酸二氢钙，使得所述第一混合体系中的磷酸二氢钙也转换为磷酸氢钙晶体， 从而将所述含磷酸废液中的磷酸全部转换为磷酸氢钙晶体，具体反应方程式为：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:
Ca(OH)2+Ca(H2PO4)2+2H2O→2CaHPO4·2H2O↓。Ca(OH) 2 + Ca(H 2 PO 4 ) 2 + 2H 2 O → 2CaHPO 4 · 2H 2 O↓.
步骤S20的二段终点PH值越高，所述Ca(OH)2料浆与磷酸二氢钙反应得越完全，然而，当所述Ca(OH)2料浆与磷酸二氢钙反应趋于完全时，可能会使部分磷酸氢钙转化为磷酸钙，因此，二段终点PH值不能过高。步骤S20其他反应条件的选择考量与所述步骤S10基本相似，在此不再赘述。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.
优选的，以5mL/min～20mL/min的速度向第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5的操作中，Ca(OH)2料浆的固液比为100g/L，Ca(OH)2料浆的添加速度为10mL/min，Ca(OH)2料浆调节pH值为5.75。Preferably, 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.
优选的，控制搅拌速度为80rpm～120rpm对第二混合体系养晶30min～60min的操作中，搅拌速度为100rpm。Preferably, in the operation of controlling the stirring speed from 80 rpm to 120 rpm to the second mixing system for 30 min to 60 min, the stirring speed is 100 rpm.
S30、将S20得到的完成养晶的第二混合体系进行过滤并保留滤渣，滤渣即为饲料级磷酸氢钙。S30, filtering the second mixed system obtained by S20 to complete the crystal growth and retaining the filter residue, and the filter residue is feed grade calcium hydrogen phosphate.
将完成养晶的第二混合体系进行过滤并保留滤渣的操作中，还包括如下操作：保留滤液，并将滤液用于配制CaCO3料浆和Ca(OH)2料浆进行循环反应，以回收滤液中残留的磷酸资源。In the operation of filtering and retaining the residue of the second mixed system for completing the crystal growth, 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还包括在得到饲料级磷酸氢钙后，对饲料级磷酸氢钙进行干燥、破碎、筛分、包装的操作。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.
这种含磷酸废液制备饲料级磷酸氢钙的方法通过采用CaCO3料浆对含磷酸废液进行一段处理，一段处理的终点pH值为2.5～3.5，接着加入Ca(OH)2料浆进行二段处理，二段处理的终点pH值为5.0～6.5，最后养晶，过滤后即 可得到饲料级磷酸氢钙。这种含磷酸废液制备饲料级磷酸氢钙的方法能够极大限度的对含磷酸废液中的磷酸资源进行回收利用。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. In the second stage treatment, 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.
这种含磷酸废液制备饲料级磷酸氢钙的方法工艺过程简单，指标容易控制，产品性质稳定，制得的饲料级磷酸氢钙产品为I型产品，也即均为二水磷酸氢钙(CaHPO4·2H2O)，二水磷酸氢钙由于不溶于水，因此产品的性质比较稳定(关键指标枸溶性磷的含量基本没有太大的变化，而且与理论值18.02％很接近)，而II型或III型产品由于还含有相当一部分的水溶性磷——磷酸二氢钙(Ca(H2PO4)2)，其在过滤或水洗的过程中容易造成损失，导致不同批次的产品性质差别会很大。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, and 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 枸 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.
这种含磷酸废液制备饲料级磷酸氢钙的方法制得的饲料级磷酸氢钙产品的转化率可达95％以上。众所周知，磷酸氢钙的制备领域存在饲/肥比的问题，也即饲料级磷酸氢钙和肥料级磷酸氢钙的产出比例问题，传统方法制备磷酸氢钙的饲/肥比一般是6∶4左右，由于饲料级磷酸氢钙的价值接近10倍于肥料级磷酸氢钙的价值，因此饲/肥比越高经济效益就越好，现有废磷酸蚀刻液制备饲料级磷酸氢钙的文献和专利的饲/肥比一般在8∶2左右，而这种含磷酸废液制备饲料级磷酸氢钙的工艺制得的饲料级磷酸氢钙的转化率接近100％(一次转化率在95％以上，剩余的5％不到的磷资源也经过S30中得到的滤液的循环得到再次利用)。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.
S30中对第二混合体系进行养晶30min～60min，可以得到颗粒更大、晶型更好的磷酸氢钙晶体，降低其湿基含水率，从而降低干燥能耗。In the 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.
S30中得到的滤液的循环利用的效果还可以降低废水的后续处理成本(传统方法由于不循环使用，每批产品都需处理一批废水，而这种含磷酸废液制备饲料级磷酸氢钙的方法由于循环使用，因此可以每10批产品或更多才处理 一批废水)。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).
此外，这种含磷酸废液制备饲料级磷酸氢钙的方法处理每批含磷酸废液的时间只需要3h左右，而且过滤操作仅有1步，工艺的操作难度较低，产能较高。In addition, 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.
这种含磷酸废液制备饲料级磷酸氢钙的方法制备得到的饲料级磷酸氢钙符合《GB/T 22549-2008饲料级磷酸氢钙》中I型产品的指标要求，其饲料级磷酸氢钙的产率在95％以上，而且产品的湿基含水率可控制在30％以下，大幅降低后续干燥能耗。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.
以下为具体实施例。The following are specific examples.
实施例1Example 1
提供来自深圳某光电企业某批次的废磷酸蚀刻液，其成分特性为磷酸含量59.02％、醋酸含量为7.81％、硝酸含量为1.73％。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%.
取上述废磷酸蚀刻液(200g)加入搅拌槽中，控制搅拌速度200rpm，待酸液温度升至40℃时，以10mL/min的速度向搅拌槽中加入浓度为200g/L水的CaCO3料浆，调整溶液pH值至3.5后，保温0.5h，相同条件下，继续加入浓度为100g/L水的Ca(OH)2料浆，调节溶液pH值至5.75，将搅拌速度降为100rpm，养晶0.5h，过滤，即得饲料级磷酸氢钙滤饼。The above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm. When the acid temperature was raised to 40 ° C, 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.
滤饼经干燥处理后，称重为203.4g，湿基含水率为27.82％，所得饲料级磷酸氢钙的产率为98.12％。After the filter cake was dried, the weight was 203.4 g, the moisture content of the wet base was 27.82%, and the yield of the obtained feed grade calcium hydrogen phosphate was 98.12%.
经检测，所得饲料级磷酸氢钙产品的平均粒径为152μm，其中，各成分的质量百分含量如下：总磷17.64％，枸溶性磷17.45％，水溶性磷1.11％，钙23.64％，氟0.0072％，砷＜0.000002％，铅＜0.001％，镉＜0.00006，细度100％。After testing, the average particle size of the obtained feed grade calcium hydrogen phosphate product is 152 μm, 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%.
实施例2 Example 2
提供来自深圳某光电企业某批次的废磷酸蚀刻液，其成分特性为磷酸含量59.02％、醋酸含量为7.81％、硝酸含量为1.73％。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%.
取上述废磷酸蚀刻液(200g)加入搅拌槽中，控制搅拌速度200rpm，待酸液温度升至40℃时，以10mL/min的速度向搅拌槽中加入浓度为200g/L水的CaCO3料浆，调整溶液pH值至3.5后，保温0.5h，相同条件下，继续加入浓度为200g/L水的Ca(OH)2料浆，调节溶液pH值至6.00，将搅拌速度降为100rpm，养晶0.5h，过滤，即得饲料级磷酸氢钙滤饼。The above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm. When the acid temperature was raised to 40 ° C, 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.
滤饼经干燥处理后，称重为199.3g，湿基含水率为28.13％，所得饲料级磷酸氢钙的产率为96.14％。After the filter cake was dried, 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%.
经检测，所得饲料级磷酸氢钙的平均粒径为142μm，其中，各成分的质量百分含量如下：总磷17.68％，枸溶性磷17.47％，水溶性磷1.17％，钙24.09％，氟0.0089％，砷＜0.000002％，铅＜0.001％，镉＜0.00006，细度100％。After testing, the average particle size of the obtained feed grade calcium hydrogen phosphate is 142 μm, 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%.
实施例3Example 3
提供来自深圳某光电企业某批次的废磷酸蚀刻液，其成分特性为磷酸含量59.02％、醋酸含量为7.81％、硝酸含量为1.73％。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%.
取上述废磷酸蚀刻液(200g)加入搅拌槽中，控制搅拌速度100rpm，待酸液温度升至40℃时，以10mL/min的速度向搅拌槽中加入浓度为250g/L水的CaCO3料浆，调整溶液pH值至3.5后，相同条件下，继续加入浓度为100g/L水的Ca(OH)2料浆，调节溶液pH值至6.50，将搅拌速度降为100rpm，养晶0.5h，过滤，即得饲料级磷酸氢钙滤饼。The above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 100 rpm. When the temperature of the acid solution was raised to 40 ° C, 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. After 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.
滤饼经干燥处理后，称重为200.5g，湿基含水率为30.94％，所得饲料级磷酸氢钙的产率为96.77％。After 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%.
经检测，所得饲料级磷酸氢钙的平均粒径为128μm，其中，各成分的质 量百分含量如下：总磷17.48％，枸溶性磷16.85％，水溶性磷0.87％，钙22.45％，氟0.0093％，砷＜0.000002％，铅＜0.001％，镉＜0.00006，细度100％。After testing, the average particle size of the obtained feed grade calcium hydrogen phosphate is 128 μm, 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%.
实施例4Example 4
提供来自深圳某光电企业某批次的废磷酸蚀刻液，其成分特性为磷酸含量61.05％、醋酸含量为4.03％、硝酸含量为1.88％。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%.
取上述废磷酸蚀刻液(200g)加入搅拌槽中，控制搅拌速度300rpm，待酸液温度升至60℃时，以20mL/min的速度向搅拌槽中加入浓度为200g/L水的CaCO3料浆，调整溶液pH值至3.0后，保温0.5h，相同条件下，继续加入浓度为100g/L水的Ca(OH)2料浆，调节溶液pH值至5.5，将搅拌速度降为100rpm，养晶0.5h，过滤，即得饲料级磷酸氢钙滤饼。The above waste phosphoric acid etching solution (200 g) was added to a stirring tank to control the stirring speed of 300 rpm. When the temperature of the acid solution was raised to 60 ° C, 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.
滤饼经干燥处理后，称重为209.2g，湿基含水率为29.47％，所得饲料级磷酸氢钙的产率为97.62％。After the filter cake was dried, the weight was 209.2 g, the moisture content of the wet base was 29.47%, and the yield of the obtained feed grade calcium hydrogen phosphate was 97.62%.
经检测，所得饲料级磷酸氢钙的平均粒径为138μm，其中，各成分的质量百分含量如下：总磷17.76％，枸溶性磷17.74％，水溶性磷1.21％，钙23.25％，氟0.0077％，砷＜0.000002％，铅＜0.001％，镉＜0.00006，细度100％。After testing, the average particle size of the obtained feed grade calcium hydrogen phosphate is 138 μm, 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%.
对比例1Comparative example 1
提供与实施例1中相同的废磷酸蚀刻液。The same waste phosphoric acid etching solution as in Example 1 was provided.
取上述废磷酸蚀刻液(200g)加入搅拌槽中，控制搅拌速度200rpm，待酸液温度升至40℃时，以10mL/min的速度向搅拌槽中加入浓度为200g/L水的CaCO3料浆，调整溶液pH值至3.5后，保温0.5h，相同条件下，继续加入浓度为100g/L水的Ca(OH)2料浆，调节溶液pH值至5.75，过滤，即得饲料级磷酸氢钙滤饼。The above waste phosphoric acid etching solution (200 g) was added to the stirring tank to control the stirring speed of 200 rpm. When the acid temperature was raised to 40 ° C, 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.
滤饼经干燥处理后，称重为203.3g，湿基含水率为31.27％，所得饲料级 磷酸氢钙的产率为98.07％。After the filter cake was dried, 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%.
经检测，所得饲料级磷酸氢钙的平均粒径为95μm，其中，各成分的质量百分含量如下：总磷17.63％，枸溶性磷17.42％，水溶性磷1.10％，钙23.60％，氟0.0071％，砷＜0.000002％，铅＜0.001％，镉＜0.00006，细度100％。After testing, the average particle size of the obtained feed grade calcium hydrogen phosphate is 95 μm, 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%.
对比实施例1～4和对比例1，对比例1中没有养晶的操作，因此导致对比例1中制得的饲料级磷酸氢钙滤饼的平均粒径相对偏低，晶型较差，含水率较高。In 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.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本申请的保护范围之中。 It is apparent that the above-described embodiments are merely illustrative of the examples, and are not intended to limit the embodiments. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. There is no need and no way to exhaust all of the implementations. Obvious changes or variations resulting therefrom are still within the scope of the present application.

Claims (10)

  1. 一种含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，包括如下步骤：A method for preparing feed grade calcium hydrogen phosphate containing phosphoric acid waste liquid, comprising the steps of:
    将含磷酸废液在搅拌状态下升温至40℃～60℃，控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向所述含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5，得到第一混合体系，对所述混合体系保温停留5min～30min；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;
    控制搅拌速度为100rpm～300rpm，并以5mL/min～20mL/min的速度向所述第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5，得到第二混合体系，控制搅拌速度为80rpm～120rpm对所述第二混合体系进行养晶30min～60min；以及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;
    将完成养晶的所述第二混合体系进行过滤并保留滤渣，所述滤渣即为饲料级磷酸氢钙。The second mixing system that completes the crystal growth is filtered and the filter residue is retained, which is feed grade calcium hydrogen phosphate.
  2. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述含磷酸废液中按照质量百分数含有50％～80％的磷酸。The method for preparing feed grade calcium hydrogen phosphate according to claim 1, wherein the phosphoric acid-containing waste liquid contains 50% to 80% of phosphoric acid by mass%.
  3. 根据权利要求2所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述含磷酸废液为废磷酸蚀刻液。The method for preparing feed grade calcium hydrogen phosphate according to claim 2, wherein the phosphoric acid-containing waste liquid is a waste phosphoric acid etching solution.
  4. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述以5mL/min～20mL/min的速度向所述含磷酸废液中加入固液比为100g/L～250g/L的CaCO3料浆至pH值为2.5～3.5的操作中，所述CaCO3料浆的固液比为200g/L。The method for preparing feed grade calcium hydrogen phosphate according to claim 1, wherein the solid-liquid ratio is 100 g to the phosphoric acid-containing waste liquid at a rate of 5 mL/min to 20 mL/min. The CaCO 3 slurry from /L to 250 g/L was brought to a pH of 2.5 to 3.5, and the solid-liquid ratio of the CaCO 3 slurry was 200 g/L.
  5. 根据权利要求4所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特 征在于，所述CaCO3料浆的添加速度为10mL/min。A method of preparing feed grade calcium hydrogen phosphate from a phosphoric acid-containing waste liquid according to claim 4, wherein the CaCO 3 slurry is added at a rate of 10 mL/min.
  6. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述以5mL/min～20mL/min的速度向所述第一混合体系中加入固液比为50g/L～200g/L的Ca(OH)2料浆至pH值为5.0～6.5的操作中，所述Ca(OH)2料浆的固液比为100g/L。The method for preparing feed grade calcium hydrogen phosphate according to claim 1, wherein the solid-liquid ratio is 50 g to the first mixed system at a rate of 5 mL/min to 20 mL/min. operation / L ~ 200g / L of Ca (OH) 2 slurry to a pH of 5.0 to 6.5, the Ca (OH) 2 slurry solid-liquid ratio is 100g / L.
  7. 根据权利要求6所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述Ca(OH)2料浆的添加速度为10mL/min。The method for preparing feed grade calcium hydrogen phosphate according to claim 6, wherein the Ca(OH) 2 slurry is added at a rate of 10 mL/min.
  8. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述控制搅拌速度为80rpm～120rpm对所述第二混合体系养晶30min～60min的操作中，所述搅拌速度为100rpm。The method for preparing feed grade calcium hydrogen phosphate according to claim 1, wherein the controlled stirring speed is 80 rpm to 120 rpm, and the second mixing system is maintained for 30 minutes to 60 minutes. The stirring speed was 100 rpm.
  9. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，所述将完成养晶的所述第二混合体系进行过滤并保留滤渣的操作中，还包括如下操作：保留滤液，并将所述滤液用于配制CaCO3料浆和Ca(OH)2料浆进行循环反应，以回收所述滤液中残留的磷酸资源。The method for preparing feed grade calcium hydrogen phosphate by using the phosphoric acid-containing waste liquid according to claim 1, wherein the operation of filtering and retaining the residue of the second mixed system for completing the crystal growth further comprises the following operations The filtrate is retained, and the filtrate is used to prepare a CaCO 3 slurry and a Ca(OH) 2 slurry for a cyclic reaction to recover the residual phosphoric acid resources in the filtrate.
  10. 根据权利要求1所述的含磷酸废液制备饲料级磷酸氢钙的方法，其特征在于，还包括在得到所述饲料级磷酸氢钙后，对所述饲料级磷酸氢钙进行干燥、破碎、筛分、包装的操作。 The method for preparing feed grade calcium hydrogen phosphate according to claim 1, further comprising drying and crushing the feed grade calcium hydrogen phosphate after obtaining the feed grade calcium hydrogen phosphate. Screening and packaging operations.
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