CN116812879A - Efficient calcium removal method for waste sulfuric acid system - Google Patents
Efficient calcium removal method for waste sulfuric acid system Download PDFInfo
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- CN116812879A CN116812879A CN202310912554.8A CN202310912554A CN116812879A CN 116812879 A CN116812879 A CN 116812879A CN 202310912554 A CN202310912554 A CN 202310912554A CN 116812879 A CN116812879 A CN 116812879A
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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Abstract
本发明公开了一种废硫酸体系的高效除钙方法，首先向废硫酸中投加硫酸钙晶种，进行预处理得到废酸体系的硫酸钙饱和溶液，再经过一定时间的停留熟化，使得晶体有足够的成长时间，同时析出得到大颗粒状的晶体，最后再经过微米级孔径滤芯式过滤器过滤，过滤得到除钙后清液。本发明易操作、成本低、不加化学药剂；通过投加少量晶种作为晶核，高效促进硫酸钙以大颗粒型形式单独析出，并拦截去除，避免后处理带来的换热表面沉积结垢现象的发生；硫酸钙的预先去除，可以有效提高副产品品级。微米级孔径滤芯式过滤器微米级孔径滤芯式过滤器。
The invention discloses a high-efficiency calcium removal method for a waste sulfuric acid system. First, calcium sulfate seed crystals are added to the waste sulfuric acid, and pretreatment is performed to obtain a saturated calcium sulfate solution of the waste acid system. Then, after a certain period of residence and maturation, the crystals are With enough growth time, large granular crystals are precipitated at the same time, and finally filtered through a micron-sized filter cartridge filter to obtain the clear liquid after calcium removal. The invention is easy to operate, has low cost and does not add chemicals; by adding a small amount of crystal seeds as crystal nuclei, it can effectively promote the separate precipitation of calcium sulfate in the form of large particles, intercept and remove them, and avoid deposits on the heat exchange surface caused by post-processing. The occurrence of scale phenomenon; the pre-removal of calcium sulfate can effectively improve the grade of by-products. Micron pore size cartridge filter Micron pore size cartridge filter.
Description
技术领域Technical field
本发明涉及硫酸工业领域，具体涉及一种废硫酸体系中的高效除钙方法。The invention relates to the field of sulfuric acid industry, and specifically relates to an efficient calcium removal method in a waste sulfuric acid system.
背景技术Background technique
硫酸作为化学领域的主要耗材之一，如钛白粉生产、湿法冶炼、粘胶行业等工业生产过程中均会产生大量的废硫酸，由于原矿或精矿、木材等原材料的原有组分均含有大量钙元素，经与硫酸发生化学反应不可避免会溶解钙离子而带入硫酸体系，再与硫酸根共存，当达到一定的饱和浓度之后，会生成沉积型，且难于复溶的硫酸钙。Sulfuric acid is one of the main consumables in the chemical field. Industrial production processes such as titanium dioxide production, hydrosmelting, and viscose industries will produce a large amount of waste sulfuric acid. Since the original components of raw ore or concentrate, wood and other raw materials are evenly distributed, Containing a large amount of calcium, the chemical reaction with sulfuric acid will inevitably dissolve calcium ions and bring them into the sulfuric acid system, and then coexist with sulfate radicals. When a certain saturation concentration is reached, sedimentary calcium sulfate will be generated that is difficult to redissolve.
目前，对于废硫酸的回收处理方法有直接蒸发浓缩法，冷冻结晶得副产品硫酸亚铁或硫酸钠等+再蒸发浓缩回收的方法等等，在这些方法当中，因为需要采用换热设备进行加热或降温处理，所以容易伴随着硫酸钙沉积于换热表面而形成厚实的垢层，从而造成换热效率的急速下降，甚至无法继续运行，往往需要通过人工拆解后进行离线型人工机械清洗，带来设备使用寿命短、操作难度大、劳动强度大、人工成本高、生产效率低下等诸多问题。At present, the recovery and treatment methods for waste sulfuric acid include direct evaporation and concentration, freezing and crystallization to obtain by-products such as ferrous sulfate or sodium sulfate + re-evaporation, concentration and recovery, etc. Among these methods, heat exchange equipment is required for heating or Cooling treatment, so it is easy to form a thick layer of scale as calcium sulfate is deposited on the heat exchange surface, resulting in a rapid decrease in heat exchange efficiency and even the inability to continue operation. It is often necessary to perform manual disassembly and then perform offline manual mechanical cleaning. The equipment has many problems such as short service life, difficult operation, high labor intensity, high labor costs, and low production efficiency.
针对废酸体系中硫酸钙结垢问题的普遍性，对于如何实现硫酸钙的有效去除，具有重要意义。Aiming at the common problem of calcium sulfate scaling in waste acid systems, it is of great significance for how to achieve effective removal of calcium sulfate.
发明内容Contents of the invention
本发明的目的在于提供一种实现硫酸钙有效去除的废硫酸体系的高效除钙方法。The object of the present invention is to provide an efficient calcium removal method for a waste sulfuric acid system that achieves effective calcium sulfate removal.
本发明的技术解决方案是：The technical solution of the present invention is:
一种废硫酸体系的高效除钙方法，其特征是：首先向废硫酸中投加硫酸钙晶种，进行预处理得到废酸体系的硫酸钙饱和溶液，再经过一定时间的停留熟化，使得晶体有足够的成长时间，同时析出得到大颗粒状的晶体，最后再经过微米级孔径滤芯式过滤器将硫酸钙颗粒进行死端拦截，过滤得到除钙后清液。An efficient calcium removal method for waste sulfuric acid system, which is characterized by: first adding calcium sulfate seed crystals to waste sulfuric acid, performing pretreatment to obtain a saturated calcium sulfate solution of the waste acid system, and then after a certain period of residence and maturation, the crystals With enough growth time, large granular crystals are precipitated at the same time. Finally, the calcium sulfate particles are intercepted at the dead end through a micron-sized filter core filter, and the calcium sulfate particles are filtered to obtain the clear liquid after calcium removal.
所述硫酸钙晶种的投加量为20～100mg/L。The dosage of the calcium sulfate seed crystal is 20-100 mg/L.
所述预处理，包括但不限于采用非间壁式换热方式的蒸发预浓缩后再冷却降温或直接冷却降温的方法。The pretreatment includes but is not limited to the method of evaporation, preconcentration and then cooling or direct cooling using non-partitioned wall heat exchange.
蒸发预浓缩终点硫酸浓度控制在25％～30％，冷却降温的温度终点控制在10～40℃.The sulfuric acid concentration at the end of evaporation pre-concentration is controlled at 25% to 30%, and the temperature end of cooling is controlled at 10 to 40°C.
所述蒸发预浓缩包括但不限于负压闪蒸、尾气浓缩或蒸汽浓缩。The evaporative pre-concentration includes but is not limited to negative pressure flash evaporation, tail gas concentration or steam concentration.
所述冷却降温的方法包括但不限于大气冷凝或夹套搅拌冷却。The cooling methods include but are not limited to atmospheric condensation or jacket stirring cooling.
所述停留熟化时间为1～3h。The residence and aging time is 1 to 3 hours.
所述微米级孔径滤芯式过滤器，其单套系统配备数量为不少于2台，其中包含备用，过滤孔径为0.1～5微米，其滤芯包括但不限于PP、PE、PES材质的滤袋或熔喷滤芯。The micron-level pore size filter cartridge type filter is equipped with no less than 2 units in a single system, including spares. The filter pore size is 0.1 to 5 microns. The filter cartridges include but are not limited to filter bags made of PP, PE, and PES. Or melt blown filter element.
所述过滤器可根据压差变化大于0.07Mpa或定期进行人工更换滤芯，或将滤芯反冲洗进行再利用。The filter can be manually replaced according to the pressure difference greater than 0.07Mpa or the filter element can be replaced regularly, or the filter element can be backwashed for reuse.
本发明的优点在于：1、提供了一种易操作、成本低、不加化学药剂的高效除钙方法。；2、投加少量晶种作为晶核，高效促进硫酸钙以大颗粒型形式单独析出，并拦截去除，避免后处理带来的换热表面沉积结垢现象的发生。3、硫酸钙的预先去除，可以有效提高副产品品级，带来更显著的经济效益。The advantages of the present invention are: 1. It provides an efficient calcium removal method that is easy to operate, low in cost and does not add chemical agents. ; 2. Add a small amount of crystal seeds as crystal nuclei to effectively promote the separate precipitation of calcium sulfate in the form of large particles, and intercept and remove them to avoid the occurrence of deposition and scaling on the heat exchange surface caused by post-processing. 3. Preliminary removal of calcium sulfate can effectively improve the grade of by-products and bring more significant economic benefits.
下面结合附图和实施例对本发明作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and examples.
附图说明Description of the drawings
图1是本发明的工艺流程示意图。Figure 1 is a schematic diagram of the process flow of the present invention.
具体实施方式Detailed ways
实施例1Example 1
某生产企业废酸H2SO4 23％，FeSO4 165g/L，CaSO4 380mg/L，取样品1000mL置于烧杯中，投加50mg CaSO4晶种，采用绝热闪蒸装置蒸发179mg水，得到预浓缩酸，倒入烧杯中，冷水浴搅拌，降温至32℃，静置1h，选用1微米孔径滤纸进行过滤得到清液，取样测得H2SO428％，FeSO4 201g/L，CaSO4 163mg/L，计算得出硫酸钙的去除率达到65％。A production company's waste acid H 2 SO 4 23%, FeSO 4 165g/L, CaSO 4 380mg/L, take 1000mL of the sample and place it in a beaker, add 50mg CaSO 4 seed crystal, use an adiabatic flash evaporation device to evaporate 179mg water, and get Preconcentrate the acid, pour it into a beaker, stir in a cold water bath, cool to 32°C, let it stand for 1 hour, filter with 1 micron pore size filter paper to obtain a clear liquid, take a sample and measure H 2 SO 4 28%, FeSO 4 201g/L, CaSO 4 163mg/L, the calculated removal rate of calcium sulfate reaches 65%.
实施例2Example 2
某生产企业废酸H2SO4 20％，CaSO4 580mg/L，取样品1000mL置于烧杯中，投加80mgCaSO4晶种，直接冰浴搅拌，降温至10℃，静置1.5h，选用2微米孔径滤纸进行过滤得到清液，取样测得CaSO463mg/L，计算得出硫酸钙的去除率达到91％。A certain manufacturer's waste acid H 2 SO 4 20%, CaSO 4 580mg/L, take 1000mL of sample and place it in a beaker, add 80mg CaSO 4 seed crystal, stir directly in ice bath, cool to 10℃, let stand for 1.5h, choose 2 The clear liquid was obtained by filtration through micron pore filter paper, and CaSO 4 was measured at 63 mg/L by sampling. It was calculated that the removal rate of calcium sulfate reached 91%.
实施例3Example 3
某生产企业废酸H2SO4 13％，CaSO4 378mg/L，取样品1000mL置于烧杯中，投加35mgCaSO4晶种，采用油浴蒸发479mg水，得到预浓缩酸，倒入烧杯中，冷水浴搅拌，降温至20℃，静置1h，选用0.5微米孔径滤纸进行过滤得到清液，取样测得H2SO4 23％，CaSO4 149mg/L，计算得出硫酸钙的去除率达到79.5％。A manufacturer's waste acid H 2 SO 4 13%, CaSO 4 378mg/L, take 1000mL of the sample and place it in a beaker, add 35mg CaSO 4 seed crystals, use an oil bath to evaporate 479mg of water, obtain pre-concentrated acid, and pour it into the beaker. Stir in a cold water bath, cool down to 20°C, and let stand for 1 hour. Use 0.5 micron pore size filter paper to filter to obtain the clear liquid. Take a sample and measure H 2 SO 4 23%, CaSO 4 149 mg/L. Calculate the calcium sulfate removal rate to reach 79.5 %.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3121620A (en) * | 1959-12-03 | 1964-02-18 | Bayer Ag | Process for the recovery of sulphuric acid in concentrated form from dilute waste sulphuric acid liquors |
| CN112209353A (en) * | 2020-10-16 | 2021-01-12 | 山东润诚特种纸业有限公司 | Method for treating and recycling waste sulfuric acid from papermaking |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | A kind of method that recovers calcium sulfate from acid leaching solution to recycle hydrochloric acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3121620A (en) * | 1959-12-03 | 1964-02-18 | Bayer Ag | Process for the recovery of sulphuric acid in concentrated form from dilute waste sulphuric acid liquors |
| CN112209353A (en) * | 2020-10-16 | 2021-01-12 | 山东润诚特种纸业有限公司 | Method for treating and recycling waste sulfuric acid from papermaking |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | A kind of method that recovers calcium sulfate from acid leaching solution to recycle hydrochloric acid |
Non-Patent Citations (1)
| Title |
|---|
| 曾汝晴;王文磊;曾德文;: "高效脱除结晶硫酸铜中杂质钙的研究", 广东化工, no. 21, 15 November 2013 (2013-11-15) * |
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