CN206872425U - A kind of highly concentrated pickle liquor regenerative system - Google Patents

A kind of highly concentrated pickle liquor regenerative system Download PDF

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CN206872425U
CN206872425U CN201720434156.XU CN201720434156U CN206872425U CN 206872425 U CN206872425 U CN 206872425U CN 201720434156 U CN201720434156 U CN 201720434156U CN 206872425 U CN206872425 U CN 206872425U
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hydrochloric acid
concentration
condenser
tower
liquid
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孟剑
杨刚
王云山
洪成峰
孟祥全
刘坤
寇洋
李超
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Anshan Chuangxin Environmental Protection Technology Co ltd
Institute of Process Engineering of CAS
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Anshan Chuangxin Waste Acid Desilication Regeneration Engineering Co ltd
Institute of Process Engineering of CAS
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Abstract

It the utility model is related to a kind of highly concentrated pickle liquor regenerative system, including hydrolysis calcining furnace, two-stage dust removal device, preconcentrator, B grade condensing unit, air cooling tower, hydrochloric acid absorption tower and scrubbing tower;The utility model is directly condensed the flue gas after preconcentrator, high concentration HCl in flue gas is got off with water condensation, avoid the constant boiling point of hydrochloric acid solution, realize regeneration target of the concentration of hydrochloric acid more than more than 22%, the HCl of higher concentration is absorbed in hydrochloric acid absorption tower with water in flue gas after condensation, the hydrochloric acid of concentration needed for acquisition.

Description

一种高浓酸洗废液再生系统A high-concentration pickling waste liquid regeneration system

技术领域technical field

本实用新型涉及酸洗废液处理技术领域,尤其涉及一种高浓酸洗废液再生系统。The utility model relates to the technical field of pickling waste liquid treatment, in particular to a high-concentration pickling waste liquid regeneration system.

背景技术Background technique

在钢材深加工过程中,需对其表面进行酸洗除锈处理。常用的酸洗液为盐酸和硫酸,目前大多数企业均采用盐酸作为酸洗液。钢材经盐酸酸洗后,会产生大量的酸洗废液。盐酸酸洗废液的组成主要是氯化氢、氯化亚铁、水及少量杂质,各成分含量随酸洗工艺、操作温度、钢材品种和规格不同而异,一般含氯化亚铁10~20%,氯化氢3~10%。其中,钢铁热轧所产生的酸洗废液一般含有1~5g/L的H+,60~250g/L的Fe2+,由于酸洗废液具有严重的腐蚀性,已被列入《国家危险废物名录》,该类废液直接排放不仅严重污染环境,而且造成极大的浪费。During the deep processing of steel, the surface needs to be pickled and derusted. Commonly used pickling solutions are hydrochloric acid and sulfuric acid, and most enterprises currently use hydrochloric acid as the pickling solution. After the steel is pickled with hydrochloric acid, a large amount of pickling waste will be produced. The composition of hydrochloric acid pickling waste liquid is mainly hydrogen chloride, ferrous chloride, water and a small amount of impurities. The content of each component varies with the pickling process, operating temperature, steel type and specification, and generally contains 10-20% of ferrous chloride. , 3-10% hydrogen chloride. Among them, the pickling waste liquid produced by hot rolling of iron and steel generally contains 1-5g/L H + , 60-250g/L Fe 2+ Hazardous Waste List", direct discharge of such waste liquid not only seriously pollutes the environment, but also causes great waste.

按国家环保要求酸洗废液是不能直接排放的,传统的处理方法有中和法、蒸发结晶法或焙烧回收盐酸法。中和法是目前钢铁企业普遍采用的方法,但其存在的缺点也较突出,一方面要消耗大量的碱性药剂(如烧碱、石灰等),处理成本十分昂贵;另一方面又会生成大量难以处置的含铁污泥,对环境造成变相二次污染;蒸发结晶法是通过对废酸液加热蒸发、冷凝器冷凝后形成稀盐酸,返回车间重新使用;通过蒸发浓缩、冷却浓缩液析出FeCl2结晶,得到固体产品。该技术的优点是能处理废酸液,回收98%以上的盐酸,盐酸浓度比废液浓度下降1%~4%;使Fe2+全部以FeCl2固体形式排出,且设备简单,投资小,处理成本低;但是,此技术存在着极大的环境风险和市场风险,为了节约成本,用于酸洗的盐酸多采用其他化工行业的副产盐酸,其中含有大量的有机物甚至是有毒的物质,虽然对钢铁行业酸洗没有影响,但蒸发浓缩后获得的氯化亚铁等产品均不可避免的含有一些有机物甚至是有毒物质,而FeCl2一般是作为净水剂使用,一旦上述有毒的氯化亚铁等产品用于水处理中,必然对所处理的水造成二次污染,后果不堪设想。加之净水剂市场需求量有限,也严重限制了该技术的应用。焙烧回收盐酸法将废液的加热、脱水、亚铁盐的氧化和水解、氯化氢气体的收集及吸收成盐酸有机地结合在一个系统内一并完成,具有处理能力大、设施紧凑、资源回收率高(可达98%~99%),再生酸浓度高、酸中含Fe2+少、氧化铁品位高(可达98%以上)及应用广等特点,因此得到了快速推广;目前,国内有两百余套焙烧法回收盐酸法装置在连续运行。现有的焙烧回收盐酸法最为广泛的技术为奥地利的Ruthner工艺技术,国内大多采用此技术。但是,随着钢铁行业对酸洗效率的要求愈来愈高,使用高浓度的盐酸作为酸洗介质以大幅度提高酸洗效率成为趋势。但是,盐酸在常压情况下,22%是其恒沸浓度,Ruthner工艺技术由于采用水吸收HCl的工艺,其再生盐酸的浓度无法超过22%wt,只能达到18%-~20%wt,无法满足企业对22%以上浓度再生盐酸的需求。According to national environmental protection requirements, pickling waste liquid cannot be discharged directly. The traditional treatment methods include neutralization method, evaporation crystallization method or roasting recovery hydrochloric acid method. The neutralization method is a method commonly used by iron and steel enterprises at present, but its shortcomings are also prominent. On the one hand, it consumes a large amount of alkaline chemicals (such as caustic soda, lime, etc.), and the treatment cost is very expensive; on the other hand, it will generate a large amount of The iron-containing sludge that is difficult to dispose of causes secondary pollution in disguised form to the environment; the evaporation crystallization method is to form dilute hydrochloric acid after heating and evaporating the waste acid solution and condensing it in the condenser, and return it to the workshop for reuse; through evaporation concentration, cooling the concentrated solution to separate out FeCl 2 crystallized to give a solid product. The advantage of this technology is that it can process waste acid liquid, recover more than 98% of hydrochloric acid, and the concentration of hydrochloric acid is 1% to 4% lower than that of waste liquid; all Fe 2+ is discharged in the form of FeCl 2 solid, and the equipment is simple and the investment is small. The processing cost is low; however, this technology has great environmental and market risks. In order to save costs, the hydrochloric acid used for pickling is mostly by-product hydrochloric acid from other chemical industries, which contains a large amount of organic matter and even toxic substances. Although it has no effect on pickling in the iron and steel industry, ferrous chloride and other products obtained after evaporation and concentration inevitably contain some organic matter or even toxic substances, and FeCl 2 is generally used as a water purifier. Once the above-mentioned toxic chlorination Products such as ferrous iron are used in water treatment, which will inevitably cause secondary pollution to the treated water, and the consequences will be disastrous. In addition, the limited market demand for water purifiers also seriously limits the application of this technology. The method of roasting and recovering hydrochloric acid organically combines the heating of waste liquid, dehydration, oxidation and hydrolysis of ferrous salt, collection and absorption of hydrogen chloride gas into hydrochloric acid in one system, and has the advantages of large processing capacity, compact facilities and high resource recovery rate. High (up to 98% ~ 99%), high concentration of regenerated acid, less Fe 2+ in the acid, high grade of iron oxide (up to 98%) and wide application, so it has been rapidly promoted; at present, domestic There are more than 200 sets of roasting method to recover hydrochloric acid method in continuous operation. The most widely used technology for recovering hydrochloric acid by roasting is Austria's Ruthner process technology, which is mostly used in China. However, as the iron and steel industry has higher and higher requirements for pickling efficiency, it has become a trend to use high-concentration hydrochloric acid as the pickling medium to greatly improve the pickling efficiency. But hydrochloric acid is under the condition of normal pressure, and 22% is its azeotropic concentration, because Ruthner process technology adopts the technology that water absorbs HCl, the concentration of its regenerated hydrochloric acid can't exceed 22%wt, can only reach 18%-~20%wt, Unable to meet the needs of enterprises for regenerated hydrochloric acid with a concentration of more than 22%.

发明内容Contents of the invention

本实用新型提供了一种高浓酸洗废液再生系统,预浓缩器后的烟气直接采用二级冷凝装置进行冷凝,将烟气中的高浓度HCl与水冷凝下来,避开盐酸溶液的恒沸点,实现再生盐酸浓度超过22%以上的目标,冷凝后烟气中更高浓度的HCl在盐酸吸收塔中用水吸收,获得所需浓度的盐酸。The utility model provides a high-concentration pickling waste liquid regeneration system. The flue gas after the pre-concentrator is directly condensed by a secondary condensing device, and the high-concentration HCl and water in the flue gas are condensed to avoid the hydrochloric acid solution. Constant boiling point, to achieve the goal of regenerated hydrochloric acid concentration exceeding 22%, after condensation, the higher concentration of HCl in the flue gas is absorbed by water in the hydrochloric acid absorption tower to obtain the required concentration of hydrochloric acid.

为了达到上述目的,本实用新型采用以下技术方案实现:In order to achieve the above object, the utility model adopts the following technical solutions to realize:

一种高浓酸洗废液再生系统,包括水解煅烧炉、二级除尘装置、预浓缩器、二级冷凝装置、空冷塔、盐酸吸收塔和洗涤塔;所述水解煅烧炉的上部烟气出口依次通过由旋风分离器和多管除尘器组成的二级除尘装置连接预浓缩器顶部烟气入口;水解煅烧炉、旋风分离器和多管除尘器的粉末出口分别连接气力输送管道,气力输送管道上设有气力输送风机;预浓缩器的底部液体出口一路通过循环浓缩泵连接预浓缩器的顶部液体入口,另一路通过给料泵连接水解煅烧炉的顶部液体喷枪;预浓缩器上的浓缩酸液入口连接高浓度酸洗废液输送管道;预浓缩器的气体出口依次通过由第一冷凝器和第二冷凝器组成的二级冷凝装置连接盐酸吸收塔底部气体入口;第一冷凝器和第二冷凝器的液体出口连接盐酸混合槽的液体入口;第一冷凝器和第二冷凝器的冷却水入口通过空冷循环泵连接空冷塔的出口,空冷循环泵入口另外连接脱盐水输送管道;第一冷凝器和第二冷凝器的冷却水出口连接空冷塔的入口;盐酸吸收塔底部液体出口连接盐酸混合槽的液体入口,盐酸混合槽的液体出口通过盐酸泵连接盐酸产品外送管道;盐酸吸收塔顶部气体出口通过耐酸风机连接洗涤塔的底部气体入口;洗涤塔的底部液体出口通过洗涤泵连接盐酸吸收塔顶部液体入口和洗涤塔顶部液体入口;洗涤塔顶部液体入口另外连接脱盐水输送管道。A high-concentration pickling waste liquid regeneration system, including a hydrolysis calciner, a secondary dust removal device, a pre-concentrator, a secondary condensation device, an air cooling tower, a hydrochloric acid absorption tower, and a washing tower; the upper flue gas outlet of the hydrolysis calciner The flue gas inlet on the top of the pre-concentrator is connected to the flue gas inlet at the top of the pre-concentrator through the secondary dust removal device composed of a cyclone separator and a multi-tube dust collector; the powder outlets of the hydrolysis calciner, the cyclone separator and the multi-tube dust collector are respectively connected to the pneumatic conveying pipeline and the pneumatic conveying pipeline There is a pneumatic conveying fan on the top; one way of the bottom liquid outlet of the pre-concentrator is connected to the top liquid inlet of the pre-concentrator through a circulating concentration pump, and the other is connected to the top liquid spray gun of the hydrolysis calciner through a feed pump; the concentrated acid on the pre-concentrator The liquid inlet is connected to the high-concentration pickling waste liquid delivery pipeline; the gas outlet of the pre-concentrator is connected to the gas inlet at the bottom of the hydrochloric acid absorption tower through the secondary condensation device composed of the first condenser and the second condenser; the first condenser and the second The liquid outlet of the second condenser is connected to the liquid inlet of the hydrochloric acid mixing tank; the cooling water inlets of the first condenser and the second condenser are connected to the outlet of the air cooling tower through the air-cooling circulation pump, and the inlet of the air-cooling circulation pump is additionally connected to the desalinated water delivery pipeline; the first The cooling water outlet of the condenser and the second condenser is connected to the inlet of the air cooling tower; the liquid outlet at the bottom of the hydrochloric acid absorption tower is connected to the liquid inlet of the hydrochloric acid mixing tank, and the liquid outlet of the hydrochloric acid mixing tank is connected to the hydrochloric acid product delivery pipeline through the hydrochloric acid pump; the hydrochloric acid absorption tower The top gas outlet is connected to the bottom gas inlet of the scrubber through an acid-resistant fan; the bottom liquid outlet of the scrubber is connected to the top liquid inlet of the hydrochloric acid absorption tower and the top liquid inlet of the scrubber through a scrubber pump; the top liquid inlet of the scrubber is also connected to the desalted water delivery pipeline.

与现有技术相比,本实用新型的有益效果是:Compared with the prior art, the beneficial effects of the utility model are:

1)能够获得浓度超过22%的高浓度再生盐酸产品,满足现有企业采用高效酸洗工艺对高浓度盐酸的需求;1) High-concentration regenerated hydrochloric acid products with a concentration exceeding 22% can be obtained to meet the needs of existing enterprises for high-concentration hydrochloric acid using efficient pickling processes;

2)基于Ruthner技术进行技术改进,广泛适用于新建工程项目及现有工程改造,改造方案简单,易于实施。2) The technical improvement based on Ruthner technology is widely applicable to new construction projects and existing engineering transformation, and the transformation scheme is simple and easy to implement.

附图说明Description of drawings

图1是本实用新型所述一种高浓酸洗废液再生系统的结构示意图。Fig. 1 is a structural schematic diagram of a high-concentration pickling waste liquid regeneration system described in the present invention.

图2是本实用新型所述一种高浓酸洗废液再生系统的原理框图。Fig. 2 is a functional block diagram of a high-concentration pickling waste liquid regeneration system described in the present invention.

图中:1.水解煅烧炉 2.旋风分离器 3.多管除尘器 4.气力输送风机 5.预浓缩器6.循环浓缩泵 7.给料泵 8.第一冷凝器 9.第二冷凝器 10.空冷塔 11.空冷循环泵 12.盐酸吸收塔 13.盐酸混合槽 14.盐酸泵 15.耐酸风机 16.洗涤塔 17.洗涤泵In the figure: 1. Hydrolysis calciner 2. Cyclone separator 3. Multi-pipe dust collector 4. Pneumatic conveying fan 5. Pre-concentrator 6. Circulating concentration pump 7. Feed pump 8. First condenser 9. Second condensation 10. Air cooling tower 11. Air cooling circulation pump 12. Hydrochloric acid absorption tower 13. Hydrochloric acid mixing tank 14. Hydrochloric acid pump 15. Acid-resistant fan 16. Washing tower 17. Washing pump

具体实施方式detailed description

下面结合附图对本实用新型的具体实施方式作进一步说明:The specific embodiment of the utility model will be further described below in conjunction with accompanying drawing:

如图1所示,本实用新型所述一种高浓酸洗废液再生系统,包括水解煅烧炉1、二级除尘装置、预浓缩器5、二级冷凝装置、空冷塔10、盐酸吸收塔12和洗涤塔16;所述水解煅烧炉1的上部烟气出口依次通过由旋风分离器2和多管除尘器3组成的二级除尘装置连接预浓缩器5顶部烟气入口;水解煅烧炉1、旋风分离器2和多管除尘器3的粉末出口分别连接气力输送管道,气力输送管道上设有气力输送风机4;预浓缩器5的底部液体出口一路通过循环浓缩泵6连接预浓缩器5的顶部液体入口,另一路通过给料泵7连接水解煅烧炉1的顶部液体喷枪;预浓缩器5上的浓缩酸液入口连接高浓度酸洗废液输送管道;预浓缩器5的气体出口依次通过由第一冷凝器8和第二冷凝器9组成的二级冷凝装置连接盐酸吸收塔12底部气体入口;第一冷凝器8和第二冷凝器9的液体出口连接盐酸混合槽13的液体入口;第一冷凝器8和第二冷凝器9的冷却水入口通过空冷循环泵11连接空冷塔10的出口,空冷循环泵11入口另外连接脱盐水输送管道;第一冷凝器8和第二冷凝器9的冷却水出口连接空冷塔10的入口;盐酸吸收塔12底部液体出口连接盐酸混合槽13的液体入口,盐酸混合槽13的液体出口通过盐酸泵14连接盐酸产品外送管道;盐酸吸收塔12顶部气体出口通过耐酸风机15连接洗涤塔16的底部气体入口;洗涤塔16的底部液体出口通过洗涤泵27连接盐酸吸收塔12顶部液体入口和洗涤塔16顶部液体入口;洗涤塔16顶部液体入口另外连接脱盐水输送管道。As shown in Figure 1, a high-concentration pickling waste liquid regeneration system described in the utility model includes a hydrolysis calciner 1, a secondary dedusting device, a pre-concentrator 5, a secondary condensing device, an air cooling tower 10, and a hydrochloric acid absorption tower 12 and a washing tower 16; the upper flue gas outlet of the hydrolysis calciner 1 is connected to the top flue gas inlet of the pre-concentrator 5 through a secondary dust removal device composed of a cyclone separator 2 and a multi-tube dust collector 3; the hydrolysis calciner 1 , the powder outlets of the cyclone separator 2 and the multi-pipe dust collector 3 are respectively connected to the pneumatic conveying pipeline, and the pneumatic conveying pipeline is provided with a pneumatic conveying fan 4; the liquid outlet at the bottom of the pre-concentrator 5 is connected to the pre-concentrator 5 through the circulating concentration pump 6 all the way The top liquid inlet of the other way is connected to the top liquid spray gun of hydrolysis calciner 1 through feeding pump 7; Connect the gas inlet at the bottom of the hydrochloric acid absorption tower 12 by a secondary condensation device consisting of the first condenser 8 and the second condenser 9; the liquid outlet of the first condenser 8 and the second condenser 9 connects the liquid inlet of the hydrochloric acid mixing tank 13 The cooling water inlet of the first condenser 8 and the second condenser 9 connects the outlet of the air cooling tower 10 through the air-cooling circulating pump 11, and the inlet of the air-cooling circulating pump 11 is connected to the desalted water delivery pipeline in addition; the first condenser 8 and the second condenser The cooling water outlet of 9 connects the inlet of air-cooling tower 10; The liquid outlet at the bottom of hydrochloric acid absorption tower 12 connects the liquid inlet of hydrochloric acid mixing tank 13, and the liquid outlet of hydrochloric acid mixing tank 13 connects the hydrochloric acid product outgoing pipeline through hydrochloric acid pump 14; Hydrochloric acid absorption tower 12 The top gas outlet is connected to the bottom gas inlet of the washing tower 16 by the acid-resistant fan 15; the bottom liquid outlet of the washing tower 16 is connected to the liquid inlet at the top of the hydrochloric acid absorption tower 12 and the liquid inlet at the top of the washing tower 16 through the washing pump 27; the liquid inlet at the top of the washing tower 16 is additionally Connect the desalted water delivery line.

如图2所示,应用本实用新型所述一种高浓酸洗废液再生系统的高浓酸洗废液再生工艺包括如下步骤:As shown in Figure 2, the high-concentration pickling waste regeneration process using a high-concentration pickling waste regeneration system described in the present invention includes the following steps:

1)Fe离子浓度>150g/L的高浓度酸洗废液在预浓缩器5中经高温烟气浓缩,浓缩后Fe离子浓度>200g/L的酸洗废液进入水解焙烧炉1中进行高温分解,分解温度400~700℃;1) The high-concentration pickling waste liquid with Fe ion concentration > 150g/L is concentrated by high-temperature flue gas in the pre-concentrator 5, and the pickling waste liquid with Fe ion concentration > 200g/L after concentration enters the hydrolysis roasting furnace 1 for high temperature Decompose, the decomposition temperature is 400~700℃;

2)将步骤1)制备的含HCl的高温烟气依次送入旋风除尘器2与多管除尘器3进行除尘处理,其中95%以上的粉尘被收集后作为氧化铁红回收利用;2) The high-temperature flue gas containing HCl prepared in step 1) is sequentially sent to the cyclone dust collector 2 and the multi-pipe dust collector 3 for dust removal treatment, wherein more than 95% of the dust is collected and recycled as iron oxide red;

3)将步骤2)得到气体送入预浓缩器5,与高浓度酸洗废液进行接触,完成除尘、液体浓缩、气体降温等过程,预浓缩器5操作温度85~95℃;3) Send the gas obtained in step 2) into the pre-concentrator 5, and contact with the high-concentration pickling waste liquid to complete the processes of dust removal, liquid concentration, and gas cooling. The operating temperature of the pre-concentrator 5 is 85-95°C;

4)将经步骤3)处理后的气体进行二级冷凝,冷凝温度分别为65~75℃和45~55℃,获得浓度为23~25%wt的高浓度再生盐酸;4) performing secondary condensation on the gas treated in step 3), the condensation temperatures are respectively 65-75°C and 45-55°C, to obtain high-concentration regenerated hydrochloric acid with a concentration of 23-25%wt;

5)将经步骤4)处理后的气体送入盐酸吸收塔12,用水吸收,获得浓度为23~25%wt的高浓度再生盐酸;吸收HCl气体后的烟气送往洗涤塔16进行洗涤,洗涤后的烟气达标排放,洗涤液作为盐酸吸收液使用。5) send the gas treated in step 4) into the hydrochloric acid absorption tower 12, absorb it with water, and obtain a high-concentration regenerated hydrochloric acid with a concentration of 23-25% wt; the flue gas after absorbing the HCl gas is sent to the scrubber 16 for washing, The flue gas after washing is discharged up to the standard, and the washing liquid is used as the hydrochloric acid absorption liquid.

所述水解焙烧炉1炉顶温度顶350~450℃,炉底温度650~750℃,表压-200~300Pa。The top temperature of the hydrolysis roasting furnace 1 is 350-450°C, the furnace bottom temperature is 650-750°C, and the gauge pressure is -200-300Pa.

本实用新型所述一种高浓酸洗废液再生系统在现有Ruthner技术进行了改进,高浓度的酸洗废液在预浓缩器5中被高温烟气浓缩后进入水解煅烧炉1中进行高温分解,获得的高温烟气经过旋风除尘器2与多管除尘器3除尘后进入预浓缩器5,与要处理的酸洗废液进行接触,温度降低至85-95℃的气体不是直接用水进行吸收,而是进入二级冷凝装置8、9进行冷凝,将烟气中的HCl与水冷凝下来;由于避免了水的加入,使高浓度的HCl与水可以同时冷凝下来,避开了盐酸溶液的恒沸点,实现再生盐酸浓度超过22%以上。冷凝处理后的烟气中含有浓度更高的HCl,在盐酸吸收塔12中利用一定配比的水进行吸收,获得所需浓度的盐酸。吸收盐酸的尾气经过洗涤塔16进一步吸收,尾气达标排放。The high-concentration pickling waste liquid regeneration system described in the utility model is improved on the existing Ruthner technology. The high-concentration pickling waste liquid is concentrated by high-temperature flue gas in the pre-concentrator 5 and then enters the hydrolysis calciner 1 for further processing. Pyrolysis, the high-temperature flue gas obtained is dedusted by the cyclone dust collector 2 and the multi-tube dust collector 3, and then enters the pre-concentrator 5, and contacts with the pickling waste liquid to be treated. The gas whose temperature is lowered to 85-95 ° C is not directly watered Instead, enter the secondary condensation device 8, 9 to condense, and condense the HCl and water in the flue gas; because the addition of water is avoided, the high-concentration HCl and water can be condensed at the same time, avoiding hydrochloric acid The azeotropic point of the solution realizes that the concentration of regenerated hydrochloric acid exceeds 22%. The condensed flue gas contains HCl with a higher concentration, which is absorbed by a certain proportion of water in the hydrochloric acid absorption tower 12 to obtain hydrochloric acid with a required concentration. The tail gas absorbed by hydrochloric acid is further absorbed through the washing tower 16, and the tail gas is discharged up to the standard.

以下实施例在以本实用新型技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本实用新型的保护范围不限于下述的实施例。下述实施例中所用方法如无特别说明均为常规方法。The following examples are carried out on the premise of the technical solution of the utility model, and detailed implementation and specific operation process are provided, but the protection scope of the utility model is not limited to the following examples. The methods used in the following examples are conventional methods unless otherwise specified.

【实施例1】【Example 1】

1)以天然气作为热源对水解煅烧炉1进行预热,然后加热到所需的温度,其中炉顶温度400℃,炉底温度700℃;将高浓度酸洗废液加入预浓缩器5中,对高温烟气降温的同时,实现高浓度酸洗废液的预浓缩。1) Preheat the hydrolysis calciner 1 with natural gas as the heat source, and then heat it to the required temperature, wherein the furnace top temperature is 400°C, and the furnace bottom temperature is 700°C; add high-concentration pickling waste liquid into the pre-concentrator 5, While cooling the high-temperature flue gas, it realizes the pre-concentration of high-concentration pickling waste liquid.

所需处理的高浓度酸洗废液成分组成如下表所示:The composition of the high-concentration pickling waste liquid to be treated is shown in the following table:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 47.9147.91 105.402105.402 Fe3+=16.51g/LFe 3+ =16.51g/L FeCl2 FeCl2 340.45340.45 748.99748.99 Fe2+=150.0g/LFe 2+ =150.0g/L HClHCl 75.7375.73 166.606166.606 H2OH 2 O 911.1911.1 2004.422004.42 总计total 1375.191375.19 3025.4183025.418

每小时处需理酸洗废液3.025吨。It needs to process 3.025 tons of pickling waste per hour.

2)经预浓缩器5预浓缩后的酸洗废液成分组成如下表所示:2) The components of the pickling waste liquid after pre-concentration by the pre-concentrator 5 are as shown in the table below:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 63.8763.87 105.3855105.3855 Fe3+=22.01g/LFe 3+ =22.01g/L FeCl2 FeCl2 453.96453.96 749.034749.034 Fe2+=200g/LFe 2+ =200g/L HClHCl 135.29135.29 223.2285223.2285 H2OH 2 O 683.32683.32 1127.4781127.478 总计total 1336.441336.44 2205.1262205.126

经高温水解后的气体成分组成如下表所示:The gas composition after high temperature hydrolysis is shown in the following table:

成分Element 体积%volume% HClHCl 10.510.5 H2OH 2 O 39.839.8 O2 O 2 3.773.77 N2 N 2 42.1642.16 CO2 CO 2 3.773.77

气体总体积为9800m3,温度400℃。气体中含有Fe2O3 60kg,经过二级除尘后,粉尘回收量为57kg,回收率达到95%。The total gas volume is 9800m 3 , and the temperature is 400°C. The gas contains 60kg of Fe 2 O 3 . After the secondary dust removal, the dust recovery is 57kg, and the recovery rate reaches 95%.

水解煅烧炉1炉底收集氧化铁红粉末450kg,其中Fe2O3含量为98.8%wt,Cl含量1.01%wt,堆密度400kg/m3450kg of red iron oxide powder was collected from the bottom of hydrolysis calciner 1 , wherein the content of Fe2O3 was 98.8%wt, the content of Cl was 1.01%wt, and the bulk density was 400kg/ m3 .

经预浓缩器5浓缩后的气体成分组成:Composition of the gas components concentrated by the pre-concentrator 5:

成分Element 体积%volume% HClHCl 7.887.88 H2OH 2 O 49.949.9 O2 O 2 3.183.18 N2 N 2 35.535.5 CO2 CO 2 3.183.18

气体总体积为6413m3/h,密度0.818kg/m3,温度93.5℃。The total gas volume is 6413m 3 /h, the density is 0.818kg/m 3 , and the temperature is 93.5°C.

3)进行二级冷凝、吸收、洗涤:3) Perform secondary condensation, absorption, and washing:

其中第一冷凝器8的冷凝温度为70℃,第二冷凝器9的冷凝温度为50℃。Wherein the condensation temperature of the first condenser 8 is 70°C, and the condensation temperature of the second condenser 9 is 50°C.

盐酸吸收塔12的进液量为224.4kg/h,其中HCl含量为2%wt。The feed rate of the hydrochloric acid absorption tower 12 is 224.4kg/h, wherein the HCl content is 2%wt.

经过二级冷凝及盐酸吸收后获得的盐酸量为2629kg/h,浓度为23%wt。The amount of hydrochloric acid obtained after secondary condensation and hydrochloric acid absorption is 2629kg/h, and the concentration is 23%wt.

经过洗涤塔16后的气体成分组成为:The gas composition after the scrubber 16 is composed of:

成分Element 体积%volume% HClHCl 1.0×10-3 1.0×10 -3 H2OH 2 O 8.878.87 O2 O 2 6.956.95 N2 N 2 77.077.0 CO2 CO 2 7.187.18

气体总体积2700m3/h,温度41℃。The total gas volume is 2700m3/h, and the temperature is 41°C.

【实施例2】[Example 2]

1)以天然气作为热源对水解煅烧炉1进行预热,然后加热到所需的温度,其中炉顶温度350℃,炉底温度650℃;将高浓度酸洗废液加入预浓缩器5中,对高温烟气降温的同时,实现高浓度酸洗废液的预浓缩;1) Preheat the hydrolysis calciner 1 with natural gas as a heat source, and then heat it to the required temperature, wherein the furnace top temperature is 350°C, and the furnace bottom temperature is 650°C; add high-concentration pickling waste liquid into the pre-concentrator 5, While cooling the high-temperature flue gas, realize the pre-concentration of high-concentration pickling waste liquid;

所处理的高浓度酸洗废液成分组成如下表所示:The composition of the treated high-concentration pickling waste liquid is shown in the following table:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 47.9147.91 105.402105.402 Fe3+=16.51g/LFe 3+ =16.51g/L FeCl2 FeCl2 340.45340.45 748.99748.99 Fe2+=150.0g/LFe 2+ =150.0g/L HClHCl 75.7375.73 166.606166.606 H2OH 2 O 911.1911.1 2004.422004.42 总计total 1375.191375.19 3025.4183025.418

每小时面需处理酸洗废液量3.025吨3.025 tons of pickling waste liquid needs to be processed per hour

2)高浓度酸洗废液经预浓缩器5预浓缩后的成分组成如下表所示:2) The composition of the high-concentration pickling waste liquid pre-concentrated by the pre-concentrator 5 is shown in the following table:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 61.1061.10 105.7105.7 Fe3+=21.21g/LFe3 + =21.21g/L FeCl2 FeCl2 435.28435.28 753.0753.0 Fe2+=191.9g/LFe2 + =191.9g/L HClHCl 130.1130.1 224.9224.9 H2OH 2 O 703.52703.52 1172.51172.5 总计total 13301330 23002300

浓缩后的液体进行高温水解,水解后的气体成分组成如下表所示:The concentrated liquid is subjected to high-temperature hydrolysis, and the composition of the gas after hydrolysis is shown in the following table:

成分Element 体积%volume% HClHCl 10.510.5 H2OH 2 O 39.539.5 O2 O 2 3.953.95 N2 N 2 42.142.1 CO2 CO 2 3.953.95

气体总体积合计8526m3/h,温度350℃。The total gas volume is 8526m 3 /h, and the temperature is 350°C.

气体中含有Fe2O3 45kg,粉尘回收量为43.2kg,回收率达到96%。The gas contains 45kg of Fe 2 O 3 , the dust recovery is 43.2kg, and the recovery rate reaches 96%.

水解煅烧炉1炉底收集氧化铁红粉末452kg,其中Fe2O3含量98.2%wt,Cl含量1.51%wt,堆密度400kg/m3452 kg of red iron oxide powder was collected from the bottom of the hydrolysis calciner 1, in which the content of Fe 2 O 3 was 98.2% wt, the content of Cl was 1.51% wt, and the bulk density was 400 kg/m 3 .

经预浓缩器5浓缩后的气体成分组成如下表所示:The composition of the gas components concentrated by the pre-concentrator 5 is shown in the table below:

成分Element 体积%volume% HClHCl 7.837.83 H2OH 2 O 48.348.3 O2 O 2 3.583.58 N2 N 2 36.836.8 CO2 CO 2 3.493.49

气体总体积为5761m3/h,密度0.819kg/m3,温度92.3℃。The total gas volume is 5761m 3 /h, the density is 0.819kg/m 3 , and the temperature is 92.3°C.

3)进行二级冷凝、吸收、洗涤;3) Perform secondary condensation, absorption, and washing;

其中第一冷凝器8的冷凝温度70℃,第二冷凝器9的冷凝温度50℃。Wherein the condensation temperature of the first condenser 8 is 70°C, and the condensation temperature of the second condenser 9 is 50°C.

盐酸吸收塔12的进液量为224.4kg/h,其中HCl含量为2%wt。The feed rate of the hydrochloric acid absorption tower 12 is 224.4kg/h, wherein the HCl content is 2%wt.

经过二级冷凝及盐酸吸收后获得的盐酸量为2314kg/h,浓度为23%wt。The amount of hydrochloric acid obtained after secondary condensation and hydrochloric acid absorption is 2314kg/h, and the concentration is 23%wt.

经过洗涤塔16后的气体成分组成如下表所示:The composition of the gas after the washing tower 16 is as shown in the table below:

成分Element 体积%volume% HClHCl 1.0×10-3 1.0×10 -3 H2OH 2 O 5.525.52 O2 O 2 8.858.85 N2 N 2 74.874.8 CO2 CO 2 10.8310.83

气体体积2537m3/h,温度42℃。The gas volume is 2537m 3 /h, and the temperature is 42°C.

【实施例3】[Example 3]

1)以天然气作为热源对水解煅烧炉1进行预热,然后加热到所需的温度,其中炉顶温度450℃,炉底温度750℃;将高浓度酸洗废液加入预浓缩器5中,对高温烟气降温的同时实现酸洗废液的预浓缩;1) Preheat the hydrolysis calciner 1 with natural gas as the heat source, and then heat it to the required temperature, wherein the furnace top temperature is 450°C, and the furnace bottom temperature is 750°C; the high-concentration pickling waste liquid is added to the pre-concentrator 5, Realize the pre-concentration of pickling waste liquid while cooling the high-temperature flue gas;

所处理的高浓度酸洗废液成分组成如下表所示:The composition of the treated high-concentration pickling waste liquid is shown in the following table:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 47.9147.91 105.402105.402 Fe3+=16.51g/LFe 3+ =16.51g/L FeCl2 FeCl2 340.45340.45 748.99748.99 Fe2+=150.0g/LFe 2+ =150.0g/L HClHCl 75.7375.73 166.606166.606 H2OH 2 O 911.1911.1 2004.422004.42 总计total 1375.191375.19 3025.4183025.418

每小时需处理高浓度酸洗废液3.025吨。It needs to process 3.025 tons of high-concentration pickling waste per hour.

2)高浓度酸洗废液经预浓缩器5预浓缩后的成分组成如下表所示:2) The composition of the high-concentration pickling waste liquid pre-concentrated by the pre-concentrator 5 is shown in the following table:

成分Element 含量g/LContentg/L 流量Kg/hFlow Kg/h 备注Remark FeCl3 FeCl3 66.9066.90 105.7105.7 Fe3+=22.01g/LFe 3+ =22.01g/L FeCl2 FeCl2 461.7461.7 729.5729.5 Fe2+=200g/LFe 2+ =200g/L HClHCl 132.1132.1 208.7208.7 H2OH 2 O 719.3719.3 1136.11136.1 总计total 13801380 2180.02180.0

预浓缩后液体进行高温水解,水解后的气体成分组成如下表所示:After pre-concentration, the liquid is subjected to high-temperature hydrolysis, and the composition of the gas after hydrolysis is shown in the following table:

成分Element 体积%volume% HClHCl 10.410.4 H2OH 2 O 38.7138.71 O2 O 2 4.334.33 N2 N 2 42.6842.68 CO2 CO 2 3.883.88

气体总体积合计10593m3,温度450℃。The total gas volume is 10593m 3 , and the temperature is 450°C.

气体中含有Fe2O3 70kg,粉尘回收量为66.5kg,回收率达到95%。The gas contains 70kg of Fe 2 O 3 , the dust recovery is 66.5kg, and the recovery rate reaches 95%.

水解煅烧炉1炉底收集氧化铁红粉末435kg,其中Fe2O3含量99.1%wt,Cl含量0.78%wt,堆密度400kg/m3435 kg of red iron oxide powder was collected from the bottom of hydrolysis calciner 1, in which Fe 2 O 3 content was 99.1% wt, Cl content was 0.78% wt, and the bulk density was 400 kg/m 3 .

经过预浓缩器后的气体成分组成如下表所示:The composition of the gas after passing through the pre-concentrator is shown in the table below:

成分Element 体积%volume% HClHCl 7.947.94 H2OH 2 O 50.4150.41 O2 O 2 3.523.52 N2 N 2 34.9534.95 CO2 CO 2 3.183.18

气体总体积为6610m3/h,密度0.818kg/m3,温度93.9℃The total gas volume is 6610m 3 /h, the density is 0.818kg/m 3 , and the temperature is 93.9℃

3)进行二级冷凝、吸收、洗涤;3) Perform secondary condensation, absorption, and washing;

其中第一冷凝器8的冷凝温度70℃,第二冷凝器9的冷凝温度50℃。Wherein the condensation temperature of the first condenser 8 is 70°C, and the condensation temperature of the second condenser 9 is 50°C.

盐酸吸收塔12的进液体为255kg/h,其中HCl含量为2%wt。The feed liquid of the hydrochloric acid absorption tower 12 is 255kg/h, wherein the HCl content is 2%wt.

经过二级冷凝,然后经过盐酸吸收后获得的盐酸量为2743kg/h,浓度为23%wt。The amount of hydrochloric acid obtained after secondary condensation and then hydrochloric acid absorption is 2743kg/h, and the concentration is 23%wt.

经过洗涤塔16后的气体组成为:The composition of the gas after the scrubber 16 is:

成分Element 体积%volume% HClHCl 1.0×10-3 1.0×10 -3 H2OH 2 O 8.918.91 O2 O 2 7.697.69 N2 N 2 76.676.6 CO2 CO 2 6.806.80

气体体积2767m3/h,温度42℃。The gas volume is 2767m 3 /h, and the temperature is 42°C.

以上所述,仅为本实用新型较佳的具体实施方式,但本实用新型的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本实用新型揭露的技术范围内,根据本实用新型的技术方案及其实用新型构思加以等同替换或改变,都应涵盖在本实用新型的保护范围之内。The above is only a preferred embodiment of the utility model, but the scope of protection of the utility model is not limited thereto. The equivalent replacement or change of the new technical solution and the concept of the utility model shall be covered by the protection scope of the utility model.

Claims (1)

1. a kind of highly concentrated pickle liquor regenerative system, it is characterised in that including hydrolysis calcining furnace, two-stage dust removal device, pre-concentration Device, B grade condensing unit, air cooling tower, hydrochloric acid absorption tower and scrubbing tower;The top exhanst gas outlet of the hydrolysis calcining furnace leads to successively Cross and connect smoke inlet at the top of preconcentrator with the two-stage dust removal device that multi-tube dust cleaner forms by cyclone separator;Hydrolysis calcining The dust outlet of stove, cyclone separator and multi-tube dust cleaner connects Pneumatic conveying pipeline respectively, and Pneumatic conveying pipeline is provided with gas Power conveying fan;The overhead-liquid that the bottom liquid outlet of preconcentrator connects preconcentrator by circulating concentrating pump all the way enters Mouthful, another way connects the overhead-liquid spray gun of hydrolysis calcining furnace by feed pump;Concentration acid solution entrance connection on preconcentrator High concentration pickle liquor conveyance conduit;The gas vent of preconcentrator passes sequentially through to be made up of the first condenser and the second condenser B grade condensing unit connection hydrochloric acid absorption tower bottom gas inlet;The liquid outlet of first condenser and the second condenser connects The liquid inlet of mixed in hydrochloric acid groove;The cooling water inlet of first condenser and the second condenser connects air cooling by air cooling circulating pump The outlet of tower, air cooling pump entry connect desalted water conveyance conduit in addition;The cooling water of first condenser and the second condenser The entrance of outlet connection air cooling tower;Hydrochloric acid absorption tower bottom liquid outlet connects the liquid inlet of mixed in hydrochloric acid groove, mixed in hydrochloric acid The liquid outlet of groove connects hydrochloric acid product by hydrochloric acid pump and sends pipeline outside;The outlet of hydrochloric acid absorption tower top gas passes through acidproof blower fan Connect the bottom gas inlet of scrubbing tower;The bottom liquid outlet of scrubbing tower connects hydrochloric acid absorption tower overhead-liquid by washing pump Liquid inlet at the top of entrance and scrubbing tower;Liquid inlet connects desalted water conveyance conduit in addition at the top of scrubbing tower.
CN201720434156.XU 2017-04-24 2017-04-24 A kind of highly concentrated pickle liquor regenerative system Withdrawn - After Issue CN206872425U (en)

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Patentee after: ANSHAN CHUANGXIN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd.

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Granted publication date: 20180112

Effective date of abandoning: 20230811

AV01 Patent right actively abandoned

Granted publication date: 20180112

Effective date of abandoning: 20230811