CN203820581U - High-concentration coking desulfurization waste liquid treatment device - Google Patents
High-concentration coking desulfurization waste liquid treatment device Download PDFInfo
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- CN203820581U CN203820581U CN201420083468.7U CN201420083468U CN203820581U CN 203820581 U CN203820581 U CN 203820581U CN 201420083468 U CN201420083468 U CN 201420083468U CN 203820581 U CN203820581 U CN 203820581U
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- 239000007788 liquid Substances 0.000 title claims abstract description 133
- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 238000004939 coking Methods 0.000 title claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 38
- 230000023556 desulfurization Effects 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 5
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000002918 waste heat Substances 0.000 description 12
- 238000009284 supercritical water oxidation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- -1 nitrogen-containing oxygen heterocyclic compounds Chemical class 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
本实用新型公开了一种高浓度焦化脱硫废液处理装置。该装置包括废液第一预热器，所述废液第一预热器与废液储罐和废液第二预热器相连，所述废液第二预热器与气液混合室相连，所述气液混合室与气体预热器相连，所述气体预热器与空气压缩机相连，所述空气压缩机与空气储罐相连，所述气液混合室与超临界快速催化氧化反应器相连，所述超临界快速催化氧化反应器与换热器相连，所述换热器与气液分离器相连，所述气液分离器与排气储罐相连。该装置操作方便、反应迅速、运行成本费用低、无二次污染、催化剂可回收再利用。
The utility model discloses a treatment device for high-concentration coking desulfurization waste liquid. The device includes a waste liquid first preheater, the waste liquid first preheater is connected to a waste liquid storage tank and a waste liquid second preheater, and the waste liquid second preheater is connected to a gas-liquid mixing chamber , the gas-liquid mixing chamber is connected to the gas preheater, the gas preheater is connected to the air compressor, the air compressor is connected to the air storage tank, and the gas-liquid mixing chamber is connected to the supercritical rapid catalytic oxidation reaction The supercritical fast catalytic oxidation reactor is connected with the heat exchanger, the heat exchanger is connected with the gas-liquid separator, and the gas-liquid separator is connected with the exhaust storage tank. The device has the advantages of convenient operation, rapid response, low operating cost, no secondary pollution, and the catalyst can be recycled and reused.
Description
技术领域technical field
本实用新型属于污水处理技术领域，具体涉及一种高浓度焦化脱硫废液处理装置。The utility model belongs to the technical field of sewage treatment, in particular to a treatment device for high-concentration coking desulfurization waste liquid.
背景技术Background technique
随着钢铁生产大型集约化发展，在生产过程中余热回收利用与难降解废水多污染物协同控制技术发展显得十分重要。我国是焦炭生产和消费大国，尤其在近年来焦炭产能得到迅猛发展。2007年焦炭产量33554万吨，占全球焦炭总产量的60％。在炼焦、煤气净化及焦化产品回收过程中产生的大量焦化废水，不仅成分复杂，组分种类繁多，而且根据煤质、工艺不同，各焦化企业的水质存在很大差别。With the development of large-scale intensification of iron and steel production, the development of waste heat recovery and utilization in the production process and the coordinated control of refractory wastewater and multi-pollutants are very important. my country is a big country of coke production and consumption, especially in recent years, coke production capacity has developed rapidly. In 2007, the output of coke was 335.54 million tons, accounting for 60% of the total output of coke in the world. A large amount of coking wastewater produced in the process of coking, gas purification and coking product recovery not only has complex components and a wide variety of components, but also has great differences in water quality among coking enterprises depending on the coal quality and process.
炼焦生产中煤在高温干馏、煤气净化以及化工产品精制过程中产生的废水，主要来源于剩余氨水、粗苯分离水、终冷富余水、焦油分离水四部分，这些废水的特点是浓度高、温度高、污染物组成复杂、毒性大，特别是焦化高浓度焦化脱硫废液，含有大量的酚、多环芳烃和含氮氧杂环化合物、NH3-N、CN-、S2-和SCN-等污染物，这些污染物形成的色度高，在水中以真溶液或准胶体的形式存在，性质非常稳定，化学需氧量（COD）及色度去除困难。The waste water produced in the process of high-temperature carbonization, gas purification and refining of chemical products in coking production mainly comes from four parts: residual ammonia water, crude benzene separation water, final cooling surplus water, and tar separation water. The waste water is characterized by high concentration, High temperature, complex composition of pollutants, high toxicity, especially high-concentration coking desulfurization waste liquid of coking, which contains a large amount of phenols, polycyclic aromatic hydrocarbons and nitrogen-containing oxygen heterocyclic compounds, NH 3 -N, CN - , S 2- and SCN - and other pollutants, these pollutants form high chroma, exist in the form of true solution or quasi-colloid in water, are very stable in nature, and it is difficult to remove chemical oxygen demand (COD) and chroma.
高浓度焦化脱硫废液进入现有的废水处理系统就会造成系统的不稳定运行，使现有的处理方法达标排放困难，目前，国内外均采用高级氧化的方法处理高浓度焦化脱硫废液，常用的Fenton试剂处理方法去除高浓度焦化脱硫废液中COD和氨氮等有机物，反应产生的铁泥会形成二次污染，催化剂难以回收，H2O2对设备也有很强的腐蚀性，操作复杂而且运行费用也高；臭氧组合氧化技术中，只有在反应条件为酸性时，臭氧才是主要的氧化剂，反应过程总需要严格控制pH，而且此法组合工艺操作复杂，反应耗时长，对COD和氨氮等有机物去除率也不是很高。The entry of high-concentration coking desulfurization waste liquid into the existing wastewater treatment system will cause unstable operation of the system, making it difficult for the existing treatment methods to meet the discharge standards. At present, advanced oxidation methods are used at home and abroad to treat high-concentration coking desulfurization waste liquid. The commonly used Fenton reagent treatment method removes organic substances such as COD and ammonia nitrogen in high-concentration coking desulfurization waste liquid. The iron sludge produced by the reaction will form secondary pollution, and the catalyst is difficult to recover. H 2 O 2 is also very corrosive to equipment and complicated to operate. Moreover, the operating cost is also high; in the ozone combined oxidation technology, only when the reaction conditions are acidic, ozone is the main oxidant, and the reaction process always needs to strictly control the pH, and the combined process of this method is complicated to operate and takes a long time to react. The removal rate of organic matter such as ammonia nitrogen is not very high.
超临界水氧化法SCWO(Supercritical Water Oxidation)是在超临界水状态下进行的湿式氧化反应。由于超临界水所具有的独特性质，超临界水氧化法可以充分地引入氧参加反应，不存在气液相界面之间的物质转移等问题。在超临界水氧化法中加入适宜的催化剂，可提高处理效率与处理容量，达到节能高效的目的，是一种新型高效的处理高浓度焦化脱硫废液的方法。Supercritical Water Oxidation SCWO (Supercritical Water Oxidation) is a wet oxidation reaction carried out in the state of supercritical water. Due to the unique properties of supercritical water, the supercritical water oxidation method can fully introduce oxygen to participate in the reaction, and there is no problem such as material transfer between the gas-liquid phase interface. Adding a suitable catalyst in the supercritical water oxidation method can improve the treatment efficiency and capacity, and achieve the goal of energy saving and high efficiency. It is a new and efficient method for treating high-concentration coking desulfurization waste liquid.
高浓度焦化脱硫废液有较高的低质余热可以在废液处理中回收利用，目前还没有关于余热回收利用这方面的报导。高浓度焦化脱硫废液具有污染物种类多、难降解的特点，通过超临界水氧化催化快反应技术，结合余热利用以迅速彻底的氧化处理高浓度焦化脱硫废液，既使实际生产中多余的热量资源得到了利用，也实现了高浓度焦化脱硫废液中COD和氨氮等有机物的快速降解去除。但是高浓度焦化脱硫废液结合余热的技术，在现有技术中没有任何报道。High-concentration coking desulfurization waste liquid has high low-quality waste heat that can be recycled in waste liquid treatment, but there is no report on waste heat recovery and utilization. High-concentration coking desulfurization waste liquid has many types of pollutants and is difficult to degrade. Through supercritical water oxidation catalytic fast reaction technology, combined with waste heat utilization, high-concentration coking desulfurization waste liquid can be quickly and thoroughly oxidized, even if the excess in actual production Heat resources have been utilized, and the rapid degradation and removal of organic matter such as COD and ammonia nitrogen in high-concentration coking desulfurization waste liquid has been realized. However, the technology of combining high-concentration coking desulfurization waste liquid with waste heat has not been reported in the prior art.
实用新型内容Utility model content
本实用新型的目的是为解决上述问题而提供了一种操作方便、反应迅速、运行成本费用低、无二次污染、催化剂可回收再利用和热量资源循环利用的高浓度焦化脱硫废液处理装置。The purpose of this utility model is to solve the above problems and provide a high-concentration coking desulfurization waste liquid treatment device with convenient operation, rapid response, low operating cost, no secondary pollution, recyclable catalyst and recycling of heat resources. .
本实用新型所采用的技术方案是：The technical scheme adopted in the utility model is:
一种高浓度焦化脱硫废液处理装置，包括废液第一预热器，所述废液第一预热器与废液储罐和废液第二预热器相连，所述废液第二预热器与气液混合室相连，所述气液混合室与气体预热器相连，所述气体预热器与空气压缩机相连，所述空气压缩机与空气储罐相连，所述气液混合室与超临界快速催化氧化反应器相连，所述超临界快速催化氧化反应器与换热器相连，所述换热器与气液分离器相连，所述气液分离器与排气储罐相连。A high-concentration coking desulfurization waste liquid treatment device, comprising a waste liquid first preheater, the waste liquid first preheater is connected with a waste liquid storage tank and a waste liquid second preheater, and the waste liquid second preheater The preheater is connected to the gas-liquid mixing chamber, the gas-liquid mixing chamber is connected to the gas preheater, the gas preheater is connected to the air compressor, the air compressor is connected to the air storage tank, and the gas-liquid The mixing chamber is connected to the supercritical rapid catalytic oxidation reactor, the supercritical rapid catalytic oxidation reactor is connected to the heat exchanger, the heat exchanger is connected to the gas-liquid separator, and the gas-liquid separator is connected to the exhaust storage tank connected.
进一步地，所述废液第一预热器和废液第二预热器之间安装有高压泵。Further, a high-pressure pump is installed between the first waste liquid preheater and the second waste liquid preheater.
进一步地，所述换热器与气液分离器之间相连通的管路上设置有采样点。Further, a sampling point is provided on the pipeline connected between the heat exchanger and the gas-liquid separator.
进一步地，所述废液第二预热器、气体预热器以及超临界快速催化氧化反应器上安装有温度控制表和压力控制表。Further, temperature control gauges and pressure control gauges are installed on the waste liquid second preheater, gas preheater and supercritical fast catalytic oxidation reactor.
进一步地，所述废液第一预热器、废液第二预热器、气体预热器、气液混合室以及超临界快速催化氧化反应器上包裹保温材料，废液第一预热器与废液第二预热器之间相连通的管路、废液第二预热器与气液混合室之间相连通的管路、气体预热器与气液混合室之间相连通的管路、气液混合室与超临界快速催化氧化反应器之间相连通的管路、换热器与废液第一预热器之间相连通的管路上包裹保温材料。Further, the first waste liquid preheater, the second waste liquid preheater, the gas preheater, the gas-liquid mixing chamber and the supercritical fast catalytic oxidation reactor are wrapped with insulation materials, and the first waste liquid preheater The pipeline that communicates with the second waste liquid preheater, the pipeline that communicates with the second waste liquid preheater and the gas-liquid mixing chamber, and the pipeline that communicates between the gas preheater and the gas-liquid mixing chamber The pipes, the pipes connected between the gas-liquid mixing chamber and the supercritical fast catalytic oxidation reactor, and the pipes connected between the heat exchanger and the first waste liquid preheater are wrapped with insulating materials.
本实用新型具有以下优点：The utility model has the following advantages:
（1）本实用新型运用焦化余热对高浓度焦化脱硫废液进行预加热，提高超临界快速催化氧化反应器的进液温度，节约了处理成本。(1) The utility model uses coking waste heat to preheat the high-concentration coking desulfurization waste liquid to increase the liquid inlet temperature of the supercritical rapid catalytic oxidation reactor and save the treatment cost.
（2）本实用新型采用的氧化剂为空气中的氧，在超临界快速催化氧化反应器中迅速发生氧化反应，降解高浓度焦化脱硫废液中的酚、多环芳烃和含氮氧杂环化合物，转化为无害的N2、CO2、H2O和小分子化合物，反应速度快，产物无二次污染。(2) The oxidant used in this utility model is oxygen in the air, and the oxidation reaction occurs rapidly in the supercritical rapid catalytic oxidation reactor to degrade phenols, polycyclic aromatic hydrocarbons and nitrogen-containing oxygen heterocyclic compounds in high-concentration coking desulfurization waste liquid , converted into harmless N 2 , CO 2 , H 2 O and small molecule compounds, the reaction speed is fast, and the product has no secondary pollution.
（3）本实用新型采用催化剂为纳米金属氧化物，具体为纳米钛铝复合物，浸渍硝酸锰水溶液，干燥焙烧制得，催化剂稳定性好，易于回收再利用。(3) The utility model adopts nano-metal oxides as catalysts, specifically nano-titanium-aluminum composites, impregnated with manganese nitrate aqueous solution, and dried and roasted. The catalyst has good stability and is easy to recycle and reuse.
（4）本实用新型工艺流程简单，易操作，反应器中压力、温度等通过一体化电控与压力系统控制，可迅速降解去除高浓度焦化脱硫废液的有机物，对焦化脱硫废液中COD和NH3-N的去除率可达97%以上。(4) The technological process of the utility model is simple and easy to operate. The pressure and temperature in the reactor are controlled by the integrated electric control and pressure system, which can quickly degrade and remove organic matter in high-concentration coking desulfurization waste liquid, and COD in coking desulfurization waste liquid And the removal rate of NH 3 -N can reach more than 97%.
本实用新型利用超临界水氧化技术，针对焦化余热的高浓度废水所具有的有机污染物浓度高、种类多、毒性大、难于降解和余热未利用等特点，对于焦化余热的高浓度焦化脱硫废液中难降解有机物具有较好的去除效果。处理过后的COD和NH3-N浓度均可达到国家排放标准，工艺简单、操作方便、反应迅速、运行成本费用低、无二次污染、催化剂可回收再利用和热量资源循环利用。The utility model utilizes supercritical water oxidation technology, aiming at the characteristics of high-concentration waste water of coking waste heat, such as high concentration of organic pollutants, many types, high toxicity, difficulty in degradation and unutilized waste heat, etc. Refractory organic matter in the liquid has a good removal effect. The concentration of COD and NH 3 -N after treatment can reach the national emission standard, the process is simple, the operation is convenient, the response is fast, the operation cost is low, no secondary pollution, the catalyst can be recycled and reused, and the heat resource can be recycled.
附图说明Description of drawings
图1为本实用新型实施例提供的高浓度焦化脱硫废液处理装置的结构示意图。Fig. 1 is a schematic structural diagram of a high-concentration coking desulfurization waste liquid treatment device provided by an embodiment of the present invention.
具体实施方式Detailed ways
下面结合附图和实施方式对本实用新型做进一步详细的说明。Below in conjunction with accompanying drawing and embodiment, the utility model is described in further detail.
本实施例提供了一种高浓度焦化脱硫废液处理装置，包括废液第一预热器4。废液第一预热器4与废液储罐3和废液第二预热器13相连，废液第一预热器4和废液第二预热器13之间安装有高压泵5。废液第二预热器13与气液混合室14相连，气液混合室14与气体预热器15相连。气体预热器15与空气压缩机1相连。空气压缩机1与空气储罐2相连。气液混合室14与超临界快速催化氧化反应器12相连。超临界快速催化氧化反应器12与换热器9相连。换热器9与气液分离器7相连，气液分离器7与排气储罐8相连。换热器9与气液分离器7之间相连通的管路上设置有采样点6。废液第二预热器13、气体预热器15以及超临界快速催化氧化反应器12上安装有温度控制表10和压力控制表11。废液第一预热器4、废液第二预热器13、气体预热器15、气液混合室14以及超临界快速催化氧化反应器12上包裹保温材料，废液第一预热器4与废液第二预热器13之间相连通的管路、废液第二预热器13与气液混合室14之间相连通的管路、气体预热器15与气液混合室14之间相连通的管路、气液混合室14与超临界快速催化氧化反应器12之间相连通的管路、换热器9与废液第一预热器4之间相连通的管路上包裹保温材料。This embodiment provides a high-concentration coking desulfurization waste liquid treatment device, which includes a first waste liquid preheater 4 . The first waste liquid preheater 4 is connected to the waste liquid storage tank 3 and the second waste liquid preheater 13 , and a high pressure pump 5 is installed between the first waste liquid preheater 4 and the second waste liquid preheater 13 . The second waste liquid preheater 13 is connected to the gas-liquid mixing chamber 14 , and the gas-liquid mixing chamber 14 is connected to the gas preheater 15 . The gas preheater 15 is connected with the air compressor 1 . The air compressor 1 is connected with the air storage tank 2 . The gas-liquid mixing chamber 14 is connected with the supercritical fast catalytic oxidation reactor 12 . The supercritical fast catalytic oxidation reactor 12 is connected with the heat exchanger 9 . The heat exchanger 9 is connected with the gas-liquid separator 7 , and the gas-liquid separator 7 is connected with the exhaust storage tank 8 . A sampling point 6 is provided on the pipeline connected between the heat exchanger 9 and the gas-liquid separator 7 . A temperature control gauge 10 and a pressure control gauge 11 are installed on the waste liquid second preheater 13 , the gas preheater 15 and the supercritical fast catalytic oxidation reactor 12 . The first waste liquid preheater 4, the second waste liquid preheater 13, the gas preheater 15, the gas-liquid mixing chamber 14, and the supercritical rapid catalytic oxidation reactor 12 are wrapped with thermal insulation materials, and the waste liquid first preheater 4 The pipeline connected with the second waste liquid preheater 13, the pipeline connected between the second waste liquid preheater 13 and the gas-liquid mixing chamber 14, the gas preheater 15 and the gas-liquid mixing chamber 14, the pipeline connected between the gas-liquid mixing chamber 14 and the supercritical rapid catalytic oxidation reactor 12, the pipe connected between the heat exchanger 9 and the waste liquid first preheater 4 Wrap insulation on the road.
本装置可以对高浓度焦化脱硫废液进行催化处理，其步骤为：This device can carry out catalytic treatment on high-concentration coking desulfurization waste liquid, and its steps are:
（1）高浓度焦化脱硫废液和氧气的预热：将废液储罐3中的高浓度焦化脱硫废液注入到废液第一预热器4中，利用焦化余热，将高浓度焦化脱硫废液的温度提升至80℃，随后将升温后的高浓度焦化脱硫废液经高压泵5注入废液第二预热器13；空气储罐2内的空气经空气压缩机1输入至气体预热器中15；高浓度焦化脱硫废液和空气分别预热后在气液混合室14内混合形成气液混合物。(1) Preheating of high-concentration coking desulfurization waste liquid and oxygen: inject the high-concentration coking desulfurization waste liquid in the waste liquid storage tank 3 into the waste liquid first preheater 4, and use coking waste heat to desulfurize high-concentration coking desulfurization The temperature of the waste liquid is raised to 80°C, and then the heated high-concentration coking desulfurization waste liquid is injected into the second waste liquid preheater 13 through the high pressure pump 5; the air in the air storage tank 2 is input into the gas preheater through the air compressor 1. Heater 15; high-concentration coking desulfurization waste liquid and air are respectively preheated and then mixed in the gas-liquid mixing chamber 14 to form a gas-liquid mixture.
（2）超临界快速催化氧化反应处理：将催化剂放入超临界快速催化氧化反应器12中，再将气液混合物通入超临界快速催化氧化反应器12中，使焦化脱硫废液发生快速催化氧化反应；超临界快速催化氧化反应过程中，超临界快速催化氧化反应器12内的压力为30MPa，温度为200℃，停留时间为0.1min。催化剂为纳米金属氧化物，纳米金属氧化物为纳米钛铝复合物和浸渍硝酸锰溶液混合后干燥焙烧制得，催化剂的使用剂量为10mg/L。空气储罐3的空气的注入量，按质量比计，注入量是进入超临界快速催化氧化反应器12的高浓度焦化脱硫废液的化学需氧量的5倍。(2) Supercritical rapid catalytic oxidation reaction treatment: Put the catalyst into the supercritical rapid catalytic oxidation reactor 12, and then pass the gas-liquid mixture into the supercritical rapid catalytic oxidation reactor 12 to rapidly catalyze the coking desulfurization waste liquid Oxidation reaction: During the supercritical rapid catalytic oxidation reaction, the pressure inside the supercritical rapid catalytic oxidation reactor 12 is 30 MPa, the temperature is 200° C., and the residence time is 0.1 min. The catalyst is a nanometer metal oxide, which is obtained by mixing the nanometer titanium-aluminum compound with an impregnated manganese nitrate solution, drying and roasting, and the dosage of the catalyst is 10 mg/L. The injection amount of air in the air storage tank 3 is 5 times of the chemical oxygen demand of the high-concentration coking desulfurization waste liquid entering the supercritical rapid catalytic oxidation reactor 12 in terms of mass ratio.
（3）焦化脱硫废液的热交换与气液分离处理：将经超临界快速催化氧化反应器12处理过后产生的气液混合物通入换热器9中进行换热，使气液混合物的温度降至25℃以下，降温后的气液混合物经减压后通入气液分离器7中，气液分离后液体排入排水池，气体排入排气储罐8。高浓度焦化脱硫废液经处理生成的气液混合物经过换热器9换热，置换出的余热回用到步骤（1）中的废液第一预热器4中。(3) Heat exchange and gas-liquid separation treatment of coking desulfurization waste liquid: the gas-liquid mixture produced after being treated in the supercritical rapid catalytic oxidation reactor 12 is passed into the heat exchanger 9 for heat exchange, so that the temperature of the gas-liquid mixture When the temperature is lowered to below 25°C, the cooled gas-liquid mixture is decompressed and then passed into the gas-liquid separator 7. After the gas-liquid separation, the liquid is discharged into the drainage pool, and the gas is discharged into the exhaust storage tank 8. The gas-liquid mixture generated by the treatment of the high-concentration coking desulfurization waste liquid passes through the heat exchanger 9 for heat exchange, and the displaced waste heat is reused in the first waste liquid preheater 4 in step (1).
本实用新型工艺流程简单，易操作，反应器中压力、温度等通过一体化电控与压力系统控制，可迅速降解去除高浓度焦化脱硫废液的有机物，对焦化脱硫废液中COD和NH3-N的去除率可达97%以上。The utility model has a simple technological process and is easy to operate. The pressure and temperature in the reactor are controlled by an integrated electric control and pressure system, which can quickly degrade and remove organic matter in high-concentration coking desulfurization waste liquid, and COD and NH 3 in coking desulfurization waste liquid The removal rate of -N can reach more than 97%.
本实用新型利用超临界水氧化技术，针对焦化余热的高浓度废水所具有的有机污染物浓度高、种类多、毒性大、难于降解和余热未利用等特点，对于焦化余热的高浓度焦化脱硫废液中难降解有机物具有较好的去除效果。处理过后的COD和NH3-N浓度均可达到国家排放标准，工艺简单、操作方便、反应迅速、运行成本费用低、无二次污染、催化剂可回收再利用和热量资源循环利用。The utility model utilizes supercritical water oxidation technology, aiming at the characteristics of high-concentration waste water of coking waste heat, such as high concentration of organic pollutants, many types, high toxicity, difficulty in degradation and unutilized waste heat, etc. Refractory organic matter in the liquid has a good removal effect. The concentration of COD and NH 3 -N after treatment can reach the national emission standard, the process is simple, the operation is convenient, the response is fast, the operation cost is low, no secondary pollution, the catalyst can be recycled and reused, and the heat resource can be recycled.
最后所应说明的是，以上实施例仅用以说明本实用新型的技术方案而非限制，尽管参照较佳实施例对本实用新型进行了详细说明，本领域的普通技术人员应当理解，可以对本实用新型的技术方案进行修改或者等同替换，而不脱离本实用新型技术方案的精神和范围，其均应涵盖在本实用新型的权利要求范围当中。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the utility model without limitation. Although the utility model has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the utility model can be Modifications or equivalent replacements of the technical solutions of the new utility model without departing from the spirit and scope of the technical solutions of the utility model shall be covered by the claims of the utility model.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819039A (en) * | 2014-02-26 | 2014-05-28 | 武汉科技大学 | High-concentration coking desulphurization waste liquid treating apparatus and method for catalytic treatment of high-concentration coking desulphurization waste liquid by using waste heat of coking |
| CN106006919A (en) * | 2016-07-19 | 2016-10-12 | 苏州英瑞特环保科技有限公司 | Supercritical water treatment equipment |
| CN107055470A (en) * | 2017-03-10 | 2017-08-18 | 同济大学 | A kind of hot utilization system of liquid organic hydrogen storage carrier reactor |
| CN112624478A (en) * | 2020-12-30 | 2021-04-09 | 济南工程职业技术学院 | Method for efficiently treating wastewater |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819039A (en) * | 2014-02-26 | 2014-05-28 | 武汉科技大学 | High-concentration coking desulphurization waste liquid treating apparatus and method for catalytic treatment of high-concentration coking desulphurization waste liquid by using waste heat of coking |
| CN106006919A (en) * | 2016-07-19 | 2016-10-12 | 苏州英瑞特环保科技有限公司 | Supercritical water treatment equipment |
| CN107055470A (en) * | 2017-03-10 | 2017-08-18 | 同济大学 | A kind of hot utilization system of liquid organic hydrogen storage carrier reactor |
| CN112624478A (en) * | 2020-12-30 | 2021-04-09 | 济南工程职业技术学院 | Method for efficiently treating wastewater |
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