CN106823750A - It is a kind of to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration - Google Patents
It is a kind of to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration Download PDFInfo
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- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 24
- 230000023556 desulfurization Effects 0.000 title claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 15
- 239000011777 magnesium Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000005587 bubbling Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 4
- 241000883990 Flabellum Species 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 229910052753 mercury Inorganic materials 0.000 abstract description 13
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002093 peripheral effect Effects 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 6
- 239000010941 cobalt Substances 0.000 abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 6
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 14
- 229910001385 heavy metal Inorganic materials 0.000 description 13
- 239000002048 multi walled nanotube Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- -1 mercury ions Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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Abstract
本发明公开了一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置,该装置用于通过浆液泵与吸收塔连接,其包括装置本体,装置本体内中部位置设置有催化网床,催化网床与装置本体内周壁可拆卸固定,催化网床呈蜂窝结构,催化网床的内、外表面粘结有负载钴量为10%的纳米碳管催化剂,装置本体上端设置有进水管,下端一侧设置有出水管,装置本体内下端还设置有一根鼓泡管,鼓泡管一端的进气口延伸至装置本体外侧,鼓泡管上端均匀分布有多个通气孔,装置本体内下端的周壁上还设置有至少一个搅拌装置。本发明的目的装置解决了亚硫酸盐的氧化不充分以及系统结垢、管道堵塞的问题,提高了亚硫酸盐的氧化速率与效率,并对残留在脱硫浆液中的汞进行脱除。
The invention discloses a device for sulfite oxidation and coordinated mercury removal in magnesium desulfurization. The device is used to connect with an absorption tower through a slurry pump. , the catalytic net bed and the inner peripheral wall of the device body can be detachably fixed, the catalytic net bed has a honeycomb structure, the inner and outer surfaces of the catalytic net bed are bonded with a carbon nanotube catalyst with a cobalt load of 10%, and the upper end of the device body is provided with a water inlet pipe , one side of the lower end is provided with an outlet pipe, and a bubbler tube is arranged at the lower end of the device body. At least one stirring device is also arranged on the peripheral wall of the lower end. The object device of the present invention solves the problems of insufficient sulfite oxidation, system fouling and pipe blockage, improves the sulfite oxidation rate and efficiency, and removes mercury remaining in the desulfurization slurry.
Description
技术领域technical field
本发明属于镁法脱硫中亚硫酸盐的催化氧化以及协同脱除重金属的技术领域,尤其是涉及一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置。The invention belongs to the technical field of catalytic oxidation of sulfite in magnesium desulfurization and coordinated removal of heavy metals, and in particular relates to a device for sulfite oxidation and coordinated demercury removal in magnesium desulfurization.
背景技术Background technique
镁法脱硫是目前中小型工业锅炉常用的烟气处理工艺,但由于副产物亚硫酸镁的氧化反应速率相对缓慢,亚硫酸镁氧化不充分,纯度较低导致副产物无法直接使用。并且容易造成系统结垢、设备堵塞、而且还存在副产物回收率低、副产物难回收利用和排放液二次污染等问题。除此之外,烟气中残留的重金属(汞)也未得到去除,降低了副产品的品质,对经济价值产生了很大的影响。Magnesium desulfurization is currently a commonly used flue gas treatment process for small and medium-sized industrial boilers. However, due to the relatively slow oxidation reaction rate of the by-product magnesium sulfite, the oxidation of magnesium sulfite is insufficient, and the purity of the by-product cannot be used directly. And it is easy to cause system fouling, equipment blockage, and there are also problems such as low recovery rate of by-products, difficult recycling of by-products and secondary pollution of discharge liquid. In addition, the heavy metal (mercury) remaining in the flue gas has not been removed, which reduces the quality of by-products and has a great impact on economic value.
目前解决脱硫系统氧化能力不足的主要手段是添加催化剂以提高亚硫酸镁的氧化速率。但由于催化剂均以溶液形式加入脱硫浆液,导致应用过程的运行成本较高,且催化剂难以回收,催化剂的应用和推广也因此受到了极大的限制。并且对重金属也未起到脱除作用。At present, the main means to solve the insufficient oxidation capacity of the desulfurization system is to add catalysts to increase the oxidation rate of magnesium sulfite. However, since the catalyst is added to the desulfurization slurry in the form of a solution, the operating cost of the application process is high, and the catalyst is difficult to recycle, which greatly limits the application and promotion of the catalyst. And it has no effect on the removal of heavy metals.
发明内容Contents of the invention
本发明的目的是提供一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置,解决了亚硫酸盐的氧化不充分以及系统结垢、管道堵塞的问题,提高了亚硫酸盐的氧化速率与效率,对残留在脱硫浆液中的汞进行脱除。The purpose of the present invention is to provide a device for sulfite oxidation and coordinated mercury removal in magnesium desulfurization, which solves the problems of insufficient oxidation of sulfite, system fouling, and pipeline blockage, and improves the efficiency of sulfite. Oxidation rate and efficiency to remove mercury remaining in the desulfurization slurry.
为解决上述技术问题,本发明采用如下技术方案:In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:
一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置,该装置用于通过浆液泵与吸收塔连接,其包括装置本体,所述装置本体内中部位置设置有催化网床,所述催化网床与所述装置本体内周壁可拆卸固定,所述催化网床呈蜂窝结构,所述催化网床的内、外表面粘结有负载钴量为10%的纳米碳管催化剂,所述装置本体上端设置有进水管,下端一侧设置有出水管,所述装置本体内下端还设置有一根鼓泡管,所述鼓泡管一端的进气口延伸至所述装置本体外侧,所述鼓泡管上端均匀分布有多个通气孔,所述装置本体内下端的周壁上还设置有至少一个搅拌装置。A device for sulfite oxidation and coordinated mercury removal in magnesium desulfurization. The device is used to connect with the absorption tower through a slurry pump. The catalytic mesh bed and the inner peripheral wall of the device body are detachably fixed, the catalytic mesh bed is in a honeycomb structure, and the inner and outer surfaces of the catalytic mesh bed are bonded with a carbon nanotube catalyst with a cobalt load of 10%. The upper end of the device body is provided with a water inlet pipe, and one side of the lower end is provided with a water outlet pipe. The inner and lower ends of the device body are also provided with a bubbling tube, and the air inlet at one end of the bubbling tube extends to the outside of the device body. The upper end of the bubbling tube is evenly distributed with a plurality of ventilation holes, and at least one stirring device is provided on the peripheral wall of the inner lower end of the device body.
进一步的,所述负载钴量为10%的纳米碳管催化剂的制备方法如下:Further, the preparation method of the carbon nanotube catalyst with a cobalt load of 10% is as follows:
预处理:称取多壁纳米碳管于锥形瓶中,加入60%HNO3,多壁纳米碳管与HNO3的质量(g)体积(ml)比为1:15,80℃电磁加热搅拌,同时冷凝水回流,回流结束,真空抽滤洗涤至中性,在烘箱内120℃干燥2h,并称重;Pretreatment: Weigh multi-walled carbon nanotubes into a conical flask, add 60% HNO 3 , the ratio of mass (g) to volume (ml) of multi-walled carbon nanotubes to HNO 3 is 1:15, and heat and stir at 80°C At the same time, the condensed water is refluxed, and the reflux is completed, vacuum filtered and washed to neutral, dried in an oven at 120°C for 2 hours, and weighed;
称取0.986重量份的Co(NO3)·6H2O和2重量份预处理后的多壁纳米碳管,将干燥后的多壁纳米碳管和Co(NO3)·6H2O一起放入锥形瓶,溶于无水乙醇,无水乙醇与称取的预处理后的多壁纳米碳管的体积(ml)质量(g)比为25:1;Weigh 0.986 parts by weight of Co(NO 3 )·6H 2 O and 2 parts by weight of pretreated multi-walled carbon nanotubes, put the dried multi-walled carbon nanotubes and Co(NO 3 )·6H 2 O together Put into conical flask, be dissolved in absolute ethanol, the volume (ml) mass (g) ratio of absolute ethanol and the pretreated multi-walled carbon nanotubes taken by weighing is 25:1;
再次30℃下电磁加热搅拌,超声分散30min,120℃干燥2h;Electromagnetic heating and stirring at 30°C again, ultrasonic dispersion for 30 minutes, and drying at 120°C for 2 hours;
将干燥后的产物放入N2保护管式炉中焙烧。The dried product was roasted in a N2 protected tube furnace.
进一步的,所述保护管式炉中焙烧条件为:1h升温120℃,120℃保持1h,2h升温500℃,500℃保持3h。Further, the calcination conditions in the protective tube furnace are as follows: heating up to 120° C. for 1 hour, maintaining 120° C. for 1 hour, raising temperature to 500° C. for 2 hours, and maintaining 500° C. for 3 hours.
进一步的,所述装置本体内下端的对称的周壁上设置有2个搅拌装置。Further, two stirring devices are arranged on the symmetrical peripheral wall at the inner and lower end of the device body.
进一步的,所述搅拌装置为马达驱动的扇叶。Further, the stirring device is a fan blade driven by a motor.
与现有技术相比,本发明的有益技术效果:Compared with prior art, beneficial technical effect of the present invention:
对现有的脱硫工艺进行改进,在吸收塔内只进行脱硫(SO2的吸收),不进行亚硫酸盐的氧化,将本装置通过浆液泵与吸收塔连接,解决了亚硫酸盐的氧化不充分以及系统结垢、管道堵塞的问题,提高了亚硫酸盐的氧化速率与效率,对残留在脱硫浆液中的汞进行脱除;同时有效降低了吸收塔的高度,减小了吸收塔的尺寸,提高了副产品的回收率和品质,杜绝了排放液二次污染的问题,增加了经济效益。To improve the existing desulfurization process, only desulfurization (SO 2 absorption) is carried out in the absorption tower, and the oxidation of sulfite is not carried out. The device is connected with the absorption tower through a slurry pump to solve the problem of oxidation of sulfite Fully solve the problems of system fouling and pipeline blockage, improve the oxidation rate and efficiency of sulfite, and remove the mercury remaining in the desulfurization slurry; at the same time, the height of the absorption tower is effectively reduced, and the size of the absorption tower is reduced , improve the recovery rate and quality of by-products, eliminate the problem of secondary pollution of the discharge liquid, and increase economic benefits.
附图说明Description of drawings
下面结合附图说明对本发明作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings.
图1为本发明用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置的结构示意图;Fig. 1 is the structural representation of the device used for sulfite oxidation and coordinated mercury removal in magnesium desulfurization according to the present invention;
附图标记说明:1-装置本体;2-催化网床;3-进水管;4-出水管;5-鼓泡管;6-搅拌装置;Explanation of reference signs: 1-device body; 2-catalytic net bed; 3-inlet pipe; 4-outlet pipe; 5-bubbling pipe; 6-stirring device;
图2为单独去除重金属、重金属/亚硫酸盐同时存在下重金属离子去除效率图;Figure 2 is a graph showing the removal efficiency of heavy metals alone, heavy metals/sulfites in the presence of heavy metal ions;
图3为亚硫酸镁氧化速率图。Figure 3 is a diagram of the oxidation rate of magnesium sulfite.
具体实施方式detailed description
如图1所示,一种用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置,该装置用于通过浆液泵与吸收塔连接,其包括装置本体1,所述装置本体1内中部位置设置有催化网床2,所述催化网床2与所述装置本体1内周壁可拆卸固定,所述催化网床2通过挂件挂接于周壁上,所述催化网床2呈蜂窝结构,所述催化网床2的内、外表面粘接有负载钴量为10%的纳米碳管催化剂,所述装置本体1上端设置有进水管3,下端一侧设置有出水管4,所述装置本体1内下端还设置有一根鼓泡管5,所述鼓泡管一端的进气口延伸至所述装置本体1外侧,所述鼓泡管5上端均匀分布有多个通气孔,所述装置本体1内下端的周壁上还对称设置有2个搅拌装置6,所述搅拌装置6为马达驱动的扇叶。As shown in Figure 1, a device for sulfite oxidation and coordinated mercury removal in magnesium desulfurization, the device is used to connect with the absorption tower through a slurry pump, it includes a device body 1, the middle part of the device body 1 The position is provided with a catalytic net bed 2, the catalytic net bed 2 and the inner peripheral wall of the device body 1 are detachably fixed, the catalytic net bed 2 is hung on the peripheral wall by a pendant, and the catalytic net bed 2 is in a honeycomb structure. The inner and outer surfaces of the catalytic mesh bed 2 are bonded with a carbon nanotube catalyst with a cobalt load of 10%. The upper end of the device body 1 is provided with a water inlet pipe 3, and one side of the lower end is provided with an outlet pipe 4. The lower end of the body 1 is also provided with a bubbling tube 5, the air inlet at one end of the bubbling tube extends to the outside of the device body 1, the upper end of the bubbling tube 5 is evenly distributed with a plurality of ventilation holes, the device Two stirring devices 6 are symmetrically arranged on the peripheral wall of the inner lower end of the body 1, and the stirring devices 6 are fan blades driven by a motor.
其中,所述负载钴量为10%的纳米碳管催化剂的制备方法如下:Wherein, the preparation method of the carbon nanotube catalyst with a cobalt load of 10% is as follows:
预处理:称取10g的多壁纳米碳管于锥形瓶中,加入150ml体积分数为60%的HNO3,80℃电磁加热搅拌,同时冷凝水回流,回流结束,真空抽滤洗涤至中性,在烘箱内120℃干燥2h,并称重;Pretreatment: Weigh 10g of multi-wall carbon nanotubes into a conical flask, add 150ml of HNO 3 with a volume fraction of 60%, heat and stir at 80°C with electromagnetic heating, and at the same time reflux the condensed water. After the reflux is complete, vacuum filter and wash until neutral , dried in an oven at 120°C for 2 hours, and weighed;
称取0.986g的Co(NO3)·6H2O和2g预处理后的多壁纳米碳管,将干燥后的多壁纳米碳管和Co(NO3)·6H2O一起放入锥形瓶,溶于50ml的无水乙醇;Weigh 0.986g of Co(NO 3 )·6H 2 O and 2g of pretreated multi-walled carbon nanotubes, put the dried multi-walled carbon nanotubes and Co(NO 3 )·6H 2 O into the conical bottle, dissolved in 50ml of absolute ethanol;
再次30℃下电磁加热搅拌,超声分散30min,120℃干燥2h;Electromagnetic heating and stirring at 30°C again, ultrasonic dispersion for 30 minutes, and drying at 120°C for 2 hours;
将干燥后的产物放入N2保护管式炉中焙烧,焙烧条件为:1h升温120℃,120℃保持1h,2h升温500℃,500℃保持3h。The dried product was roasted in a N2 -protected tube furnace under the following conditions: heating up to 120°C for 1h, keeping at 120°C for 1h, heating up to 500°C for 2h, and keeping at 500°C for 3h.
使用时,现有的吸收塔内只进行脱硫(SO2的吸收),不进行亚硫酸盐的氧化,而是将本发明的用于镁法脱硫中亚硫酸盐氧化与协同脱汞的装置的进水口通过浆液泵与吸收塔连接,然后以鼓泡的形式在经鼓泡管5由装置本体1内底部鼓入空气气泡,在该装置下部安装的搅拌装置6会对通入的浆液进行搅拌,粘结了负载钴的多壁纳米碳管催化剂的催化网床浸在浆液面以下,保证亚硫酸盐的充分氧化以及协同脱汞,反应以后的溶液基本澄清。本发明解决了亚硫酸盐的氧化不充分以及系统结垢、管道堵塞的问题,提高了亚硫酸盐的氧化速率与效率,同时有效降低了吸收塔的高度,减小了吸收塔的尺寸;并对残留在脱硫浆液中的汞进行脱除,解决了副产物MgSO4品质与回收率较低的问题,提高了副产品MgSO4的回收率和品质,减少了排放液二次污染的问题,增加了经济效益。During use, only desulfurization (SO 2 absorption) is carried out in the existing absorption tower, and the oxidation of sulfite is not carried out, but the device for sulfite oxidation and coordinated demercuration in the magnesium desulfurization of the present invention is used The water inlet is connected to the absorption tower through a slurry pump, and then air bubbles are blown into the bottom of the device body 1 through the bubbling tube 5 in the form of bubbling, and the stirring device 6 installed at the bottom of the device will stir the incoming slurry The catalytic mesh bed bonded with the cobalt-loaded multi-wall carbon nanotube catalyst is immersed below the slurry surface to ensure sufficient oxidation of sulfite and synergistic mercury removal, and the solution after the reaction is basically clarified. The invention solves the problems of insufficient sulfite oxidation, system fouling and pipe blockage, improves the oxidation rate and efficiency of sulfite, effectively reduces the height of the absorption tower, and reduces the size of the absorption tower; and The mercury remaining in the desulfurization slurry is removed, which solves the problem of low quality and recovery rate of the by-product MgSO 4 , improves the recovery rate and quality of the by-product MgSO 4 , reduces the problem of secondary pollution of the discharge liquid, and increases the economic benefits.
如图2所示,在亚硫酸镁和汞离子共存在、亚硫酸镁和镉离子共存在、亚硫酸镁和镍离子共存下三种重金属离子共存在,以及重金属离子单独存在下的吸附效率。由图可知,对于,Hg2+、Cd2+离子来说,单独存在下的Co-CNTs催化剂对其的去除效率要高于与亚硫酸盐共存时的去除效率,但影响不大,亚硫酸盐的存在对Ni2+的去除基本没有影响,Hg2+、Cd2+、Ni2+的去除效率分别下降了2.0%、2.9%、0.01%,对镍离子的影响也有可能是实验误差造成的。亚硫酸盐存在下,Co-CNTs对Hg2+、Cd2+、Ni2+的去除效率虽然有所降低,但依然在90%以上,说明Co-CNTs对重金属有很好的吸附性能。As shown in Figure 2, the adsorption efficiency of the three heavy metal ions in the coexistence of magnesium sulfite and mercury ions, the coexistence of magnesium sulfite and cadmium ions, the coexistence of magnesium sulfite and nickel ions, and the presence of heavy metal ions alone. It can be seen from the figure that for Hg 2+ and Cd 2+ ions, the removal efficiency of the Co-CNTs catalyst in the presence of alone is higher than that of the co-existence of sulfite, but the effect is not significant. The presence of salt has almost no effect on the removal of Ni2+. The removal efficiency of Hg 2+ , Cd 2+ , and Ni 2+ decreased by 2.0%, 2.9%, and 0.01%, respectively. The effect on nickel ions may also be caused by experimental errors. In the presence of sulfite, the removal efficiency of Co-CNTs to Hg 2+ , Cd 2+ , and Ni 2+ was reduced, but still above 90%, which indicated that Co-CNTs had good adsorption performance for heavy metals.
如图3所示,在亚硫酸镁单独存在下、亚硫酸镁和汞离子共存在、亚硫酸镁和镉离子共存在、亚硫酸镁和镍离子共存下以及亚硫酸镁和三种重金属离子共存在,亚硫酸镁氧化速率图。由图可知,重金属离子存在下会对亚硫酸镁的氧化起到抑制作用,抑制作用强弱为Hg2++Cd2++Ni2+>Hg2+>Cd2+>Ni2+。虽然重金属离子会对亚硫酸盐的氧化速率有一定的抑制作用,但在与三种重金属离子共存的条件下氧化速率依然是没有催化剂时的4.5倍左右,依然对亚硫酸根的氧化有很好的催化性能。As shown in Figure 3, in the presence of magnesium sulfite alone, the coexistence of magnesium sulfite and mercury ions, the coexistence of magnesium sulfite and cadmium ions, the coexistence of magnesium sulfite and nickel ions, and the coexistence of magnesium sulfite and three heavy metal ions Existence, Magnesium Sulfite Oxidation Rate Diagram. It can be seen from the figure that the presence of heavy metal ions can inhibit the oxidation of magnesium sulfite, and the inhibitory effect is Hg 2+ +Cd 2+ +Ni 2+ >Hg 2+ >Cd 2+ >Ni 2+ . Although heavy metal ions will have a certain inhibitory effect on the oxidation rate of sulfite, the oxidation rate is still about 4.5 times that of no catalyst under the condition of coexistence with three heavy metal ions, and it still has a good effect on the oxidation of sulfite. catalytic performance.
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。The above-mentioned embodiments are only to describe the preferred mode of the present invention, not to limit the scope of the present invention. Without departing from the design spirit of the present invention, those skilled in the art may make various Variations and improvements should fall within the scope of protection defined by the claims of the present invention.
Claims (5)
- It is 1. a kind of to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration, it is characterised in that:The device is used to lead to Cross slurries pump to be connected with absorption tower, it includes device body, medium position is provided with catalysis net bed in described device body, described Catalysis net bed is detachably fixed with described device body internal perisporium, and the catalysis net bed is in honeycomb, the catalysis net bed Inner and outer surfaces are bonded with the CNT catalyst that Supported Co amount is 10%, and described device body upper end is provided with water inlet pipe, under End side is provided with outlet pipe, and lower end is additionally provided with a bubbling pipe, the air inlet of described bubbling pipe one end in described device body Mouth extends to described device outer body, under the bubbling pipe upper end is evenly distributed with multiple passages, described device body At least one agitating device is additionally provided with the perisporium at end.
- 2. according to claim 1 to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration, its feature exists In:The Supported Co amount is that the preparation method of 10% CNT catalyst is as follows:Pretreatment:Multiple-wall carbon nanotube is weighed in conical flask, 60%HNO is added3, multiple-wall carbon nanotube and HNO3Quality (g) Volume (ml) is than being 1:The stirring of 15,80 DEG C of Electromagnetic Heatings, while condensate return, backflow terminates, and vacuum filtration is washed to neutrality, 120 DEG C dry 2h in baking oven, and weigh;Weigh the Co (NO of 0.986 weight portion3)·6H2O and the pretreated multiple-wall carbon nanotube of 2 weight portions, will be dried more Wall carbon nanotube and Co (NO3)·6H2O is put into conical flask together, is dissolved in absolute ethyl alcohol, after absolute ethyl alcohol and the pretreatment for weighing Multiple-wall carbon nanotube volume (ml) quality (g) than be 25:1;Electromagnetic Heating stirring, ultrasonic disperse 30min at 30 DEG C again, 120 DEG C dry 2h;Dried product is put into N2Protection tubular type kiln roasting.
- 3. according to claim 2 to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration, its feature exists In:It is described protection tubular type kiln roasting condition be:1h heats up 120 DEG C, 120 DEG C of 500 DEG C of holding 1h, 2h intensifications, 500 DEG C of holdings 3h。
- 4. according to claim 1 to be aoxidized for magnesium processes desulfurization sulfite salt and the device for cooperateing with demercuration, its feature exists In:2 agitating devices are provided with described device body on the symmetrical perisporium of lower end.
- 5. according to claim 1 or 4 for magnesium processes desulfurization sulfite salt oxidation and the device for cooperateing with demercuration, its feature It is:The agitating device is the flabellum that motor drives.
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