CN106731644A - A kind of method that modified pyrolusite processes coal-fired flue-gas - Google Patents
A kind of method that modified pyrolusite processes coal-fired flue-gas Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003546 flue gas Substances 0.000 title claims abstract description 80
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 104
- 230000005855 radiation Effects 0.000 claims abstract description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 85
- 239000011707 mineral Substances 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 26
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 75
- 229910052753 mercury Inorganic materials 0.000 description 13
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- 238000010298 pulverizing process Methods 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01D53/81—Solid phase processes
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
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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
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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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
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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Abstract
本发明涉及燃煤烟气处理技术领域，尤其是一种改性软锰矿处理燃煤烟气的方法，通过将软锰矿微波辐射制备成矿粉后，将矿粉采用Li2MnTiO4和MnFe2O4的混合物料改性处理，使得软锰矿中的二氧化锰活性增强，对燃煤烟气中的硫氧化物以及单质汞的脱除更加精确，提高了对燃煤烟气中硫氧化物和单质汞的脱除率，使得对硫氧化物和单质汞的脱除率达到了96％以上，并且采用的原料易得，成本较低，处理过程中，还能获得附加值较高的硫酸锰产品，增大了对燃煤烟气处理的利润。The invention relates to the technical field of coal-fired flue gas treatment, in particular to a method for treating coal-fired flue gas with modified pyrolusite. After microwave radiation of pyrolusite is used to prepare ore powder, the ore powder is made of Li 2 MnTiO 4 and MnFe 2 The modification of O 4 mixed materials enhances the activity of manganese dioxide in pyrolusite, and removes sulfur oxides and elemental mercury in coal-fired flue gas more accurately, improving the efficiency of sulfur oxides in coal-fired flue gas. And the removal rate of elemental mercury makes the removal rate of sulfur oxide and elemental mercury reach more than 96%, and the raw materials used are easy to get, the cost is low, and sulfuric acid with high added value can be obtained during the treatment process Manganese products increase the profit of coal-fired flue gas treatment.
Description
技术领域technical field
本发明涉及燃煤烟气处理技术领域，尤其是一种改性软锰矿处理燃煤烟气的方法。The invention relates to the technical field of coal-burning flue gas treatment, in particular to a method for treating coal-burning flue gas with modified pyrolusite.
背景技术Background technique
煤碳是我国主要的能源结构，其产量占据我国一次能量产量的70％左右，成为我国能源应用过程中的主要支撑。煤碳中含有大量的废弃物，尤其是含有大量的硫氧化物和汞成分，在煤碳燃烧过程中，硫氧化物以二氧化硫的形态、汞成分以汞蒸气的形式，随着烟气排放在环境中，二氧化硫再与雨水接触形成酸雨，汞蒸气在遇到冷空气的条件下，跟随雨水返回地表，使得地表严重受到污染。Coal is my country's main energy structure, and its output accounts for about 70% of my country's primary energy output, becoming the main support in my country's energy application process. Coal contains a large amount of waste, especially a large amount of sulfur oxides and mercury components. During the combustion of coal, sulfur oxides are in the form of sulfur dioxide, and mercury components are in the form of mercury vapor. In the environment, sulfur dioxide contacts with rainwater to form acid rain, and mercury vapor returns to the surface with the rainwater under the condition of cold air, making the surface seriously polluted.
随着人们对环境质量的要求越来越高，对于废气排放过程中，也出现了严格的标准，这使得煤碳燃烧过程中，有必要将燃烧产生的烟气进行脱硫脱汞处理，使得烟气排放中的硫氧化物和单质汞的含量达标，降低烟气排放对环境的污染；现有技术中，同时脱硫脱汞的研究技术得到了研究，如专利申请号为201610149557采用低品位软锰矿进行脱硫脱汞处理；如专利号为200810118580提供脱硫脱汞剂等。As people's requirements for environmental quality are getting higher and higher, strict standards have also appeared in the process of exhaust gas discharge, which makes it necessary to desulfurize and demercurize the flue gas generated during coal combustion, so that the smoke The content of sulfur oxides and elemental mercury in the gas emissions is up to the standard, reducing the pollution of flue gas emissions to the environment; in the existing technology, the research technology of simultaneous desulfurization and mercury removal has been studied, such as the patent application number 201610149557 using low-grade pyrolusite Carry out desulfurization and mercury removal treatment; for example, the patent No. 200810118580 provides desulfurization and mercury removal agents, etc.
目前，由于专门的脱硫脱汞剂制备的原料难以获得，使得对烟气脱硫脱汞处理的成本较高；而采用软锰矿对烟气进行脱硫脱汞处理的方案，虽然其成本较低，并且能够在脱硫脱汞过程中，获得附加的硫酸锰产品，提高了产品的附加值；但是其对烟气脱硫脱汞脱除率较为不理想，对于脱硫脱除率能够达到70％左右，脱汞脱除率由传统的54％左右提高到64％左右，使得排放的烟气中，依然含有大量的硫、汞成分；为此，对于将烟气中的硫、汞成分的脱除率进一步的提高，依然是本领域技术人员不断努力的方向。At present, due to the difficulty in obtaining raw materials for the preparation of special desulfurization and mercury removal agents, the cost of flue gas desulfurization and mercury removal treatment is relatively high; and the use of pyrolusite for flue gas desulfurization and mercury removal, although its cost is relatively low, and In the desulfurization and mercury removal process, additional manganese sulfate products can be obtained, which increases the added value of the product; however, its removal rate for flue gas desulfurization and mercury removal is not ideal, and the desulfurization removal rate can reach about 70%. The removal rate is increased from about 54% to about 64%, so that the discharged flue gas still contains a large amount of sulfur and mercury components; Improvement is still the direction of continuous efforts of those skilled in the art.
发明内容Contents of the invention
为了解决现有技术中存在的上述技术问题，本发明提供一种改性软锰矿处理燃煤烟气的方法。In order to solve the above-mentioned technical problems existing in the prior art, the present invention provides a method for treating coal-fired flue gas with modified pyrolusite.
具体是通过以下技术方案得以实现的：Specifically, it is achieved through the following technical solutions:
一种改性软锰矿处理燃煤烟气的方法，包括以下步骤：A method for treating coal-burning flue gas with modified pyrolusite, comprising the following steps:
(1)将软锰矿采用微波辐射处理后，将其制备成粉末，得到矿粉；(1) After pyrolusite is treated with microwave radiation, it is prepared into powder to obtain ore powder;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为50-70℃中处理0.5-1.7h，加入4-12倍质量步骤(1)的矿粉，超声波处理10-30min，浇水，使得矿粉湿润，采用温度为130-210℃处理3-7min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 50-70°C for 0.5-1.7h, add 4-12 times the mass step (1 ) mineral powder, ultrasonic treatment for 10-30min, watering to make the mineral powder moist, and adopting a temperature of 130-210°C for 3-7min to obtain modified mineral powder;
(3)将改性矿粉填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气与改性矿粉接触反应的时间为20-30min，将其排出，即可。(3) Fill the modified mineral powder in the fixed-bed reactor, and after the coal-fired flue gas enters the fixed-bed reactor to contact and react with the filled modified mineral powder layer, the contact reaction between the coal-fired flue gas and the modified mineral powder The time is 20-30min, just discharge it.
所述的制备成粉末，是将微波辐射处理的软锰矿升温至300-600℃，浇水，使得软锰矿发生水热化反应，粉化，获得矿粉。The preparation into powder is to raise the temperature of the pyrolusite treated with microwave radiation to 300-600° C., and water it, so that the pyrolusite undergoes a hydrothermal reaction and pulverizes to obtain mineral powder.
所述的微波辐射，微波功率为80-230W，微波辐射时间为15-33min。For the microwave radiation, the microwave power is 80-230W, and the microwave radiation time is 15-33min.
所述的超声波，频率为40-70Hz。The frequency of the ultrasonic wave is 40-70Hz.
所述的燃煤烟气，其通入固定床反应器的流速为10-15L/min。The flow rate of the coal-fired flue gas passing into the fixed-bed reactor is 10-15L/min.
所述的燃煤烟气，其温度为80-140℃。The temperature of the coal-fired flue gas is 80-140°C.
所述的改性矿粉，在填充进入固定床反应器中前，还向其中加入有占改性矿粉质量3-11％的氧化铜粉末。Before the modified mineral powder is filled into the fixed-bed reactor, copper oxide powder accounting for 3-11% of the mass of the modified mineral powder is added therein.
所述的改性矿粉，其粒度为20-80目。The particle size of the modified mineral powder is 20-80 mesh.
所述的步骤，还包括在改性矿粉与燃煤烟气接触反应后，将其置于温度为40-70℃的水中浸泡、过滤。The step also includes soaking and filtering the modified mineral powder in water at a temperature of 40-70° C. after the contact reaction of the modified mineral powder with the coal-fired flue gas.
与现有技术相比，本发明创造的技术效果体现在：Compared with the prior art, the technical effects created by the present invention are reflected in:
通过将软锰矿微波辐射制备成矿粉后，将矿粉采用Li2MnTiO4和MnFe2O4的混合物料改性处理，使得软锰矿中的二氧化锰活性增强，对燃煤烟气中的硫氧化物以及单质汞的脱除更加精确，提高了对燃煤烟气中硫氧化物和单质汞的脱除率，使得对硫氧化物和单质汞的脱除率达到了96％以上，并且采用的原料易得，成本较低，处理过程中，还能获得附加值较高的硫酸锰产品，增大了对燃煤烟气处理的利润。After the pyrolusite is prepared into ore powder by microwave radiation, the ore powder is modified with a mixture of Li 2 MnTiO 4 and MnFe 2 O 4 , so that the activity of manganese dioxide in the pyrolusite is enhanced. The removal of sulfur oxides and elemental mercury is more precise, which improves the removal rate of sulfur oxides and elemental mercury in coal-fired flue gas, making the removal rate of sulfur oxides and elemental mercury reach more than 96%, and The raw materials used are easy to obtain, the cost is low, and manganese sulfate products with high added value can be obtained during the treatment process, which increases the profit of coal-fired flue gas treatment.
为了能够进一步的说明本发明创造的技术方案能够对燃煤烟气中硫氧化物和单质汞的脱除效率，本发明创造的研究者将实施例1-6的处理方法对下列模拟燃煤烟气进行脱硫脱汞处理，并对处理前后的模拟烟气中的硫氧化物、单质汞的含量检测，同时对处理模拟烟气后的改性矿粉采用温度为40-70℃的热水浸泡处理10-20min后，再将其过滤，并将滤液进行浓缩结晶，回收硫酸锰，检测硫酸锰的纯度，其结果如下表1所示：In order to further illustrate the technical solution created by the present invention to the removal efficiency of sulfur oxides and elemental mercury in coal-fired flue gas, the researchers of the present invention applied the treatment methods of Examples 1-6 to the following simulated coal-fired smoke Desulfurization and mercury removal of the flue gas is carried out, and the content of sulfur oxides and elemental mercury in the simulated flue gas before and after treatment is detected. At the same time, the modified mineral powder after the simulated flue gas is soaked in hot water at a temperature of 40-70 ° C. After processing for 10-20min, it is filtered again, and the filtrate is carried out concentrated crystallization, reclaims manganese sulfate, detects the purity of manganese sulfate, and its result is as shown in table 1 below:
模拟烟气是以氮气为载体，调整温度为70-150℃之间，向其中充入二氧化硫和单质汞，获得。The simulated flue gas is obtained by using nitrogen as the carrier, adjusting the temperature between 70-150°C, and filling it with sulfur dioxide and elemental mercury.
表1Table 1
由上表数据可以看出，对于改性软锰矿粉能够将燃煤烟气中的硫氧化物和单质汞的脱除率提高到96％以上，而且获得的附加产品的纯度较高，产品附加值较高，降低了燃煤烟气处理的成本，提高了经济效益。It can be seen from the data in the above table that the modified pyrolusite powder can increase the removal rate of sulfur oxides and elemental mercury in coal-fired flue gas to more than 96%, and the additional products obtained are of high purity. The value is higher, which reduces the cost of coal-fired flue gas treatment and improves economic benefits.
具体实施方式detailed description
下面结合具体的实施方式来对本发明的技术方案做进一步的限定，但要求保护的范围不仅局限于所作的描述。The technical solutions of the present invention will be further limited below in conjunction with specific embodiments, but the scope of protection is not limited to the descriptions made.
在某些实施例中，改性软锰矿处理燃煤烟气的方法，包括以下步骤：In some embodiments, the method for treating coal-fired flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理后，将其制备成粉末，得到矿粉；(1) After pyrolusite is treated with microwave radiation, it is prepared into powder to obtain ore powder;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为50-70℃中处理0.5-1.7h，加入4-12倍质量步骤(1)的矿粉，超声波处理10-30min，浇水，使得矿粉湿润，采用温度为130-210℃处理3-7min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 50-70°C for 0.5-1.7h, add 4-12 times the mass step (1 ) mineral powder, ultrasonic treatment for 10-30min, watering to make the mineral powder moist, and adopting a temperature of 130-210°C for 3-7min to obtain modified mineral powder;
(3)将改性矿粉填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气与改性矿粉接触反应的时间为20-30min，将其排出，即可。(3) Fill the modified mineral powder in the fixed-bed reactor, and after the coal-fired flue gas enters the fixed-bed reactor to contact and react with the filled modified mineral powder layer, the contact reaction between the coal-fired flue gas and the modified mineral powder The time is 20-30min, just discharge it.
在某些实施例中，所述的制备成粉末，是将微波辐射处理的软锰矿升温至300-600℃，浇水，使得软锰矿发生水热化反应，粉化，获得矿粉。水热化反应，使得软锰矿粉化过程更加均匀，并且改变传统的软锰矿机械粉化造成的晶体结构破坏的缺陷，使得软锰矿粉化过程温和化，提高了软锰矿粉化后的活性，有利于提高燃煤烟气脱硫脱汞的脱除率。In some embodiments, the preparation into powder is heating the pyrolusite treated with microwave radiation to 300-600° C., watering, so that the pyrolusite undergoes a hydrothermal reaction and pulverizes to obtain mineral powder. The hydrothermal reaction makes the pyrolusite pulverization process more uniform, and changes the defects of crystal structure damage caused by traditional pyrolusite mechanical pulverization, which makes the pyrolusite pulverization process milder and improves the activity of pyrolusite pulverization. It is beneficial to improve the removal rate of coal-fired flue gas desulfurization and mercury removal.
在某些实施例中，所述的微波辐射，微波功率为80-230W，微波辐射时间为15-33min。In some embodiments, for the microwave radiation, the microwave power is 80-230W, and the microwave radiation time is 15-33min.
在某些实施例中，所述的超声波，频率为40-70Hz。In some embodiments, the ultrasonic wave has a frequency of 40-70 Hz.
在某些实施例中，所述的燃煤烟气，其通入固定床反应器的流速为10-15L/min。确保燃煤烟气在固定床反应器中停留一定时间，提高与改性矿粉接触的时间，有利于提高脱除率。In some embodiments, the coal-burning flue gas is passed into the fixed-bed reactor at a flow rate of 10-15 L/min. Ensure that the coal-fired flue gas stays in the fixed-bed reactor for a certain period of time, and increase the contact time with the modified mineral powder, which is conducive to improving the removal rate.
在某些实施例中，所述的燃煤烟气，其温度为80-140℃。该温度条件下，能够使得软锰矿中的有效成分的活化能较高，有利于提高脱除率。In some embodiments, the temperature of the coal-fired flue gas is 80-140°C. Under this temperature condition, the activation energy of the effective components in the pyrolusite can be made higher, which is beneficial to improve the removal rate.
在某些实施例中，所述的改性矿粉，在填充进入固定床反应器中前，还向其中加入有占改性矿粉质量3-11％的氧化铜粉末。氧化铜粉末能够起到催化以及活化改性软锰矿粉的目的，提高脱除率。In some embodiments, before the modified mineral powder is filled into the fixed-bed reactor, copper oxide powder is added to it, accounting for 3-11% by mass of the modified mineral powder. The copper oxide powder can catalyze and activate the modified pyrolusite powder to improve the removal rate.
在某些实施例中，所述的改性矿粉，其粒度为20-80目。In some embodiments, the particle size of the modified mineral powder is 20-80 mesh.
在某些实施例中，所述的步骤，还包括在改性矿粉与燃煤烟气接触反应后，将其置于温度为40-70℃的水中浸泡、过滤。实现了产品附加值的提高。In some embodiments, the step further includes immersing and filtering the modified mineral powder in water at a temperature of 40-70° C. after contacting and reacting with the coal-fired flue gas. Realized the improvement of product added value.
实施例1Example 1
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理后，将其粉碎制备成粉末，得到矿粉；(1) After pyrolusite is treated with microwave radiation, it is pulverized and prepared into powder to obtain ore powder;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为50℃中处理0.5h，加入4倍质量步骤(1)的矿粉，超声波处理10min，浇水，使得矿粉湿润，采用温度为130℃处理3min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 50°C for 0.5h, add 4 times the mass of the mineral powder in step (1), and ultrasonically Treat for 10 minutes, water to make the mineral powder moist, and use a temperature of 130°C for 3 minutes to obtain modified mineral powder;
(3)将改性矿粉填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气与改性矿粉接触反应的时间为20min，将其排出，即可。(3) Fill the modified mineral powder in the fixed-bed reactor, and after the coal-fired flue gas enters the fixed-bed reactor to contact and react with the filled modified mineral powder layer, the contact reaction between the coal-fired flue gas and the modified mineral powder The time is 20min, just discharge it.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为40℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 40°C and filtered.
实施例2Example 2
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理，微波功率为80W，微波辐射时间为15min，升温至300℃，浇水，使得软锰矿发生水热化反应，粉化，得到矿粉；(1) The pyrolusite is treated with microwave radiation, the microwave power is 80W, the microwave radiation time is 15min, the temperature is raised to 300° C., watered, so that the pyrolusite undergoes hydrothermal reaction, pulverization, and mineral powder is obtained;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为70℃中处理1.7h，加入12倍质量步骤(1)的矿粉，超声波处理30min，浇水，使得矿粉湿润，采用温度为210℃处理7min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 70°C for 1.7h, add 12 times the mass of the mineral powder in step (1), and ultrasonically Treat for 30 minutes, water to make the mineral powder moist, and use a temperature of 210°C for 7 minutes to obtain modified mineral powder;
(3)将改性矿粉填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气与改性矿粉接触反应的时间为30min，将其排出，即可。(3) Fill the modified mineral powder in the fixed-bed reactor, and after the coal-fired flue gas enters the fixed-bed reactor to contact and react with the filled modified mineral powder layer, the contact reaction between the coal-fired flue gas and the modified mineral powder The time is 30min, just discharge it.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为70℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 70°C and filtered.
实施例3Example 3
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理，微波功率为230W，微波辐射时间为33min，升温至600℃，浇水，使得软锰矿发生水热化反应，粉化，得到矿粉；(1) The pyrolusite is treated with microwave radiation, the microwave power is 230W, the microwave radiation time is 33min, the temperature is raised to 600°C, watered, so that the pyrolusite undergoes hydrothermal reaction, pulverization, and mineral powder is obtained;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为60℃中处理1.1h，加入11倍质量步骤(1)的矿粉，超声波处理20min，超声波频率为50Hz，浇水，使得矿粉湿润，采用温度为180℃处理5min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 60°C for 1.1h, add 11 times the mass of the mineral powder in step (1), and ultrasonically Treat for 20 minutes, the ultrasonic frequency is 50Hz, water to make the mineral powder moist, and the temperature is 180°C for 5 minutes to obtain modified mineral powder;
(3)将改性矿粉填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气通入固定床反应器的流速为10L/min，燃煤烟气与改性矿粉接触反应的时间为25min，将其排出，即可。(3) Fill the modified mineral powder in the fixed-bed reactor, and after the coal-fired flue gas enters the fixed-bed reactor to contact and react with the filled modified mineral powder layer, the flow rate of the coal-fired flue gas entering the fixed-bed reactor It is 10L/min, and the contact reaction time between coal-burning flue gas and modified mineral powder is 25min, and it is enough to discharge it.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为50℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 50°C and filtered.
实施例4Example 4
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理，微波功率为170W，微波辐射时间为25min，升温至500℃，浇水，使得软锰矿发生水热化反应，粉化，得到矿粉；(1) The pyrolusite is treated with microwave radiation, the microwave power is 170W, the microwave radiation time is 25min, the temperature is raised to 500° C., watered, so that the pyrolusite undergoes hydrothermal reaction, pulverization, and mineral powder is obtained;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为50℃中处理1.7h，加入5倍质量步骤(1)的矿粉，超声波处理30min，超声波频率为40Hz，浇水，使得矿粉湿润，采用温度为210℃处理5min，得到改性矿粉；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 50°C for 1.7h, add 5 times the mass of the mineral powder in step (1), and ultrasonically Treat for 30 minutes, the ultrasonic frequency is 40Hz, water to make the mineral powder moist, and the temperature is 210°C for 5 minutes to obtain modified mineral powder;
(3)向改性矿粉加入有占改性矿粉质量3％的氧化铜粉末，填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气通入固定床反应器的流速为13L/min，燃煤烟气与改性矿粉接触反应的时间为25min，将其排出，即可。(3) Add copper oxide powder accounting for 3% of the mass of the modified mineral powder to the modified mineral powder, fill it in a fixed-bed reactor, and enter the coal-fired flue gas into the fixed-bed reactor to contact the filled modified mineral powder layer After the reaction, the flow rate of the coal-fired flue gas into the fixed-bed reactor is 13L/min, and the contact reaction time between the coal-fired flue gas and the modified mineral powder is 25min, and then it is discharged.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为50℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 50°C and filtered.
实施例5Example 5
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理，微波功率为120W，微波辐射时间为15min，升温至600℃，浇水，使得软锰矿发生水热化反应，粉化，得到矿粉；(1) The pyrolusite is treated with microwave radiation, the microwave power is 120W, the microwave radiation time is 15min, the temperature is raised to 600° C., watered, so that the pyrolusite undergoes hydrothermal reaction, pulverization, and mineral powder is obtained;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为70℃中处理1.7h，加入7倍质量步骤(1)的矿粉，超声波处理17min，超声波频率为55Hz，浇水，使得矿粉湿润，采用温度为190℃处理6min，得到改性矿粉，其粒度为20目；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 70°C for 1.7h, add 7 times the mass of the mineral powder in step (1), and ultrasonically Treat for 17 minutes, the ultrasonic frequency is 55 Hz, water to make the mineral powder moist, and the temperature is 190 ° C for 6 minutes to obtain modified mineral powder with a particle size of 20 mesh;
(3)向改性矿粉加入有占改性矿粉质量11％的氧化铜粉末，填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气通入固定床反应器的流速为14L/min，燃煤烟气与改性矿粉接触反应的时间为23min，将其排出，即可。(3) Add copper oxide powder accounting for 11% of the mass of the modified mineral powder to the modified mineral powder, fill it in a fixed-bed reactor, and enter the coal-fired flue gas into the fixed-bed reactor to contact the filled modified mineral powder layer After the reaction, the flow rate of the coal-fired flue gas into the fixed-bed reactor is 14L/min, and the contact reaction time between the coal-fired flue gas and the modified mineral powder is 23min, and then it is discharged.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为50℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 50°C and filtered.
实施例6Example 6
改性软锰矿处理燃煤烟气的方法，包括以下步骤：The method for treating coal-burning flue gas with modified pyrolusite comprises the following steps:
(1)将软锰矿采用微波辐射处理，微波功率为230W，微波辐射时间为20min，升温至500℃，浇水，使得软锰矿发生水热化反应，粉化，得到矿粉；(1) The pyrolusite is treated with microwave radiation, the microwave power is 230W, the microwave radiation time is 20min, the temperature is raised to 500°C, and watered, so that the pyrolusite undergoes a hydrothermal reaction and is pulverized to obtain mineral powder;
(2)将Li2MnTiO4和MnFe2O4按照不为零的任意质量比混合后，将其置于温度为65℃中处理0.9h，加入11倍质量步骤(1)的矿粉，超声波处理10min，超声波频率为70Hz，浇水，使得矿粉湿润，采用温度为190℃处理4min，得到改性矿粉，其粒度为80目；(2) After mixing Li 2 MnTiO 4 and MnFe 2 O 4 according to any mass ratio that is not zero, place it at a temperature of 65°C for 0.9h, add 11 times the mass of the mineral powder in step (1), and ultrasonically Treat for 10 minutes, the ultrasonic frequency is 70 Hz, water to make the mineral powder moist, and the temperature is 190 ° C for 4 minutes to obtain modified mineral powder with a particle size of 80 mesh;
(3)向改性矿粉加入有占改性矿粉质量8％的氧化铜粉末，填充在固定床反应器中，将燃煤烟气进入固定床反应器与填充的改性矿粉层接触反应后，燃煤烟气通入固定床反应器的流速为12L/min，燃煤烟气与改性矿粉接触反应的时间为27min，将其排出，即可。(3) Add copper oxide powder accounting for 8% of the modified mineral powder mass to the modified mineral powder, fill it in a fixed-bed reactor, and bring the coal-fired flue gas into the fixed-bed reactor to contact with the filled modified mineral powder layer After the reaction, the flow rate of the coal-fired flue gas into the fixed-bed reactor is 12L/min, and the contact reaction time between the coal-fired flue gas and the modified mineral powder is 27min, and then it is discharged.
在改性矿粉与燃煤烟气接触反应后，将其置于温度为63℃的水中浸泡、过滤。After the modified mineral powder contacts and reacts with the coal-fired flue gas, it is immersed in water at a temperature of 63°C and filtered.
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Application publication date: 20170531 |
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