CN102357505B - Combined additive for burnt fly ash vitrification and burnt fly ash vitrification method - Google Patents
Combined additive for burnt fly ash vitrification and burnt fly ash vitrification method Download PDFInfo
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- CN102357505B CN102357505B CN201110212907.0A CN201110212907A CN102357505B CN 102357505 B CN102357505 B CN 102357505B CN 201110212907 A CN201110212907 A CN 201110212907A CN 102357505 B CN102357505 B CN 102357505B
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- fly ash
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- 239000010881 fly ash Substances 0.000 title claims abstract description 43
- 238000004017 vitrification Methods 0.000 title claims abstract description 25
- 239000000654 additive Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 13
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910052925 anhydrite Inorganic materials 0.000 abstract description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
本发明公开了一种用于焚烧飞灰玻璃化的组合添加剂，包括：B2O3和石墨。本发明还公开了一种焚烧飞灰玻璃化方法，包括如下步骤：按照B2O3和飞灰的重量比为1∶4～10，石墨和飞灰的重量比为1∶20～50将B2O3和石墨添加到飞灰中；玻璃化处理温度为1150～1350℃，处理时间30～80分钟。本发明由于添加了一定比例的石墨，因此可以在加热过程中与焚烧飞灰中的CaSO4发生反应：促进硫元素的挥发，从而降低了黄相的影响，缩短了处理时间，提高了重金属的滞留率。The invention discloses a combined additive for vitrification of incineration fly ash, comprising: B 2 O 3 and graphite. The invention also discloses a vitrification method of incineration fly ash, comprising the following steps: according to the weight ratio of B2O3 and fly ash is 1 :4-10, and the weight ratio of graphite and fly ash is 1:20-50. B 2 O 3 and graphite are added to the fly ash; the vitrification treatment temperature is 1150-1350°C, and the treatment time is 30-80 minutes. Due to the addition of a certain proportion of graphite in the present invention, it can react with CaSO4 in the incineration fly ash during the heating process: the volatilization of sulfur element is promoted, thereby reducing the influence of the yellow phase, shortening the processing time, and improving the concentration of heavy metals. retention rate.
Description
技术领域technical field
本发明涉及固体废物处理领域，尤其涉及焚烧飞灰玻璃化方法用于该方法的组合添加剂和焚烧飞灰玻璃化方法，能够降低玻璃化难度，提高玻璃化效果。The invention relates to the field of solid waste treatment, in particular to a combined additive used in the incineration fly ash vitrification method and the incineration fly ash vitrification method, which can reduce the difficulty of vitrification and improve the vitrification effect.
背景技术Background technique
焚烧飞灰是焚烧法处理固体废物（如生活垃圾）的燃烧产物，由于重金属浸出率高于国家标准，被列为危险废物。玻璃化是无害化焚烧飞灰的先进技术，将焚烧飞灰和添加剂加热到熔融状态，经冷却形成化学性质稳定的玻璃体，凭借玻璃体极低的重金属浸出率达到无害化的目的。Incineration fly ash is the combustion product of solid waste (such as domestic waste) treated by incineration. Because the heavy metal leaching rate is higher than the national standard, it is listed as hazardous waste. Vitrification is an advanced technology for harmless incineration fly ash. It heats incineration fly ash and additives to a molten state and cools to form a chemically stable glass body. The purpose of harmlessness is achieved by virtue of the extremely low heavy metal leaching rate of the glass body.
玻璃化技术的关键是形成化学性质稳定的玻璃体，如何降低玻璃化处理温度，提高重金属滞留率是该技术的难点。降低玻璃化的处理温度就是要求在较低温度下可以形成良好的玻璃体，同时降低处理温度、缩短处理时间都是提高重金属滞留率的有效途径。The key to vitrification technology is to form a chemically stable glass body. How to reduce the temperature of vitrification treatment and increase the retention rate of heavy metals is the difficulty of this technology. Reducing the treatment temperature of vitrification requires that a good glass body can be formed at a lower temperature. At the same time, reducing the treatment temperature and shortening the treatment time are effective ways to increase the retention rate of heavy metals.
焚烧飞灰一般收集于脱酸处理后的布袋除尘器，所以含钙量很高，而硅铝含量很低，大部分不能直接玻璃化，一般需要配合添加剂才能得到良好的玻璃体，即冷却后形成澄清透明的玻璃化物质。玻璃体的形成条件与处理温度和物料成分相关，当处理温度较高时，杂质少易玻璃化，但能耗高、成本高，也会极大降低重金属的滞留率；当处理温度较低时，焚烧飞灰的杂质较多，玻璃化困难。由于受到焚烧飞灰中含硫化合物的影响，熔体冷却时会在产物表面形成一层黄色物质—黄相，黄相的存在会阻碍玻璃体网络结构的形成，无法在较短的处理时间内得到良好的玻璃体，而延长处理时间也会降低重金属的滞留率。以上因素制约了玻璃化技术的应用和发展，阻碍了我国焚烧飞灰的无害化进程。Incineration fly ash is generally collected in the bag filter after deacidification treatment, so the calcium content is very high, while the silicon and aluminum content is very low, and most of them cannot be vitrified directly. Generally, additives are needed to obtain a good glass body, that is, formed after cooling. Clear and transparent vitrified substance. The formation conditions of the glass body are related to the processing temperature and material composition. When the processing temperature is high, the impurities are less and easy to vitrify, but the energy consumption is high, the cost is high, and the retention rate of heavy metals will be greatly reduced; when the processing temperature is low, Incineration fly ash has more impurities and is difficult to vitrify. Due to the influence of sulfur-containing compounds in the incineration fly ash, a layer of yellow substance-yellow phase will be formed on the surface of the product when the melt is cooled. The existence of the yellow phase will hinder the formation of the vitreous network structure and cannot be obtained in a short processing time Good vitreous body, and prolonging the treatment time will also reduce the retention rate of heavy metals. The above factors have restricted the application and development of vitrification technology and hindered the harmless process of incineration fly ash in my country.
发明内容Contents of the invention
针对玻璃化技术存在的问题，本发明的目的在于提供一种焚烧飞灰玻璃化的组合添加剂和焚烧飞灰玻璃化方法，可以降低玻璃化处理温度，同时降低黄相的影响，缩短物料处理时间。进而通过降低处理温度、缩短处理时间来提高重金属的滞留率。In view of the problems existing in the vitrification technology, the purpose of the present invention is to provide a combined additive for vitrification of incineration fly ash and a vitrification method of incineration fly ash, which can reduce the vitrification treatment temperature, reduce the influence of the yellow phase, and shorten the material processing time . Furthermore, the retention rate of heavy metals can be increased by lowering the treatment temperature and shortening the treatment time.
为实现上述目的，本发明的一种用于焚烧飞灰玻璃化的组合添加剂包括：B2O3和石墨；所述B2O3和飞灰的重量比为1:4～10，所述石墨和飞灰的重量比为1:20～50。In order to achieve the above object, a combined additive for vitrification of incineration fly ash according to the present invention includes: B2O3 and graphite; the weight ratio of B2O3 and fly ash is 1:4-10, and the The weight ratio of graphite and fly ash is 1:20-50.
本发明的一种焚烧飞灰玻璃化方法包括如下步骤：按照B2O3和飞灰的重量比为1:4～10，石墨和飞灰的重量比为1:20～50将B2O3和石墨添加到飞灰中；玻璃化处理温度为1150～1350℃，处理时间30～80分钟。A vitrification method of incineration fly ash of the present invention comprises the following steps: according to the weight ratio of B2O3 and fly ash is 1:4～10 , and the weight ratio of graphite and fly ash is 1:20～50, B2O 3 and graphite are added to the fly ash; the vitrification treatment temperature is 1150-1350°C, and the treatment time is 30-80 minutes.
本发明由于添加了一定比例的石墨，因此可以在加热过程中与焚烧飞灰中的CaSO4发生反应：促进硫元素的挥发，从而降低了黄相的影响，缩短了处理时间，提高了重金属的滞留率。Due to the addition of a certain proportion of graphite in the present invention, it can react with CaSO4 in the incineration fly ash during the heating process: promote the volatilization of sulfur, thereby reducing the influence of the yellow phase, shortening the processing time, and improving the concentration of heavy metals. retention rate.
具体实施方式Detailed ways
实施例1Example 1
添加剂组成为：B2O3和飞灰的重量比为1:10，石墨和飞灰的重量比为1:20。The additive composition is: the weight ratio of B 2 O 3 and fly ash is 1:10, and the weight ratio of graphite and fly ash is 1:20.
按照上述比例将B2O3和石墨添加到飞灰中，在1250℃下，处理30分钟。Add B 2 O 3 and graphite to the fly ash according to the above ratio, and treat at 1250°C for 30 minutes.
在处理过程中，首先利用B2O3良好的助熔性能来降低玻璃化的处理温度，其次以B2O3作为网络形成体氧化物，可以组建四面体网络结构，促进玻璃体形成，另外以B2O3形成的玻璃体可以增大硫在玻璃体当中的溶解度，可以减少黄相的形成；新添加剂石墨在加热过程中会与焚烧费飞灰中的CaSO4发生如下反应：In the process of treatment, firstly, the good fluxing performance of B2O3 is used to reduce the treatment temperature of vitrification, and secondly, B2O3 is used as a network former oxide, which can form a tetrahedral network structure and promote the formation of glass bodies. The glass body formed by B 2 O 3 can increase the solubility of sulfur in the glass body and reduce the formation of yellow phase; the new additive graphite will react with CaSO 4 in the incineration fly ash during the heating process as follows:
C+CaSO4→CaS+CO2(g)C+CaSO 4 →CaS+CO 2 (g)
CaS+CaSO4→CaO+SO2(g)CaS+CaSO 4 →CaO+SO 2 (g)
经过处理并空冷后，可以得到澄清透明的玻璃体，大大降低了黄相的影响，可以缩短处理时间10分钟，同时可以提高重金属的滞留率10%。而没有含加添加剂时，焚烧飞灰的熔点高于1350℃，无法形成玻璃体。若只添加B2O3而不添加石墨，处理时间延长至40分钟，重金属滞留率下降10%。After treatment and air cooling, a clear and transparent glass body can be obtained, which greatly reduces the influence of the yellow phase, can shorten the processing time by 10 minutes, and can increase the retention rate of heavy metals by 10%. When no additives are added, the melting point of incineration fly ash is higher than 1350°C, and glass cannot be formed. If only B 2 O 3 was added without adding graphite, the treatment time was extended to 40 minutes, and the retention rate of heavy metals decreased by 10%.
实施例2Example 2
添加剂组成为：B2O3和飞灰的重量比为1:7，石墨和飞灰的重量比为1:30。The additive composition is: the weight ratio of B 2 O 3 and fly ash is 1:7, and the weight ratio of graphite and fly ash is 1:30.
处理方式同上，处理温度是1200℃，处理时间是40分钟，空冷后可以得到澄清透明的玻璃体。不添加石墨的实验，处理时间延长至60分钟，重金属滞留率下降20%。The treatment method is the same as above, the treatment temperature is 1200° C., the treatment time is 40 minutes, and a clear and transparent glass body can be obtained after air cooling. In the experiment without adding graphite, the treatment time was extended to 60 minutes, and the retention rate of heavy metals decreased by 20%.
实施例3Example 3
添加剂组成为：B2O3和飞灰的重量比为1:5，石墨和飞灰的重量比为1:50。The additive composition is: the weight ratio of B 2 O 3 and fly ash is 1:5, and the weight ratio of graphite and fly ash is 1:50.
处理方式同上，处理温度是1150℃，处理时间是80分钟，空冷后可以得到澄清透明的玻璃体。不添加石墨的实验，处理时间延长至120分钟，重金属滞留率下降40%。The treatment method is the same as above, the treatment temperature is 1150° C., the treatment time is 80 minutes, and a clear and transparent glass body can be obtained after air cooling. In the experiment without adding graphite, the treatment time was extended to 120 minutes, and the retention rate of heavy metals decreased by 40%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2052400C1 (en) * | 1993-06-01 | 1996-01-20 | Сергей Геннадьевич Баякин | Method for production of glass material from ash-slag waste |
| CN1931458A (en) * | 2006-09-06 | 2007-03-21 | 中国科学院生态环境研究中心 | Vacuum assisted heat treatment process with incinerated fly ash |
| CN1963304A (en) * | 2006-12-01 | 2007-05-16 | 清华大学 | Method for stabilizing treatment of refuse burning fly ash by using accelerated carbonation process |
| CN101531492A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for preparing light concrete by municipal solid waste incineration fly ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2099460A1 (en) * | 1992-07-02 | 1994-01-03 | Michelle G. Alexander | Process for vitrifying incinerator ash |
| JP3336890B2 (en) * | 1996-12-26 | 2002-10-21 | 日本鋼管株式会社 | Waste incineration fly ash treatment method |
| US7645095B2 (en) * | 2004-04-08 | 2010-01-12 | Newearth Pte Ltd. | Method for waste stabilisation and products obtained therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2052400C1 (en) * | 1993-06-01 | 1996-01-20 | Сергей Геннадьевич Баякин | Method for production of glass material from ash-slag waste |
| CN1931458A (en) * | 2006-09-06 | 2007-03-21 | 中国科学院生态环境研究中心 | Vacuum assisted heat treatment process with incinerated fly ash |
| CN1963304A (en) * | 2006-12-01 | 2007-05-16 | 清华大学 | Method for stabilizing treatment of refuse burning fly ash by using accelerated carbonation process |
| CN101531492A (en) * | 2009-04-17 | 2009-09-16 | 上海应用技术学院 | Method for preparing light concrete by municipal solid waste incineration fly ash |
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| JP特开平10-180222A 1998.07.07 |
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