CN100352763C - Method for producing desulfurization and denitrification activated carbon by using byproduct carbon black - Google Patents

Method for producing desulfurization and denitrification activated carbon by using byproduct carbon black Download PDF

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CN100352763C
CN100352763C CNB02137838XA CN02137838A CN100352763C CN 100352763 C CN100352763 C CN 100352763C CN B02137838X A CNB02137838X A CN B02137838XA CN 02137838 A CN02137838 A CN 02137838A CN 100352763 C CN100352763 C CN 100352763C
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China
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carbon black
furnace
steam
carbon
product
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CN1385367A (en
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郝德山
高晓玲
蔡斋如
王明权
卜西军
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

The present invention belongs to the field of environment protecting technology, and proposes that carbon black water produced through gasifying heavy oil, residual oil, asphalt, etc. is first pelletized and then activated with steam and air to form granular active carbon, and the active carbon has the features of adsorption and catalysis to eliminate sulfide and nitrogen oxide from fume. The method not only develops an application market with wide prospect for the byproduct carbon black, but also provides a new way for the dry flue gas desulfurization technology.

Description

Method for producing desulfurization and denitrification activated carbon by using byproduct carbon black
The technical field is as follows: the invention belongs to the field of environmental protection, and is particularly suitable for chemical fertilizers and electric power industries.
Background art: with the development of petrochemical industry and chemical fertilizer industry, a large amount of carbon black by-product should be transported and generated, and the treatment modes of carbon black water from a gasification furnace are roughly divided into two types: one is oil extraction, and the other is filtration drying.
The oil extraction method for recovering carbon black is a process of separating carbon black from water by using oil as an extracting agent and utilizing the lipophilicity of the carbon black to be larger than the hydrophilicity. The mixture of carbon black and oil is called carbon black oil, and is sent to a gasification furnace as a raw material to be combusted together with fuel gas. Because the ash content of the byproduct carbon black is high, the furnace returning operation has certain influence on the furnace body.
The research of the filtering and drying process starts in the early seventies, which is to concentrate and thicken carbon black water into carbon black slurry, enter a rotary drum vacuum filter or a vacuum belt filter to obtain a filter cake with water content of about 85 percent, and then carry out secondary drying treatment by a pre-dryer and an enhanced dryer to obtain dry carbon black with water content of less than 5 percent. The carbon black byproduct can be applied to the production of middle-grade and low-grade rubber, zinc-manganese batteries, decoloration and the like only by taking proper measures in the aspect of process or reasonably designing a formula according to the characteristics of the carbon black byproduct, but the yield is often over-demanded.
Therefore, the method for producing the activated carbon by using the byproduct carbon black has important significance for desulfurization and denitration.
China is a big coal-fired country, and dust, sulfur dioxide, nitrogen oxide and carbon dioxide in flue gas generated by coal firing cause serious pollution to the atmosphere. Over the years, the nation takes many measures in the aspect of dust removal, so that the electric dust removal technology is fully developed and used, and the dust pollution is effectively controlled. However, the pollution problem of sulfur dioxide, nitrogen oxide and carbon dioxide is not fundamentally solved, and the reason is that a large amount of water resources are consumed during wet desulphurization, which is almost impossible for domestic regional desulphurization and denitration which is short of water resources; and the cost of introducing foreign dry desulfurization technology is too high. Therefore, the desulfurization and denitration technology by using the activated carbon is a desulfurization and denitration technology which is very suitable for the situation of China both economically and technically.
In particular, patent CN1229055 emphasizes that waste such as waste tires and plastics to be treated or carbon black generated by burning heavy oil, coal, gas and the like in thermal power plants and boilers is activated to form activated carbon with high added value. Firstly, carbon black is preheated by an outer barrel segmented temperature control screw conveyor, is conveyed to a microwave chamber at the same time, and is heated to 250-400 ℃ by microwave to generate powdery active carbon; then put into a flow type steam activation furnace to be activated in steam atmosphere at high temperature of 700-900 ℃ to prepare the powdered activated carbon.
The invention content is as follows: the invention provides a process route aiming at developing various applications of the existing byproduct carbon black, which not only develops an application market with wide prospect for the byproduct carbon black, but also provides a new way for the current flue gas desulfurization technology.
The invention utilizes the by-product carbon black of heavy oil, residual oil and asphalt to produce granular active carbon firstly, and then utilizes the inherent adsorption and catalysis characteristics of the active carbon to remove sulfide and nitrogen oxide in flue gas, thus being a more advanced desulfurization and denitrification technology.
The invention adopts a process route different from that of CN1229055, firstly, the selected raw materials are different, the production process is different, the obtained products are different, the application is different, and finally, the active carbon produced by the invention is suitable for occasions of desulfurization and denitration.
The raw material provided by the invention is the byproduct carbon black generated by gasifying heavy oil, residual oil and asphalt, and the carbon black has small particle size (usually in nanometer level), high specific surface area, high oil absorption value and high iodine absorption value, but high ash content. The ash content has certain influence on the performance of other activated carbon, but has no influence on the desulfurization and denitrification activated carbon.
The invention is realized by the following steps: firstly, the by-product carbon black produced by gasifying heavy oil, residual oil and asphalt is directly utilized, filtered and mixed with an adhesive to form a plastic material, and then the plastic material is granulated, extruded, molded and dried and enters a steam activation furnace at the temperature of about 700-900 ℃ for cremation, wherein the activating agent adopts air and steam.
The specific implementation mode is as follows:
firstly, directly using the carbon black which is filtered by a filter and contains 85 percent of water content to mix with a bonding agent to form a plastic material, wherein the mixing proportion of the carbon black and the bonding agent can be determined according to the type of the carbon black, and the carbon black is generally about 1 percent of the carbon black. Then the carbon black is sent into a granulator from an intermediate storage tank through a star valve, the diameter of the granulator is 600 mm, an electric heating device is arranged outside the shell to prevent the carbon black cake from adhering to the inner wall of the shell, and the carbon black cake is extruded into a formed product with the diameter of about 2 mm by an extruder. The formed product is dried and then enters a steam activation furnace with the temperature of about 700-900 ℃ from the side surface through a spiral feeder. The activation furnace adopts a rotary furnace, in order to keep the activation to be uniformly carried out, the activation furnace adopts air and water vapor, the steam and the air respectively enter the furnace from the side surface of the activation furnace, and the ratio of the steam to the air is determined according to the actual condition. The furnace is electrically heated to maintain the temperature between 800 ℃ and 900 ℃, granular carbon black is contacted with high-temperature steam, firstly, the non-tissue carbon such as tar and the like in the raw material carbon is removed, the originally closed pores are opened and unblocked or the existing small pores are enlarged, after about one hour of contact, the active carbon with developed micropores is generated and falls into a hopper from the side by gravity, and the waste gas is discharged after the dust removal of a roof electric precipitator from the furnace top.
The synthesized active carbon has good adsorption performance on sulfur dioxide, and can desorb the adsorbed sulfur dioxide at a higher temperature, so that sulfur dioxide gas with higher concentration is obtained, and the desorbed active carbon can be used as a desulfurizer for repeated use. It can also be used as catalyst to make nitrogen oxide react with ammonia gas to produce harmless nitrogen gas to remove nitrogen oxide in flue gas.
Compared with the existing industrial desulfurization and denitration activated carbon, the generated activated carbon has the characteristics of low price, high rigidity and strong adsorption capacity, and the BET surface area representing the adsorption performance of the activated carbon is almost similar to the surface area of the activated carbon produced by taking coconut shells as raw materials. It is especially suitable for industrial desulfurization and denitrogenation.

Claims (2)

1. A process for preparing the desulfurized and denitrified activated carbon from the by-product carbon black includes such steps as filtering the by-product carbon black generated by gasifying heavy oil, residual oil and asphalt, mixing it with adhesive, granulating, extruding for shaping, drying, and activating in 700-900 deg.C steam activating furnace.
2. A method for producing desulfurization and denitrification activated carbon by using by-product carbon black as claimed in claim 1, wherein the by-product carbon black produced by gasifying heavy oil, residual oil and pitch is directly used, the filtered carbon black containing 85% of water is mixed with a binder to form a plastic material, the mixing ratio of the carbon black and the binder is generally about 1% of the amount of the carbon black, then the carbon black is fed into a granulator through a star valve from an intermediate tank, the diameter of the granulator is 600 mm, an electric heating device is arranged outside the casing to prevent the carbon black cake from adhering to the inner wall of the casing, the carbon black cake is extruded into a molded product of about 2 mm by an extruder, the molded product is dried and then fed into a steam activation furnace of 700 ℃ to 900 ℃ from the side through a screw feeder, the activation furnace adopts a rotary furnace, in order to keep the activation uniformly performed, the activator adopts air and steam, the steam and the air are respectively fed into the activation furnace from the side of the activation furnace, the furnace is electrically heated to maintain the temperature of 800 ℃ to 900 ℃, the granular carbon black and after the contact of the high temperature steam for about one hour, the granular carbon black is produced into the activated carbon, and falls into a hopper from the hopper through gravity, and the dust collector, the top of the furnace is removed by an electric roof.
CNB02137838XA 2002-06-25 2002-06-25 Method for producing desulfurization and denitrification activated carbon by using byproduct carbon black Expired - Fee Related CN100352763C (en)

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101559318B (en) * 2009-05-25 2013-10-30 天津城市建设学院 Thermal carbon composite denitration method for coal-fired boiler
CN102126722A (en) * 2010-01-20 2011-07-20 神华新疆能源有限责任公司 Process for preparing coal-based agglomerated activated carbon
CN101817524A (en) * 2010-05-05 2010-09-01 卞奎友 Process for producing activated carbon by physical activation method
CN105858650B (en) * 2016-03-22 2018-03-20 黎城蓝天燃气开发有限公司 Utilize the method for waste and old activated carbon manufacture desulphurization denitration activated carbon
CN107855103B (en) * 2017-03-15 2019-10-11 吉林大学 Using coal gasification fine slag prepare adsorbent material method and adsorbent material obtained
CN107539988A (en) * 2017-09-21 2018-01-05 南京林业大学 A kind of method of ature of coal particle gasifying electricity generation or heat supply co-producing active carbon
CN108612577B (en) * 2018-04-13 2021-12-07 哈尔滨工程大学 Device and method for denitration of tail gas of ship by activated carbon method
CN111574858A (en) * 2019-02-15 2020-08-25 中国石油化工股份有限公司 Method for removing organic matters in carbon black by-product in preparation of acetylene by partial oxidation of natural gas
CN113120902B (en) * 2019-12-31 2022-11-11 中国石油化工股份有限公司 Preparation method of activated carbon

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86107847A (en) * 1986-11-18 1988-06-01 山西省大同市云光化工厂 The production method of weakly caking coal columnar activated carbon
CN1078727A (en) * 1992-04-07 1993-11-24 克瓦纳尔工程有限公司 Production of carbon black

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86107847A (en) * 1986-11-18 1988-06-01 山西省大同市云光化工厂 The production method of weakly caking coal columnar activated carbon
CN1078727A (en) * 1992-04-07 1993-11-24 克瓦纳尔工程有限公司 Production of carbon black

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