CN114029032A - Preparation method of coal granular active coke for removing low-concentration VOCs and product - Google Patents

Preparation method of coal granular active coke for removing low-concentration VOCs and product Download PDF

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CN114029032A
CN114029032A CN202111129271.3A CN202111129271A CN114029032A CN 114029032 A CN114029032 A CN 114029032A CN 202111129271 A CN202111129271 A CN 202111129271A CN 114029032 A CN114029032 A CN 114029032A
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temperature
lignite
carbonization
preparation
active coke
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昌健
刘丹丹
龚得喜
吕小玲
严铭
魏艳立
左文华
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Beijing SPC Environment Protection Tech Co Ltd
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Abstract

The invention discloses a preparation method and a product of coal granular active coke for removing low-concentration VOCs. The preparation method comprises the following steps: mixing, kneading, molding and aging the lignite semicoke, a binder, water and an additive to obtain an aged material; and carrying out carbon activation integrated treatment on the aged material to obtain an activated material. The coal granular active coke produced by the method has high strength, developed porosity and high toluene adsorption rate, can be widely applied to the field of removal and recovery of low-concentration VOCs, and is suitable for large-scale industrial production.

Description

Preparation method of coal granular active coke for removing low-concentration VOCs and product
Technical Field
The invention relates to the technical field of preparation of VOCs removing adsorbents, in particular to a preparation method and a product of coal granular active coke for removing low-concentration VOCs.
Background
The activated coke is an adsorption material with high comprehensive strength (pressure resistance, wear resistance and impact resistance) and small specific surface area than activated carbon, overcomes the defects of high price, low mechanical strength and easy crushing of the activated carbon, and simultaneously keeps the advantage of strong adsorption performance of the activated carbon. The environmental problem is increasingly prominent at present, and especially in the aspects of atmospheric treatment, waste water treatment and the like, the activated carbon is replaced by the activated coke, so that the method has practical significance.
With the increasing importance of society on VOCs treatment, the research on VOCs treatment technology by activated carbon adsorption method is more and more in recent years, and various production processes and products are formed. For example, in one conventional process, coconut shells and a binder are mixed uniformly, and then are cured and activated to obtain common activated carbon, and then nitrates of various metal cations are loaded in the activated carbon in an impregnation mode to obtain modified wood activated carbon for treating medium-high concentration VOCs. In another existing process, the shells and phosphoric acid or zinc chloride are uniformly mixed, then are subjected to high-pressure closed impregnation, then are activated, and the finished product is subjected to high-temperature modulation to obtain the granular wood activated carbon with concentrated micropore distribution, which is used for adsorbing VOCs. The 2 preparation methods of the activated carbon for VOCs treatment are all carried out by carrying out later-stage impregnation on the basis of wood activated carbon, so that the production cost is increased, the production process is more complicated, and the secondary investment is higher. In addition, the wood activated carbon has high cost, is limited by price, and cannot be popularized and applied in large scale in industrial production.
Coal is used as a raw material for producing the active coke, the modified additive is directly added into the raw material in the production process, and the active coke is produced by adopting a carbon activation one-step method, so that the production cost is reduced, the equipment investment is reduced, the energy is effectively utilized, and the purposes of energy conservation and emission reduction are achieved. In addition, various additives play a role in effectively developing the pore structure of the active coke in the production process of the active coke, and simultaneously, the catalytic performance and the basic functional groups of the active coke are also improved, thereby being beneficial to the adsorption of VOCs in the later period.
Disclosure of Invention
Therefore, the invention provides a preparation method and a product of coal granular active coke for removing low-concentration VOCs, aiming at least partially solving the technical problems of less coal granular active coke products, higher cost and more complex process for removing VOCs in the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of coal granular active coke for removing low-concentration VOCs comprises the following steps:
(1) mixing, kneading, molding and aging the lignite semicoke, a binder, water and an additive to obtain an aged material;
(2) and carrying out carbon-activated integrated treatment on the aged material under a preset process condition to obtain an activated material.
Further, the granularity of the lignite semicoke is 140-200 meshes.
Further, the binder includes medium temperature tar.
According to the present invention, the additive primarily serves as a catalyst in the subsequent removal of VOCs. According to some embodiments of the invention, the additive comprises any one or more of sodium bicarbonate, sodium hydroxide, copper chloride and cerium nitrate or a hydrate thereof.
According to some embodiments of the invention, the ratio of the mass of the lignite semicoke to the mass of the tar is (65-85) based on the sum of the mass of the lignite semicoke and the mass of the tar being 100: (35-15). If the tar content is higher than the ratio, the molding material strips are softer and have lower strength; if the tar content is less than this ratio, the molding is difficult or difficult.
According to some embodiments of the invention, the ratio of the total mass of lignite semicoke and tar to the mass of the additive is 100:2 to 100: 10.
According to some embodiments of the invention, the ratio of the total mass of the lignite semicoke and the tar to the mass of the water is 100: 5-100: 20. in the step (1), the lignite semicoke, the binder, the water and the additive are blended to obtain a primary mixed material, and then the primary mixed material is placed in a kneader to be kneaded for the second time.
Further, the kneading temperature is 40-70 ℃, and the kneading time is 5-20 min.
Furthermore, the molded state is a smooth cylinder with the diameter of 2-10 mm, the moisture of the aged material is less than or equal to 12%, and the aged material is crushed into the length of 1-2 cm.
Further, the carbon and activity integration comprises a carbonization stage, a supplementary carbonization stage and an activation stage which are continuously carried out.
Furthermore, in the carbonization stage, the temperature is controlled to be 200-610 ℃, the carbonization time is controlled to be 30-50 min, and the rotating speed of the converter is 20-30 Hz. The carbonization temperature is 200-610 ℃, the carbonization temperature is a temperature range, the carbonization is not fixed-point carbonization, and the molding material strip is subjected to continuous temperature-changing carbonization along with the rise of the temperature of the carbonization furnace.
The supplementary carbonization is a high-temperature supplement to the carbonization at the stage that the carbonization is finished and the activation is not started to be filled with water, so that the strength of the material strip is further improved, and meanwhile, a higher temperature is kept for the subsequent activation.
Further, in the supplementary carbonization stage, the temperature is controlled to be 610-700 ℃, the time is controlled to be 10-15 min, and the rotating speed of the converter is 20-30 Hz.
Furthermore, in the activation stage, the temperature is controlled to be 700-850 ℃, the activation time is controlled to be 40-70 min, the water passing rate is 20-40 g/min, and the rotating speed of the converter is 40-60 Hz.
The invention also provides coal granular active coke for removing low-concentration VOCs, which is prepared by the method. Furthermore, the coal particle active coke is cylindrical, preferably smooth cylindrical, has the particle size of 2-10 mm and the specific surface area of more than or equal to 350m2The toluene adsorption rate is more than or equal to 100 mg/g.
The preparation method of the coal granular active coke provided by the invention can utilize the lignite with low metamorphic degree to prepare the coal granular active coke with low production cost, excellent quality, obviously improved removal effect of low-concentration VOCs and strong market competitiveness, improves the production level of the adsorbent for removing the VOCs, provides a high-quality adsorbent for VOCs waste gas treatment equipment and systems, and simultaneously expands a new way for the industrial utilization of the lignite with low metamorphic degree.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are illustrative only.
FIG. 1 is a flow diagram of a process for producing coal particulate activated coke that may be used to remove low concentrations of VOCs according to some embodiments of the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. In a specific embodiment, the preparation method of the coal granular activated coke for removing the low-concentration VOCs provided by the invention is characterized in that lignite semicoke and medium-temperature tar are used as main raw materials, a certain proportion of additives are added, and the coal granular activated coke is subjected to mixing, kneading, forming and aging and then subjected to carbon activation integrated preparation. As shown in fig. 1, the method specifically comprises the following steps:
s1: mixing, kneading, molding and aging lignite semicoke with a preset granularity, a binder, water and an additive according to a preset proportion, wherein the binder, the water and the additive are required to obtain an aged material. Specifically, the lignite semicoke is preset to have a particle size of 140-200 meshes, the binder is medium-temperature tar, the additive is any one or more of sodium bicarbonate, sodium hydroxide, copper chloride and cerous nitrate hexahydrate, and the preset proportion is a preset mass proportion, wherein: semi-coking lignite: tar (65-85): (35-15), namely the sum of the preset mass of the lignite semicoke and the tar is 100; under the condition, the preset mass ratio of the lignite semicoke, the tar and the additive is 100: 2-100: 10, and the preset mass ratio of the lignite semicoke, the tar and the water is 100: 5-100: 20; manually mixing lignite semicoke with a preset particle size, a binder, water and an additive according to a preset proportion to obtain a primary mixed material, and then placing the primary mixed material in a kneading machine for secondary kneading, wherein the kneading temperature is 40-70 ℃, and the kneading time is 5-20 min; the molding state is a smooth cylinder with the diameter of 2-10 mm, the moisture of the aging material is less than or equal to 12%, and the aging material is crushed into the length of 1-2 cm.
S2: and carrying out carbon-activated integrated treatment on the aged material under a preset process condition to obtain an activated material so as to obtain the coal granular activated coke with the low-concentration VOCs removed. Specifically, the carbon activation is integrated into three stages of carbonization, supplementary carbonization and activation which are continuously carried out; the carbon-activated integrated preset process refers to a carbonization stage, wherein the temperature is controlled to be 200-610 ℃, the carbonization time is controlled to be 30-50 min, and the rotating speed of a converter is 20-30 Hz; a supplementary carbonization stage, wherein the temperature is controlled to be 610-700 ℃, the time is controlled to be 10-15 min, and the rotating speed of the converter is 20-30 Hz; in the activation stage, the temperature is controlled to be 700-850 ℃, the activation time is controlled to be 40-70 min, the water passing rate is 20-40 g/min, and the rotating speed of the converter is 40-60 Hz.
S3: and (4) taking out the reactor after stopping heating, cooling to normal temperature, taking out the coal granular active coke, and sealing for storage.
In the above embodiment, the method for preparing coal granular active coke for removing low-concentration VOCs provided by the invention can utilize lignite with low metamorphic degree to prepare coal granular active coke with low production cost, excellent quality, significantly improved low-concentration VOCs removal effect and great market competitiveness, improves the production level of the adsorbent for removing VOCs, provides a high-quality adsorbent for VOCs waste gas treatment equipment and systems, and simultaneously expands a new way for industrially utilizing lignite with low metamorphic degree.
The following examples 1-6 are given as examples to briefly describe the implementation of the method provided by the present invention.
Example 1
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; and secondly, taking 75g of lignite semi-coke powder and 25g of medium temperature tar, weighing 8g of sodium hydroxide accounting for 8% of the total mass of the lignite semi-coke and the medium temperature tar in proportion, adding the sodium hydroxide into 10g of water, dissolving, and manually mixing and stirring the materials in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 45 deg.C for 10min, extruding to form into 5mm cylindrical shape, aging, and crushing. The aged material has water content of 10% and length of 2 cm.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 37min, and the rotating speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 9 min; the activation temperature is 700-848 ℃, the activation time is 45min, the water passing rate is 33g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
The specific surface area of the coal particle active coke for removing the low-concentration VOCs prepared in the embodiment is 422m2The ratio of micropores to micropores is 92 percent, the diameter of the largest possible pore is 0.5659nm, the iodine adsorption value is 363mg/g, and the toluene adsorption rate is 121 mg/g.
Example 2
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; and secondly, taking 71g of lignite semi-coke powder and 29g of medium temperature tar, weighing 10g of sodium bicarbonate with the total mass of the lignite semi-coke and the medium temperature tar being 10% according to the proportion, adding the sodium bicarbonate into 8g of water, dissolving, and manually mixing and stirring the materials in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 45 deg.C for 8min, extruding to form into 5mm cylindrical shape, aging, and crushing. The aged material has water content of 11% and length of 2 cm.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 39min, and the rotation speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 7 min; the activation temperature is 700-841 ℃, the activation time is 42min, the water passing rate is 35g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
The specific surface area of the coal particle active coke for removing the low-concentration VOCs prepared in the embodiment is 481m2The ratio of micropores is 94 percent, the most probable pore diameter is 0.5581nm, the iodine adsorption value is 403mg/g, and the toluene adsorption rate is 143 mg/g.
Example 3
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; and secondly, taking 80g of lignite semi-coke powder and 20g of medium temperature tar, weighing 6g of copper chloride accounting for 6% of the total mass of the lignite semi-coke and the medium temperature tar in proportion, adding the copper chloride into 20g of water, dissolving, and manually mixing and stirring the materials in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 65 ℃ for 15min, extruding and forming into a 7mm cylinder, aging and crushing. The aged material has 12% of water and 2cm of length.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 39min, and the rotation speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 10 min; the activation temperature is 700-844 ℃, the activation time is 44min, the water passing rate is 34g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
Removal of Low concentration V obtained in this exampleSpecific surface area of coal particle active coke of OCs 382m2The ratio of micropores to micropores is 91%, the diameter of the largest possible pore is 0.5702nm, the iodine adsorption value is 353mg/g, and the toluene adsorption rate is 167 mg/g.
Example 4
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; and secondly, taking 75g of lignite semi-coke powder and 25g of medium temperature tar, weighing 6g of cerium nitrate hexahydrate with the total mass of the lignite semi-coke and the medium temperature tar being 6% according to the proportion, adding the weighed materials into 12g of water, dissolving, and manually mixing and stirring the materials in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 50 deg.C for 15min, extruding to form into 5mm cylindrical shape, aging, and crushing. The aged material has a water content of 7% and a length of 2 cm.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 37min, and the rotating speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 9 min; the activation temperature is 700-851 ℃, the activation time is 45min, the water passing rate is 33g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
The specific surface area of the coal particle active coke for removing the low-concentration VOCs prepared in the embodiment is 472m2The ratio of micropores is 98 percent, the most probable pore diameter is 0.5531nm, the iodine adsorption value is 453mg/g, and the toluene adsorption rate is 192 mg/g.
Example 5
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; and secondly, taking 77g of lignite semi-coke powder and 23g of medium temperature tar, weighing 4g of sodium hydroxide and 5g of copper chloride according to the total mass of the lignite semi-coke and the medium temperature tar, adding the sodium hydroxide and the copper chloride into 16g of water, dissolving, and manually mixing and stirring the materials in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 60 deg.C for 15min, extruding to form 7mm cylindrical shape, aging, and crushing. The aged material has water content of 8% and length of 2 cm.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 36min, and the rotating speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 8 min; the activation temperature is 700-840 ℃, the activation time is 44min, the water passing rate is 34g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
The specific surface area of the coal particle active coke of which the VOCs is removed at low concentration is 519m2The content of micropores is 97%, the diameter of the most probable pore is 0.5559nm, the iodine adsorption value is 483mg/g, and the toluene adsorption rate is 213 mg/g.
Example 6
Firstly, the granularity of lignite semicoke selected for the test is 140-200 meshes; secondly, 79g of lignite semi-coke powder and 21g of medium temperature tar are taken, 4g of sodium bicarbonate with the total mass of 4% and 5g of cerous nitrate hexahydrate with the total mass of the lignite semi-coke and the medium temperature tar are weighed according to the proportion and added into 20g of water, and after the materials are dissolved, the materials are manually mixed and stirred in a glass container to obtain a primary mixed material.
Kneading the initial mixture in a kneader at 55 deg.C for 13min, extruding to form 9mm cylindrical shape, aging, and crushing. The aged material has 12% of water and 2cm of length.
And setting parameters according to a preset process, and carrying out carbon activation integrated treatment on the aged material. Wherein the carbonization temperature of the carbonization stage is 200-610 ℃, the carbonization time is 39min, and the rotation speed is 25 Hz; the supplementary carbonization temperature is 610-700 ℃, and the time is 10 min; the activation temperature is 700-843 ℃, the activation time is 45min, the water passing rate is 33g/min, and the rotating speed is 50 Hz. And stopping the test after the reaction time is up, cooling, taking out the coal granular active coke, and sealing and storing.
The specific surface area of the coal particle active coke for removing the low-concentration VOCs prepared in the embodiment is 542m2The ratio of micropores is 98 percent, the most probable pore diameter is 0.5479nm, the iodine adsorption value is 513mg/g, and the toluene adsorption rate is 234 mg/g.
The product indexes of the coal granular activated coke prepared by the 6 examples for removing the low-concentration VOCs are shown in the specification. In the above 5 examples, the results were averaged by performing 2 parallel replicates. The coal granular active coke for removing the low-concentration VOCs prepared by the technical scheme provided by the invention has the characteristics of high strength, developed porosity, high toluene adsorption rate and the like, and each index is superior to or reaches the VOCs removing material in the current market; the lignite with low metamorphic grade is adopted, the production cost is low, the market competitiveness is high, and meanwhile, a new approach for the industrial utilization of the lignite with low metamorphic grade is also expanded.
For the performance index of the coal particle active coke without the low-concentration VOCs, the porosity is determined by adopting the determination of the nitrogen adsorption isotherm of the active coke under the condition of liquid nitrogen, a static nitrogen adsorption instrument is used for detection, the iodine adsorption value is determined according to GB/T7702.7-2008, and the toluene adsorption rate is determined according to the national standard GB/T35815-2018.
Besides the method, the invention also provides coal granular active coke for removing the low-concentration VOCs, which is prepared by applying the method, the active coke is smooth and cylindrical, the granularity is 2-10 mm, and the specific surface area is more than or equal to 350m2The toluene adsorption rate is more than or equal to 100 mg/g. The coal granular active coke for removing the low-concentration VOCs has high strength, developed porosity and higher toluene adsorption rate, and has remarkable capacity of removing the low-concentration VOCs; the particle size is moderate, and the method is suitable for subsequent regeneration operation and achieves the aim of recycling.

Claims (10)

1. A preparation method of coal granular active coke capable of removing low-concentration VOCs is characterized by comprising the following steps:
(1) mixing, kneading, molding and aging lignite semicoke, a binder, water and an additive in sequence to obtain an aged material;
(2) and carrying out carbon-activated integrated treatment on the aged material to obtain an activated material.
2. The preparation method according to claim 1, wherein the lignite semicoke has a particle size of 140 to 200 mesh.
3. The method of manufacturing according to claim 1 or 2, characterized in that the binder comprises medium temperature tar; the additive comprises any one or more of sodium bicarbonate, sodium hydroxide, copper chloride and cerium nitrate or hydrate thereof.
4. The production method according to any one of claims 1 to 3, wherein the ratio of the mass of the lignite semicoke to the mass of the tar is (65 to 85): (35-15); the ratio of the total mass of the lignite semicoke and the tar to the mass of the additive is 100: 2-100: 10, and the ratio of the total mass of the lignite semicoke and the tar to the mass of the water is 100: 5-100: 20.
5. The production method according to any one of claims 1 to 4, wherein in the step (1), the lignite semicoke is blended with the binder, the water and the additive to obtain a primary mix; and secondly kneading the primary mixed material by a kneader, wherein the kneading temperature is 40-70 ℃, and the kneading time is 5-20 min.
6. The method according to any one of claims 1 to 5, wherein the molded state is a smooth cylindrical shape having a diameter of 2mm to 10mm, the aged material has a water content of 12% or less and is crushed to a length of 1cm to 2 cm.
7. The preparation method according to any one of claims 1 to 6, wherein the carbon-activation integration comprises a carbonization stage, a supplementary carbonization stage and an activation stage which are carried out continuously.
8. The preparation method according to claim 7, characterized in that in the carbonization stage, the temperature is controlled to be 200-610 ℃, the carbonization time is controlled to be 30-50 min, and the revolving speed of the revolving furnace is 20-30 Hz; in the supplementary carbonization stage, the temperature is controlled to be 610-700 ℃, the time is controlled to be 10-15 min, and the rotating speed of the converter is 20-30 Hz; in the activation stage, the temperature is controlled to be 700-850 ℃, the activation time is controlled to be 40-70 min, the water passing rate is 20-40 g/min, and the rotating speed of the converter is 40-60 Hz.
9.The coal granular active coke for removing the low-concentration VOCs is prepared by the method according to any one of claims 1 to 8, and preferably has a cylindrical shape, the granularity of 2mm to 10mm, and the specific surface area of more than or equal to 350m2The toluene adsorption rate is more than or equal to 100 mg/g.
10. The use of the coal-based granular activated coke of claim 9 in the field of removal of VOCs.
CN202111129271.3A 2021-09-26 2021-09-26 Preparation method of coal granular active coke for removing low-concentration VOCs and product Pending CN114029032A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709688A (en) * 2016-01-29 2016-06-29 西安科技大学 Super-pure active semi-coke preparation method and application
CN106669601A (en) * 2016-11-29 2017-05-17 西安科技大学 High-absorbability activated semi-coke and preparation method and application thereof
CN110227428A (en) * 2019-05-31 2019-09-13 萍乡市华星环保工程技术有限公司 The activating and regenerating treatment process of industrial smoke dry desulfurization semicoke
CN111591986A (en) * 2020-04-10 2020-08-28 山东大学 Plant VOCs treatment method and system based on petrochemical enterprise byproduct petroleum coke upgrading utilization

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709688A (en) * 2016-01-29 2016-06-29 西安科技大学 Super-pure active semi-coke preparation method and application
CN106669601A (en) * 2016-11-29 2017-05-17 西安科技大学 High-absorbability activated semi-coke and preparation method and application thereof
CN110227428A (en) * 2019-05-31 2019-09-13 萍乡市华星环保工程技术有限公司 The activating and regenerating treatment process of industrial smoke dry desulfurization semicoke
CN111591986A (en) * 2020-04-10 2020-08-28 山东大学 Plant VOCs treatment method and system based on petrochemical enterprise byproduct petroleum coke upgrading utilization

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张永奇，等: ""半焦制备烟气脱硫用成型活性焦的研究"", pages 258 - 294 *
李昌贤，秦廷武主编: "《煤质活性炭》", 30 July 1993, 煤炭工业出版社, pages: 187 - 188 *

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