CN115970645A - Coal and biomass co-pyrolysis coke demercuration adsorbent and preparation method thereof - Google Patents
Coal and biomass co-pyrolysis coke demercuration adsorbent and preparation method thereof Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 61
- 239000003245 coal Substances 0.000 title claims abstract description 55
- 239000002028 Biomass Substances 0.000 title claims abstract description 52
- 239000003463 adsorbent Substances 0.000 title claims abstract description 30
- 239000000571 coke Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 239000010431 corundum Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 13
- 239000010902 straw Substances 0.000 claims description 16
- 240000008042 Zea mays Species 0.000 claims description 14
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 14
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 14
- 239000002802 bituminous coal Substances 0.000 claims description 14
- 235000005822 corn Nutrition 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 10
- 241000018646 Pinus brutia Species 0.000 claims description 10
- 235000011613 Pinus brutia Nutrition 0.000 claims description 10
- 239000003077 lignite Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 241000209140 Triticum Species 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011335 coal coke Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to a coal and biomass co-pyrolysis coke mercury removal adsorbent and a preparation method thereof, wherein the preparation method comprises the following steps: selecting raw materials: selecting coal and biomass; mixing raw materials: mixing the coal with the biomass to obtain a mixture; mechanical mixing: feeding the mixture into a crusher for crushing, and then mixing for the second time to obtain a sample to be dried; and (3) drying: sending the sample to be dried into a dryer for drying, and obtaining a sample after drying is finished; pyrolysis: putting the sample into a corundum crucible, feeding the corundum crucible into a resistance furnace, heating, and starting pyrolysis; cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product. The invention provides a mercury removal adsorbent for coal and biomass co-pyrolysis coke and a preparation method thereof, which have the advantages of coal coke and biomass coke, improve the removal rate of Hg0, reduce the preparation cost and eliminate the potential risk of environmental pollution in the preparation process. Meanwhile, the efficient clean utilization of coal and biomass is realized.
Description
Technical Field
The invention belongs to the field of demercuration adsorption, and particularly relates to a coal and biomass co-pyrolysis coke demercuration adsorbent and a preparation method thereof.
Background
In the coal-fired flue gas, besides carbon dioxide, sulfur dioxide, nitrogen oxides, smoke dust and other pollutants, trace heavy metal elements such as mercury are also generated, and after entering the environment, the mercury causes great harm to organisms including human beings. The mercury in flue gas of coal-fired power plants has three main forms: zero-valent mercury (Hg 0), divalent mercury (Hg 2 +), and granular mercury (Hgp), the existing coal-fired power plant environmental protection equipment has certain synergistic Hg removal efficiency, but Hg0 removal is always a difficult problem. Currently, demercuration adsorbents include: active carbon adsorbent, active coke adsorbent, fly ash adsorbent, calcium-based adsorbent, mineral adsorbent, transition metal and oxide adsorbent. The advantages and disadvantages are as follows: the preparation process of the activated carbon adsorbent is mature, the specific surface area of the carbon is high, the surface functional groups are rich, the average mercury removal rate can reach 65%, but the cost is high, and the preparation process has potential environmental pollution risks (caused by acid washing); the activated coke adsorbent is similar to activated coke, but has lower mercury removal efficiency than activated carbon; the demercuration efficiency of fly ash adsorbents is seriously affected by the components of fly ash; the calcium-based adsorbent has limited adsorption capacity to Hg0, the surface functional groups of the mineral adsorbent are few, and the demercuration efficiency is low; transition metal and its oxide adsorbents, while maintaining their removal efficiency for Hg0 over long periods of time, are cost prohibitive.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a coal and biomass co-pyrolysis coke demercuration adsorbent, which comprises the following steps:
selecting raw materials: selecting coal and biomass;
mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: feeding the mixture into a crusher for crushing, and then mixing for the second time to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, and obtaining the sample after drying is completed;
pyrolysis: putting the sample into a corundum crucible, sending the corundum crucible into a resistance furnace, heating, and starting pyrolysis;
cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
The further preferable technical scheme is as follows: the coal comprises one or more of bituminous coal, lignite and eastern Junggar coal, and the biomass comprises one or more of corn stalks, pine wood and wheat straws.
The further preferable technical scheme is as follows: the mass ratio of coal to biomass is 20:3-20:5.
the further preferable technical scheme is as follows: in mechanical mixing, the mixture is fed into a crusher and crushed to below 70 mesh.
The further preferable technical scheme is as follows: the secondary mixing is mechanical mixing, and the mixing time is more than 10 minutes.
The further preferable technical scheme is as follows: in the drying process, the drying time is 12 to 24 hours, and the drying temperature is 80 to 120 ℃.
The further preferable technical scheme is as follows: in the pyrolysis, the resistance furnace is a vacuum atmosphere type resistance furnace, the protective atmosphere is nitrogen, the heating rate is 5-20 ℃/min in the heating process, and the pyrolysis temperature is 400-1000 ℃.
The further preferable technical scheme is as follows: the heating rate is 15 ℃/min to 20 ℃/min, the pyrolysis temperature is 600 ℃ to 900 DEG C
The further preferable technical scheme is as follows: the pyrolysis retention time is 20 min-60 min.
The invention has the beneficial effects that: the mercury removal adsorbent for co-pyrolysis coke of coal and biomass and the preparation method thereof have the advantages of both coal coke and biomass coke, improve the removal rate of Hg0, reduce the preparation cost and eliminate the potential risk of environmental pollution in the preparation process. Meanwhile, the efficient clean utilization of coal and biomass is realized.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
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 embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 shows a process flow for producing pyrolysis coke, activated carbon.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
selecting raw materials: selecting coal and biomass;
wherein the coal is bituminous coal, the mass of the bituminous coal is 10g, the biomass is corn straws, and the mass of the corn straws is 1.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: sending the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then carrying out secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is completed;
pyrolysis: and (2) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, starting to heat up under the protective atmosphere of nitrogen at the heating rate of 5 ℃/min to 400 ℃, starting pyrolysis, and keeping the pyrolysis for 20min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
Example 2:
selecting raw materials: selecting coal and biomass;
wherein the coal is bituminous coal, the mass of the bituminous coal is 10g, the biomass is corn stalks, and the mass of the corn stalks is 2.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: sending the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then carrying out secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is completed;
pyrolysis: and (3) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, wherein the protective atmosphere is nitrogen, heating up at the heating rate of 5 ℃/min to 400 ℃, starting pyrolysis, and keeping the pyrolysis for 20min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
Example 3:
selecting raw materials: selecting coal and biomass;
the coal comprises bituminous coal and lignite, the mass of the bituminous coal is 10g, the mass of the lignite is 10g, the biomass comprises corn straws and pine wood, the mass of the corn straws is 1.5g, and the mass of the pine wood is 1.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: sending the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then carrying out secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is finished;
pyrolysis: and (3) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, wherein the protective atmosphere is nitrogen, heating up at the heating rate of 20 ℃/min to 1000 ℃, starting pyrolysis, and keeping the pyrolysis for 60min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
Example 4:
selecting raw materials: selecting coal and biomass;
the coal comprises bituminous coal and lignite, the mass of the bituminous coal is 10g, the mass of the lignite is 10g, the biomass comprises corn straws and pine wood, the mass of the corn straws is 1.5g, and the mass of the pine wood is 1.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: sending the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then carrying out secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is completed;
pyrolysis: and (2) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, starting to heat up under the protective atmosphere of nitrogen at the heating rate of 15 ℃/min to 600 ℃, starting pyrolysis, and keeping the pyrolysis for 60min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
The coal and biomass co-pyrolysis coke for demercuration prepared by the invention has the advantages of coal coke and biomass coke, the co-pyrolysis coke has a developed pore structure, a large specific surface area, a large number of surface functional groups, a large number of mercury adsorption sites and a large adsorption amount, the preparation process is not applicable to an acid pickling process, and the influence on the environment is eliminated.
Example 5: selecting raw materials: selecting coal and biomass;
the coal comprises bituminous coal, lignite and eastern Junggar coal, the mass of the bituminous coal is 10g, the mass of the lignite is 10g, the mass of the eastern Junggar coal is 10g, the biomass comprises corn straws, pine and wheat straws, the mass of the corn straws is 1.5g, the mass of the pine is 1.5g, and the mass of the wheat straws is 1.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: feeding the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then performing secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is completed;
pyrolysis: and (2) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, starting to heat up under the protective atmosphere of nitrogen at the heating rate of 15 ℃/min to 600 ℃, starting pyrolysis, and keeping the pyrolysis for 60min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
Example 6:
selecting raw materials: selecting coal and biomass;
the biomass-based bituminous coal is prepared from coal, lignite and eastern Junggar coal, wherein the coal comprises 10g of bituminous coal, 10g of lignite, 10g of eastern Junggar coal, corn straws, pine trees and wheat straws, the mass of the corn straws is 1.5g, the mass of the pine trees is 1.5g, and the mass of the wheat straws is 1.5g.
Mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: sending the mixture into a crusher for crushing, crushing the mixture to 70 meshes, and then carrying out secondary mixing by using a machine, wherein the mixing time is 10 minutes, so as to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, wherein the drying time is 24 hours, the drying temperature is 100 ℃, and the sample is obtained after drying is completed;
pyrolysis: and (3) putting the sample into a corundum crucible, sending the corundum crucible into a vacuum atmosphere type resistance furnace, wherein the protective atmosphere is nitrogen, heating up at the heating rate of 10 ℃/min to 900 ℃, starting pyrolysis, and keeping the pyrolysis for 45min.
Cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
The method has the advantages of both coal coke and biomass coke, improves the removal rate of Hg0, reduces the preparation cost, and eliminates the potential risk of environmental pollution in the preparation process.
It should be noted that the terms "first," "second," and the like in this application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It should be understood that the data so used may be interchanged under appropriate circumstances such that embodiments of the application described herein may be used. In this application, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "middle", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a coal and biomass co-pyrolysis coke demercuration adsorbent is characterized by comprising the following steps:
selecting raw materials: selecting coal and biomass;
mixing raw materials: mixing the coal with the biomass to obtain a mixture;
mechanical mixing: feeding the mixture into a crusher for crushing, and then mixing for the second time to obtain a sample to be dried;
and (3) drying: sending the sample to be dried into a dryer for drying, and obtaining the sample after drying is completed;
pyrolysis: putting the sample into a corundum crucible, sending the corundum crucible into a resistance furnace, heating, and starting pyrolysis;
cooling: and after the pyrolysis is finished, cooling the pyrolyzed sample to room temperature to obtain a finished product.
2. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 1, wherein the coal comprises one or more of bituminous coal, lignite and eastern Junggar coal, and the biomass comprises one or more of corn stalks, pine wood and wheat straws.
3. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 2, wherein the mass ratio of the coal to the biomass is 20:3-20:5.
4. the method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 3, wherein in the mechanical mixing, the mixture is sent to a crusher to be crushed to below 70 meshes.
5. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 4, wherein the secondary mixing is mechanical mixing, and the mixing time is 10 minutes or more.
6. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 5, wherein in the drying, the drying time is 12-24 hours, and the drying temperature is 80-120 ℃.
7. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 6, wherein in the pyrolysis, the electric resistance furnace is a vacuum atmosphere type electric resistance furnace, the protective atmosphere is nitrogen, in the temperature rise, the temperature rise rate is 5 ℃/min to 20 ℃/min, and the pyrolysis temperature is 400 ℃ to 1000 ℃.
8. The method for preparing the coal and biomass co-pyrolysis coke demercuration adsorbent according to claim 7, wherein the temperature rise rate is 15 ℃/min to 20 ℃/min, and the pyrolysis temperature is 600 ℃ to 900 ℃.
9. The method for preparing the coal and biomass co-pyrolysis coke mercury removal adsorbent according to any one of claims 1 to 8, wherein the pyrolysis retention time is 20min to 60min.
10. The coal and biomass co-pyrolysis coke demercuration adsorbent is characterized by being prepared according to the preparation method of claim 9.
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