CN113831927A - Method for improving yield of low-metamorphic coal pyrolysis tar by utilizing biomass - Google Patents
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- 239000003245 coal Substances 0.000 title claims abstract description 101
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 98
- 239000002028 Biomass Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 19
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 18
- 235000011613 Pinus brutia Nutrition 0.000 claims description 18
- 241000018646 Pinus brutia Species 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 150000003254 radicals Chemical group 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 2
- 239000011269 tar Substances 0.000 description 45
- 238000002474 experimental method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 244000141359 Malus pumila Species 0.000 description 2
- 235000011430 Malus pumila Nutrition 0.000 description 2
- 235000015103 Malus silvestris Nutrition 0.000 description 2
- 244000241463 Cullen corylifolium Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for improving the yield of low metamorphic coal pyrolysis tar by using biomass, which comprises the following steps: when coal pyrolysis is used for obtaining tar, biomass is mixed into the coal; wherein the pyrolysis process is carried out in an inert gas atmosphere, and the mass ratio of the coal to the biomass is 1: (0.1-0.5). When the coal is pyrolyzed to obtain tar, biomass is mixed into the coal, the biomass has a high hydrogen-carbon ratio, hydrogen-rich free radical fragments generated in the pyrolysis process can react with macromolecular aromatic hydrocarbon compounds in the coal to promote the pyrolysis of the macromolecular aromatic hydrocarbon compounds, and meanwhile, the hydrogen-rich free radical fragments can be used as a hydrogen supply source to improve the pyrolysis conversion rate of the coal. However, the amount of added biomass becomes an important problem in the co-pyrolysis process, and excessive biomass pyrolysis products can be attached to the surfaces of coal particles and generate coking reaction to inhibit the release of volatile components in the co-pyrolysis process.
Description
Technical Field
The invention belongs to the technical field of coal chemical industry, and particularly relates to a method for improving the yield of low-metamorphic coal pyrolysis tar by using biomass.
Background
The low metamorphic coal in northern Shaanxi area of China has the characteristics of high oil content and large reserve, and the problem of increasingly shortage of domestic petroleum resources can be effectively relieved by adopting the efficient and clean pyrolysis process to utilize the low metamorphic coal. But the yield of coal tar is low when the coal is pyrolyzed because of the low hydrogen-carbon ratio of the coal. Therefore, how to improve the tar yield is a problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for improving the yield of low-metamorphic coal pyrolysis tar by using biomass, and the method can further improve the yield of the tar during coal pyrolysis.
The technical scheme adopted by the invention is as follows:
a method for improving the yield of low metamorphic coal pyrolysis tar by using biomass comprises the following steps:
when coal pyrolysis is used for obtaining tar, biomass is mixed into the coal;
wherein the pyrolysis process is carried out in an inert gas atmosphere, and the mass ratio of the coal to the biomass is 1: (0.1-0.5).
Preferably, the pyrolysis temperature is 500-.
Preferably, the heating rate during pyrolysis is 8-15 ℃/min.
Preferably, the coal is low metamorphic coal.
Preferably, the coal is coal of Malayong province.
Preferably, the biomass is any one or a mixture of more of straw, walnut shells, apple wood and wood.
Preferably, pine wood chips are used as the biomass.
Preferably, the inert gas atmosphere is a nitrogen atmosphere.
Preferably, the coal has a particle size not exceeding 200 mesh.
Preferably, the biomass has a particle size of no more than 200 mesh.
The invention has the following beneficial effects:
when the coal is pyrolyzed to obtain tar, biomass is mixed into the coal, the biomass has a high hydrogen-carbon ratio, hydrogen-rich free radical fragments generated in the pyrolysis process can react with macromolecular aromatic hydrocarbon compounds in the coal to promote the pyrolysis of the macromolecular aromatic hydrocarbon compounds, and meanwhile, the hydrogen-rich free radical fragments can be used as a hydrogen supply source to improve the pyrolysis conversion rate of the coal. However, the amount of added biomass becomes an important problem in the co-pyrolysis process, and excessive biomass pyrolysis products can be attached to the surfaces of coal particles and generate coking reaction to inhibit the release of volatile components in the co-pyrolysis process. Therefore, the mass ratio of the coal to the biomass is controlled to be 1: (0.1-0.5), under the condition, the tar yield can be obviously improved, and can reach 11.58-15.82%. In conclusion, the invention solves the problem of low yield of coal pyrolysis tar and simultaneously makes full use of biomass resources.
Drawings
FIG. 1 is a graphical representation comparing the tar yield from co-pyrolysis of coal and biomass to the tar yield from pyrolysis of coal alone under different conditions in the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and the specific embodiments can be determined according to actual situations.
The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass comprises the following steps:
firstly, coal and biomass are respectively crushed and screened, and two raw materials with the grain size not more than 200 meshes are taken. Mixing coal and biomass in a mass ratio of 1: (0.1-0.5) performing co-pyrolysis at a pyrolysis temperature of 500-700 deg.C and a heating rate of 8-15 deg.C/min, introducing N before pyrolysis2After the air in the furnace is expelled, the nitrogen is closed, and a horizontal fixed bed is arrangedThe experiment of coal and biomass co-pyrolysis is completed in the reactor, tar generated by pyrolysis is condensed and collected in a water-cooling bottle, gas is collected through a gas collection bag, and finally the total amount of semicoke is weighed. The coal is low metamorphic coal; the biomass is any one or a mixture of more common straws, walnut shells, apple trees and woods in any proportion.
In the preferred embodiment of the method, the selected coal raw material is coal in Mahuadong, the coal in Mahuadong has the characteristics of high oil content, high heat generation and low deterioration degree, and the selected biomass raw material is pine sawdust which is rich in lignin and cellulose. Coal and biomass are pyrolyzed in a horizontal fixed bed reactor.
The yield of pyrolysis tar was calculated as follows:
wherein M isadRepresents the moisture content,%; a. theadRepresents ash content,%; m istarRepresents tar mass,%; m represents the mass of the mixed raw materials, g; y istarRepresents the tar yield,%.
In the scheme of the invention, the hydrogen-rich free radical fragments generated in the biomass pyrolysis process can promote the cracking reaction of macromolecular aromatic hydrocarbon compounds in coal, so that the aim of improving the tar yield can be achieved, and the problem of low tar yield in the low-metamorphic coal pyrolysis process is solved.
Example 1:
taking 50g of Maliandong coal and pine sawdust according to a mass ratio of 1: performing pyrolysis experiment on the 0.1 blend, putting the blend into a quartz tube of a pyrolysis reactor for pyrolysis, wherein the temperature of the co-pyrolysis experiment is 700 ℃, the heating rate is 8 ℃/min, and introducing N before pyrolysis2Close nitrogen gas behind the expulsion stove air, carry out the pyrolysis experiment altogether of ma huai dong coal and pine saw-dust in horizontal fixed bed reactor, the tar that the pyrolysis produced is condensed in the water-cooling bottle and is collected, and gas is collected through air collecting bag, carries out the productivity of different products through productivity formula to carry outAnd (4) calculating. FIG. 1 is a comparison of tar yields of inventive examples 1-5 with a comparative example. The results show that example 1 had a temperature of 700 ℃ and a formulation of 1: the yield of tar obtained by co-pyrolysis under the condition of 0.1 is increased by 5.78% compared with the yield of a comparative example (the coal in Ma Huaitong is independently pyrolyzed at 700 ℃), the yield reaches 11.58%, and the yield of tar is obviously improved. This is because the pyrolysis of pine wood chips produces many hydrogen-containing radical fragments, and these small fragments react with the macromolecular aromatic hydrocarbon compounds in the coal to promote the cracking thereof. Meanwhile, the high hydrogen-carbon ratio can prevent the free radical fragments in the pyrolysis process from undergoing polycondensation reaction or secondary reaction with semicoke. Thus, the tar yield in the product can be increased.
Example 2:
taking 50g of coal and pine wood chips of Maliandong as a mixture, wherein the weight ratio of the coal to the pine wood chips is 1: 0.2 blend was subjected to pyrolysis test at 650 deg.C at a rate of 10 deg.C/min, and N was added before pyrolysis2Close nitrogen gas behind the expulsion stove air, carry out the pyrolysis experiment altogether of ma huai dong coal and pine saw-dust in horizontal fixed bed reactor, the tar that the pyrolysis produced is condensed in the water-cooling bottle and is collected, and gas is collected through air collecting bag, calculates the productivity of different products through productivity computational formula. The results show that example 2 had a temperature of 650 ℃ and a formulation of 1: the yield of tar obtained by co-pyrolysis under the condition of 0.2 was 12.98%, and the yield of tar obtained by pyrolysis of coal in shandong at 650 ℃ alone was 5.21%, which was seen to be significantly greater than that obtained by the comparative example (pyrolysis of coal in shandong at 650 ℃ alone).
Example 3:
taking 50g of coal and pine wood chips of Maliandong as a mixture, wherein the weight ratio of the coal to the pine wood chips is 1: 0.3 of the blend was subjected to a pyrolysis experiment at 600 ℃ at a rate of 10 ℃/min and N was added before pyrolysis2Close nitrogen gas behind the expulsion stove air, carry out the pyrolysis experiment altogether of ma huai dong coal and pine saw-dust in horizontal fixed bed reactor, the tar that the pyrolysis produced is condensed in the water-cooling bottle and is collected, and gas is collected through air collecting bag, calculates the productivity of different products through productivity computational formula. The results show that example 3 was formulated at a temperature of 600 deg.CIs 1: the yield of tar obtained by co-pyrolysis under the condition of 0.3 was 15.02%, and the yield of tar obtained by pyrolysis of coal in shandong at 600 ℃ alone was 4.61%, which was seen to be significantly greater than that obtained by comparative example (pyrolysis of coal in shandong at 600 ℃ alone).
Example 4:
taking 50g of coal and pine wood chips of Maliandong as a mixture, wherein the weight ratio of the coal to the pine wood chips is 1: 0.4 blend was subjected to pyrolysis test at 550 deg.C with a heating rate of 10 deg.C/min, and N was added before pyrolysis2Close nitrogen gas behind the expulsion stove air, carry out the pyrolysis experiment altogether of ma huai dong coal and pine saw-dust in horizontal fixed bed reactor, the tar that the pyrolysis produced is condensed in the water-cooling bottle and is collected, and gas is collected through air collecting bag, calculates the productivity of different products through productivity computational formula. The results show that example 4 had a temperature of 550 ℃ and a formulation of 1: the yield of tar obtained by co-pyrolysis at 0.4 was 15.53%, and the yield of tar obtained by pyrolysis of coal in shandong at 550 ℃ alone was 4.15%, indicating that the yield of tar obtained by pyrolysis of coal and biomass blend was significantly greater than that of the comparative example (coal in shandong at 550 ℃ alone).
Example 5:
taking 50g of coal and pine wood chips of Maliandong as a mixture, wherein the weight ratio of the coal to the pine wood chips is 1: 0.5 blend was subjected to a pyrolysis experiment at 500 deg.C with a temperature rise rate of 15 deg.C/min, N was added before pyrolysis2Close nitrogen gas behind the expulsion stove air, carry out the pyrolysis experiment altogether of ma huai dong coal and pine saw-dust in horizontal fixed bed reactor, the tar that the pyrolysis produced is condensed in the water-cooling bottle and is collected, and gas is collected through air collecting bag, calculates the productivity of different products through productivity computational formula. The results show that example 5 had a temperature of 500 ℃ and a formulation of 1: the yield of tar from the co-pyrolysis at 0.5 was 15.82%, and the yield of tar from the individual pyrolysis of coal in shandong at 650 ℃ was 3.87%, indicating that the yield of tar from the pyrolysis of coal and biomass blend was significantly greater than the comparative example (the individual pyrolysis of coal in shandong at 500 ℃).
Comparative example:
the test procedure of the comparative example is the same as that of the example, except that the raw material is different, and the raw material in the comparative example is subjected to pyrolysis test only by using coal of Malaytea.
According to the technical scheme, the product distribution in the coal pyrolysis process is obviously influenced by different proportions of coal and biomass in the coal and biomass co-pyrolysis process, and by means of the characteristic that the tar yield can be improved to the maximum extent by co-pyrolysis of coal and biomass in a certain proportion, the hydrogen-rich radical fragments generated in the biomass pyrolysis process can fully promote the cracking reaction of macromolecular aromatic hydrocarbon compounds in coal to generate more tar. The method solves the problem of how to effectively utilize the biomass to improve the yield of coal pyrolysis tar to the maximum extent. The invention solves the problem of low yield of coal pyrolysis tar and simultaneously makes full use of biomass resources.
Compared with the single coal pyrolysis process, the tar yield of the embodiment is obviously improved, the implementation effect is better, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations. The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes made according to the technical idea of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A method for improving the yield of low metamorphic coal pyrolysis tar by using biomass is characterized by comprising the following steps:
when coal pyrolysis is used for obtaining tar, biomass is mixed into the coal;
wherein the pyrolysis process is carried out in an inert gas atmosphere, and the mass ratio of the coal to the biomass is 1: (0.1-0.5).
2. The method as claimed in claim 1, wherein the pyrolysis temperature is 500-700 ℃.
3. The method for improving the yield of the low-rank coal pyrolysis tar by using the biomass as claimed in claim 2, wherein the heating temperature rise rate during pyrolysis is 8-15 ℃/min.
4. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 1, wherein the coal is low metamorphic coal.
5. The method for improving the yield of the low-rank coal pyrolysis tar by using the biomass as claimed in claim 4, wherein the coal is Malantong coal.
6. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 1, wherein the biomass is any one or a mixture of straw, walnut shell, apple wood and wood.
7. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 6, wherein the biomass adopts pine wood chips.
8. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 1, wherein the inert gas atmosphere is a nitrogen atmosphere.
9. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 1, wherein the particle size of the coal is not more than 200 meshes.
10. The method for improving the yield of the low metamorphic coal pyrolysis tar by utilizing the biomass as claimed in claim 1, wherein the particle size of the biomass is not more than 200 meshes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115970645A (en) * | 2022-12-27 | 2023-04-18 | 国家电投集团远达环保工程有限公司 | Coal and biomass co-pyrolysis coke demercuration adsorbent and preparation method thereof |
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| CN115970645A (en) * | 2022-12-27 | 2023-04-18 | 国家电投集团远达环保工程有限公司 | Coal and biomass co-pyrolysis coke demercuration adsorbent and preparation method thereof |
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Application publication date: 20211224 |