CN115772424A - Alkali lignin reinforced coal coke powder chemical chain cooperative gasification method - Google Patents
Alkali lignin reinforced coal coke powder chemical chain cooperative gasification method Download PDFInfo
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Abstract
The invention discloses a method for alkali lignin reinforced coal coke powder chemical chain cooperative gasification. The method comprises the following steps: chemical chain gasification: carrying out chemical chain cooperative gasification reaction on the coal coke powder, the alkali lignin and the oxygen carrier at 700-1000 ℃; gas-solid separation: and (2) separating the reaction product in the step (S1) at the temperature of between 20 and 450 ℃ to obtain a gas-phase product and a solid-phase product. The invention realizes the cooperative resource utilization of the industrial byproduct alkali lignin and the coal coke powder, not only solves the problems of harsh reaction conditions and low conversion rate in the conventional coal coke powder thermal conversion process, but also breaks through the bottleneck of alkali metal in the alkali lignin resource utilization process, and realizes the high-efficiency utilization of the industrial byproduct alkali lignin.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment. More particularly, relates to a method for alkali lignin reinforced chemical chain cooperative gasification of coal coke powder.
Background
China is a big coal country, and the energy structure taking coal as basic energy is difficult to change in a short period. Coking is one of the main utilization modes of coal, the yield of coal coke in China is about 4.31 million tons in 2017, the consumed coke coal is 5.7 million tons, and the total consumption of coal in China is 12.7%. The coal coke powder is a byproduct in the production process of coking enterprises, generally the powder yield accounts for 3% -5% of the coke finished product, and the components of the coal coke powder mainly comprise fixed carbon, volatile components and ash. Because the coke powder is generated through complex processes of high-temperature devolatilization, crushing, sieving and the like, the reaction activity is low, the particle size is small (less than 5 mm), the coke powder does not meet the requirements of industries such as metallurgy, chemical engineering and the like, and the coke powder is difficult to directly recycle, so that most of the coke powder is treated or discarded at low cost. This not only results in a large amount of waste of resources, but also more serious because of lack of effective management, a large amount of waste coke powder is accumulated in the open air, and the air is exposed to the sun, which causes serious pollution to the environment and harms human health.
The coal coke powder is mainly used for blending coal for coking and preparing active carbon at present. The Chinese invention patent 'preparation method of activated coke powder for carbon fuel cells' discloses a preparation method of activated coke powder for carbon fuel cells, which is characterized in that industrial coke is crushed and ground, and then is subjected to modification treatment of physicochemical properties by using a KOH chemical activation method, so as to obtain the activated coke powder. The invention patent of China discloses a method and equipment for burning coal coke powder, which is characterized in that the coal coke powder sequentially passes through a low-speed bed and a high-speed bed to be burnt, the burnt particles are mixed with newly added coal coke powder after gas-solid separation, and the mixture enters the circulating burning of the steps again to improve the burning efficiency of the coal coke powder.
The above patents relate to the activation of the coke powder and the improvement of the combustion efficiency, but do not relate to the process of preparing synthesis gas by high-efficiency gasification of the coke powder. In the conventional gasification process of the coal coke powder, the reaction kinetics bottleneck exists, the conversion condition is harsh, the conversion rate is low, the gasification media such as oxygen enrichment, water vapor and the like need to be prepared, the operation is complex, the cost is high, and the problem of nitrogen dilution exists when the air gasification is directly adopted.
The alkali lignin is a byproduct generated after cellulose is separated from plants in the paper industry, is rich in lignin and alkali metals, has huge alkali lignin yield, and reaches 5000 ten thousand tons of industrial alkali lignin generated in the paper industry all the year around, wherein only about 10 percent of the alkali lignin is prepared into products such as an adhesive, a water reducer, a dispersing agent and the like through complex processes such as oxidation, sulfonation and the like, most of the products are directly discarded or used for alkali recovery fuel, so that the resource waste is caused, and the environmental risk is also caused.
The invention patent of China discloses a demethylated lignin phenolic resin adhesive modified by halogen acid, which is characterized in that the demethylated lignin phenolic resin adhesive prepared by halogen acid modification has the advantages of high curing speed, good bonding strength and low formaldehyde emission. The invention patent of China 'a high-performance lignin-based polyurethane and a preparation method thereof' discloses a high-performance lignin-based polyurethane and a preparation method thereof, which are characterized in that the high-performance lignin-based polyurethane is prepared by carrying out polymerization reaction on lignin-containing polyester polyol, diisocyanate, lignin and an organic amine catalyst in a solvent, and carrying out curing molding. The Chinese invention patent 'a preparation method of a heavy metal adsorbent-lignin microspheres' discloses a preparation method of a heavy metal adsorbent-lignin microspheres, which is characterized in that imidazole ionic liquid is used as a solvent, the lignin microspheres are prepared under the condition of microwave-assisted dissolution, and the obtained product can efficiently treat heavy metal ion wastewater. The Chinese invention patent 'a composite oxygen carrier, a preparation method and application thereof in solid fuel gasification' discloses a composite oxygen carrier, a preparation method thereof, a method for preparing clean synthesis gas by gasifying carbon-containing solid fuel by using the oxygen carrier, and a chemical chain gasification process method and a device for solid fuel by using the oxygen carrier and a calcium-based absorbent, thereby improving gasification efficiency and removing CO 2 To obtain clean syngas. However, the above process is complicated and the conversion efficiency is low.
In conclusion, the problems of harsh reaction conditions and low conversion rate exist in the conventional thermal conversion process of the coal coke powder, and the coal coke powder is also prepared by gasification media such as oxygen enrichment and water vapor. The thermal conversion process of the alkali lignin has a bottleneck of alkali metal limitation, and the current treatment mode not only causes resource waste, but also has environmental risks.
Disclosure of Invention
Aiming at the prior technical problems, the invention aims to provide a method for alkali lignin reinforced coal coke powder chemical chain cooperative gasification, which realizes cooperative resource utilization of industrial byproduct alkali lignin and coal coke powder, solves the problems of harsh reaction conditions and low conversion rate in the conventional coal coke powder thermal conversion process, breaks through the bottleneck of alkali metal in the alkali lignin resource utilization process, and realizes high-efficiency utilization of industrial byproduct alkali lignin.
The above purpose of the invention is realized by the following technical scheme:
a method for alkali lignin reinforced coal coke powder chemical chain cooperative gasification comprises the following steps:
s1, chemical chain gasification: carrying out chemical chain cooperative gasification reaction on the coal coke powder, alkali lignin and an oxygen carrier at 700-1000 ℃;
s2, gas-solid separation: and (2) separating the reaction product in the step (S1) at the temperature of between 20 and 450 ℃ to obtain a gas-phase product and a solid-phase product.
Compared with the existing method for preparing synthesis gas by coal coke powder alone, the alkali lignin-reinforced coal coke powder chemical chain synergistic gasification method greatly improves the yield of the synthesis gas in the coal coke powder thermal conversion process and the final fuel carbon conversion rate by synergistic use of the alkali lignin and the coal coke powder, and the yield of the synthesis gas in the final gas-phase product is more than 2m 3 Kg, and a fuel carbon conversion of between 65 and 86%. The invention realizes the cooperative resource utilization of the industrial byproduct alkali lignin and the coal coke powder, not only solves the problems of harsh reaction conditions and low conversion rate in the conventional coal coke powder thermal conversion process, but also breaks through the bottleneck of alkali metal in the alkali lignin resource utilization process, and realizes the high-efficiency utilization of the industrial byproduct alkali lignin. The invention has the advantages of mild reaction conditions, high resource utilization rate, simple and convenient process, low conversion cost and the like, and can perform cooperative resource treatment on industrial organic wastes and improve social efficiencyThe resource utilization benefit and the improvement of the ecological environment have important significance.
Specifically, the gas in the gas phase product is H 2 、CO、CH 4 、CO 2 And the like are dominant.
Specifically, the alkali lignin used in the present invention comprises: 43.99% of carbon, 0.29% of nitrogen and 4.77% of hydrogen.
Further preferably, in the step S1, the temperature of the chemical-looping synergistic gasification reaction is 900 to 1000 ℃.
Preferably, in step S1, the mass ratio of the alkali lignin to the coal coke powder is 0.05 to 0.3:0.4 to 0.5.
Preferably, in the step S1, the mass ratio of the oxygen carrier to the coke powder is 0.3 to 0.5:0.4 to 0.5.
Preferably, in the step S1, the reaction time of the chemical-looping synergetic gasification reaction is 35 to 60min.
Further preferably, in the step S1, the reaction time of the chemical-looping synergetic gasification reaction is 45min.
Preferably, in the step S1, the synthesis gas H is regulated by introducing steam in the chemical looping co-gasification reaction 2 And the ratio of CO.
More preferably, in the step S1, the mass ratio of the water vapor to the oxygen carrier is 0.1 to 0.2:1. the inventors have found through studies that when the ratio of water vapor to oxygen carrier is in the above range, H in the gas phase product 2 The ratio of the carbon dioxide to the CO can be controlled to be (1.85-2.15): 1. when the gas phase product in the ratio range is beneficial to the subsequent Fischer-Tropsch synthesis, the occurrence of side reactions in the Fischer-Tropsch synthesis process is reduced, the efficiency is high, and the raw materials are saved.
Preferably, the preparation method of the oxygen carrier comprises the following steps: calcining the oxygen carrier precursor at 800-1000 ℃, crushing and screening to obtain the oxygen carrier.
More preferably, the particle size of the oxygen carrier after pulverization and sieving is controlled to 0.01 to 0.65mm.
More preferably, the reaction temperature range of the oxygen carrier is 650 to 1000 ℃.
Further preferably, the oxygen carrier precursor may be prepared by a conventional process such as a mechanical preparation method, a chemical self-assembly method, or a chemical synthesis method.
Specifically, as an alternative embodiment, the preparation method of the oxygen carrier is: taking pine as a raw material, and pyrolyzing the pine in a nitrogen atmosphere to obtain biochar; uniformly mixing a nitrate solution, adding a carrier under the stirring condition, uniformly mixing, then adding the biochar, vibrating at constant temperature to completely infiltrate the biochar, and standing to obtain an oxygen carrier precursor; and calcining the oxygen carrier precursor to obtain the oxygen carrier.
Preferably, the pine is 20 to 40 meshes.
Preferably, the temperature of the pyrolysis is 300 to 400 ℃. Further preferably, the temperature of the pyrolysis is 350 ℃.
Preferably, the pyrolysis time is 1h.
Further preferably, the nitrate solution is Ni (NO) 3 ) 2 Solution, fe (NO) 3 ) 3 Solution, al (NO) 3 ) 3 Solution, mn (NO) 3 ) 2 Solution or Co (NO) 3 ) 2 One or more of the solutions; the carrier is dodecyl silane.
Preferably, the constant-temperature oscillation time is 1-3 h. Further preferably, the constant temperature oscillation time is 2h.
Preferably, the standing time is 10-12 h. Further preferably, the standing time is 12h.
Preferably, the temperature of the calcination is 800 to 1000 ℃. Further preferably, the temperature of the calcination is 1000 ℃.
Preferably, the calcination time is 4 to 6 hours.
Preferably, after the step S2, the method further comprises oxygen carrier calcination: and (3) calcining the solid-phase product separated in the step (S2) at 800-1000 ℃, recovering lattice oxygen of the calcined oxygen carrier, and returning to the step (S2) for carrying out chemical chain gasification reaction.
Preferably, the solid phase product is calcined at 800-1000 ℃ for 30-90 min.
The invention has the following beneficial effects: the alkali lignin reinforced coal coke powder chemical chain cooperative gasification method provided by the invention not only solves the problems of harsh reaction conditions and low conversion rate in the conventional coal coke powder thermal conversion process, but also breaks through the bottleneck of alkali metal in the alkali lignin resource utilization process, and realizes the efficient utilization of the industrial byproduct alkali lignin; the preparation of gasification media such as oxygen enrichment, water vapor and the like in the conventional gasification process is avoided. The invention greatly improves the yield of the synthetic gas in the thermal conversion process of the coal coke powder and the final carbon conversion rate of the fuel, and the yield of the synthetic gas in the final gas-phase product is more than 2m 3 Kg, and a fuel carbon conversion of between 65 and 86%. The method has the advantages of mild reaction conditions, high resource utilization rate, simple and convenient process, low conversion cost and the like, has important significance for the cooperative resource treatment of the industrial organic wastes, the improvement of social resource utilization benefits and the improvement of ecological environment, and has wide project application prospect.
Drawings
FIG. 1 is a flow chart of alkali lignin enhanced chemical-looping synergistic gasification of coal coke powder according to the present invention.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
As shown in fig. 1, a method for alkali lignin enhanced coal coke powder chemical chain synergistic gasification comprises the following steps:
(1) Preparing an oxygen carrier: the oxygen carrier is prepared by adopting a chemical self-assembly method, and specifically, the oxygen carrier is prepared by taking 20-40 meshes of pine as a raw material and N 2 Slowly pyrolyzing for 1h at 350 ℃ in the atmosphere to prepare biochar; taking Ni (NO) according to molar ratio 3 ) 2 Solution, fe (NO) 3 ) 3 、Al(NO 3 ) 3 The solution is mixed evenly and added with dodecyl under the stirring conditionAdding biochar into silane (wherein the atomic ratio of Fe/Ni/Al/Si is 0.5/0.3/0.1/0.1) after uniformly mixing; oscillating the mixture in a constant-temperature oscillator for 2 hours to completely infiltrate the biochar, and standing for 12 hours; putting the mixture into a drying oven at 105 ℃ until the biochar is completely dried to obtain an oxygen carrier precursor; calcining the precursor of the composite oxygen carrier at 950 ℃ for 4h, crushing and screening to obtain the composite oxygen carrier with the particle size range of 0.15-0.25 mm, wherein the temperature range of the composite oxygen carrier is 650-1000 ℃.
(2) Chemical chain gasification: carrying out chemical chain cooperative gasification reaction on the composite oxygen carrier, the coke powder and the alkali lignin which are obtained in the step (1) at 850 ℃, wherein the reaction retention time is 45min, and introducing steam to regulate and control synthesis gas H in the chemical chain cooperative gasification reaction 2 The ratio of/CO to obtain a reaction product; the mass ratio of the water vapor to the composite oxygen carrier is 0.1:1, the mass ratio of alkali lignin, coal coke powder and oxygen carrier is 0.1:0.4:0.5.
(3) Gas-solid separation: and (3) carrying out gas-solid separation on the reaction product obtained in the step (2) at 150 ℃, wherein the range of the cut particle size of the solid-phase product is 0.25mm, and obtaining a gas-phase product and a solid-phase product. The gas phase product is H 2 And synthesis gas mainly containing CO, which can be subsequently used for Fischer-Tropsch synthesis and the like; the solid phase product contains incompletely reacted coal coke powder and alkali lignin semicoke.
(4) Calcining the oxygen carrier: and (4) calcining the solid-phase product subjected to gas-solid separation in the step (3) at 900 ℃ for 60min by adopting air, recovering lattice oxygen of the calcined oxygen carrier, and returning to the step (2) for carrying out chemical chain gasification reaction. In the calcining process, the oxygen carrier, the incompletely reacted coal coke powder and the alkali lignin semicoke react with air to release heat, and the heat is transferred to the chemical chain gasification process through the circulating oxygen carrier, so that the heat balance in the whole process is realized; the calcination process comprises a separation process of combustion tail gas and reaction ash, and the ash has a cut particle size of 0.05mm-0.15mm.
The relative composition of the gas product in step (3) as tested by Gas Chromatography (GC): h 2 Content of (2%) CO of 52.39% 2 Has a content of 15.87%, a content of CO of 26.61%, and CH 4 4.18%; fuel conversion 68.73% with syngas yield 2.03(m 3 /kg)，H 2 The ratio/CO was 1.97.
Examples 2 to 6
The differences between examples 2 to 6 and example 1 are shown in table 1 below.
TABLE 1
The gas products of examples 1 to 4 and comparative example 1 were tested for relative composition by Gas Chromatography (GC), with the results shown in table 2 below:
TABLE 2
The invention provides a method for alkali lignin reinforced coal coke powder chemical chain cooperative gasification, which greatly improves the yield of synthesis gas and the final fuel carbon conversion rate in the coal coke powder thermal conversion process, and as can be seen from the data in the table 2, in the gas-phase products prepared in the final examples 1 to 4, the yield of the synthesis gas is more than 2m 3 Kg, and a fuel carbon conversion of between 65 and 86%. The synthesis gas yields and final fuel carbon conversions for the gas phase products of examples 5-6 were similar to those of example 1. As can be seen from the data in Table 2 above, comparative example 1 is a comparative example where no alkali lignin is used, and the syngas yield in comparative example 1 is 0.82m 3 Per kg, while the fuel carbon conversion was 46.35%, which is much lower than the fuel carbon conversion and syngas yield in examples 1-6. This demonstrates that the alkali lignin and the coal coke powder have synergistic utilization, and can greatly improve the fuel carbon conversion rate and the synthesis gas yield of the product.
The alkali lignin reinforced coal coke powder chemical chain cooperative gasification method provided by the invention not only solves the problems of harsh reaction conditions and low conversion rate in the conventional coal coke powder thermal conversion process, but also breaks through the problems of alkali lignin reinforced coal coke powder chemical chain cooperative gasificationThe alkali metal bottleneck in the resource utilization process of the lignin realizes the high-efficiency utilization of the industrial byproduct alkali lignin; the preparation of gasification media such as oxygen enrichment, water vapor and the like in the conventional gasification process is avoided. The invention greatly improves the yield of the synthetic gas in the thermal conversion process of the coal coke powder and the final conversion rate of the fuel carbon, and the yield of the synthetic gas in the final gas-phase product is more than 2m 3 Kg, and a fuel carbon conversion of between 65 and 86%. The method has the advantages of mild reaction conditions, high resource utilization rate, simple and convenient process, low conversion cost and the like, has important significance for the cooperative resource treatment of the industrial organic wastes, the improvement of social resource utilization benefits and the improvement of ecological environment, and has wide project application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for alkali lignin reinforced coal coke powder chemical chain cooperative gasification comprises the following steps:
s1, chemical chain gasification: carrying out chemical chain cooperative gasification reaction on the coal coke powder, the alkali lignin and the oxygen carrier at 700-1000 ℃;
s2, gas-solid separation: and (2) separating the reaction product in the step (S1) at the temperature of between 20 and 450 ℃ to obtain a gas-phase product and a solid-phase product.
2. The method of claim 1, wherein the mass ratio of the alkali lignin to the coal coke powder is 0.05-0.3: 0.4 to 0.5.
3. The method according to claim 1 or 2, wherein the mass ratio of the oxygen carrier to the coal coke powder is 0.3 to 0.5:0.4 to 0.5.
4. The method according to claim 1, wherein in the step S1, the reaction time of the chemical-looping co-gasification reaction is 35-60 min.
5. The method according to claim 1, wherein in step S2, the syngas H is conditioned by introducing steam in a chemical looping co-gasification reaction 2 And CO, wherein the mass ratio of the water vapor to the oxygen carrier is 0.1-0.2: 1.
6. the method of claim 1, wherein the oxygen carrier is prepared by: taking pine as a raw material, and pyrolyzing the pine in a nitrogen atmosphere to obtain biochar; uniformly mixing a nitrate solution, adding a carrier under the stirring condition, uniformly mixing, then adding the biochar, vibrating at constant temperature to completely infiltrate the biochar, and standing to obtain an oxygen carrier precursor; and calcining the oxygen carrier precursor to obtain the oxygen carrier.
7. The method of claim 6, wherein the nitrate solution is Ni (NO) 3 ) 2 Solution, fe (NO) 3 ) 3 Solution, al (NO) 3 ) 3 Solution, mn (NO) 3 ) 2 Solution or Co (NO) 3 ) 2 One or more of a solution; the carrier is dodecyl silane.
8. The method of claim 6, wherein the pyrolysis temperature is 300 to 400 ℃.
9. The method of claim 6, wherein the temperature of the calcination is 800 to 1000 ℃.
10. The method of claim 1, wherein after the step S2, further comprising an oxygen carrier calcination: and (3) calcining the solid-phase product separated in the step (S2) at 800-1000 ℃, recovering lattice oxygen of the calcined oxygen carrier, and returning to the step (S2) for carrying out chemical chain gasification reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI45064B (en) * | 1962-11-15 | 1971-11-30 | Prototech Incorp | |
| CN102786994A (en) * | 2012-07-25 | 2012-11-21 | 中国科学院广州能源研究所 | Method for preparing methane-rich gas through autocatalytic gasification of biomass |
| CN112795405A (en) * | 2020-12-04 | 2021-05-14 | 大连理工大学 | System for coal gas circulation coal pyrolysis coupling chemical chain gasification coproduction oil gas |
-
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- 2022-11-15 CN CN202211427017.6A patent/CN115772424A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI45064B (en) * | 1962-11-15 | 1971-11-30 | Prototech Incorp | |
| CN102786994A (en) * | 2012-07-25 | 2012-11-21 | 中国科学院广州能源研究所 | Method for preparing methane-rich gas through autocatalytic gasification of biomass |
| CN112795405A (en) * | 2020-12-04 | 2021-05-14 | 大连理工大学 | System for coal gas circulation coal pyrolysis coupling chemical chain gasification coproduction oil gas |
Non-Patent Citations (1)
| Title |
|---|
| YUQIAN HUANG等: "Investigation into the Interactions during Staged Thermal Co-conversion of Kraft Lignin and Lignite", 《ENERGY FUELS》, vol. 31, no. 11, 12 October 2017 (2017-10-12), pages 12263 - 12271 * |
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