Biomass and coal coupled pyrolysis process
Through the coupled pyrolysis process of biomass and coal, the stability and environmental pollution problems of low-order coal pyrolysis technology are solved, efficient and low-carbon industrial applications are achieved, and the utilization efficiency and economic benefits of low-order coal are improved.
Patent Information
- Application Number
- CN202510630517.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-16
- Publication Date
- 2025-07-04
AI Technical Summary
Low-order coal pyrolysis technology has not yet achieved long-term safe and stable operation, limiting its large-scale commercial application, and the existing processes have problems of energy waste and environmental pollution.
The coupled pyrolysis process of biomass and coal is adopted to achieve efficient desulfurization and decarbonization through gasification raw material pretreatment, drying and powder making, gas flow bed pyrolysis and high-temperature synthesis gas separation, and obtain high-grade synthesis gas and coal tar, which is suitable for different industrial scenarios.
It improves the development and conversion efficiency of low-end coal, reduces carbon emissions, increases economic benefits, and provides flexible industrial application solutions.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of pyrolysis processes and relates to a coupled pyrolysis process for biomass and coal. Background Art
[0002] Low-rank coal refers to coal with relatively low degree of coalification, mainly including long-flame coal, lignite, non-caking coal, weakly caking coal and other coal types with relatively low degree of coalification. China has rich low-rank coal resources, accounting for more than 55% of the proven coal reserves. Due to the high moisture content, high ash content, easy weathering and spontaneous combustion, and difficulty in washing and storage of low-rank coal, the development and utilization of low-rank coal are greatly restricted. The low-rank coal pyrolysis technology has the advantages of utilizing low-quality coal resources, improving energy utilization efficiency, reducing environmental pollution, etc., so it has important significance in the energy field.
[0003] There have been various low-rank coal pyrolysis technologies at home and abroad for pilot tests, industrial demonstrations and industrialization promotions, which have proved the technical feasibility. So far, no low-rank coal powder pyrolysis technology has achieved long-term safe and stable operation, and all are still in the initial stages of experimental research and engineering. This restricts the large-scale commercial application of low-rank coal powder pyrolysis technology.
[0004] In the low-temperature carbonization process, gas and solid heat carriers each have their unique characteristics and application considerations. Gas heat carriers, with their high heat transfer efficiency and ability to quickly and evenly distribute heat, significantly improve the reaction rate and production efficiency, while ensuring high-quality reaction products. Solid heat carriers have relatively low heat transfer efficiency and relatively slow reaction rates. For different downstream users' requirements for gas, gas heat carriers or a combination of gas / solid heat carriers can be selected accordingly.
[0005] The gas heat carrier carbonization process uses high-temperature gas as the heat transfer medium to transfer heat to solid materials, enabling them to undergo pyrolysis reactions without contacting oxygen. This process can effectively remove volatile components from solid materials, obtaining high-quality solid products and gas products.
[0006] 1. Energy conservation: The gas heat carrier carbonization process uses high-temperature gas as the heat carrier, with high thermal efficiency and small energy loss, and can save a large amount of energy compared with traditional processes. For different application scenarios, gas heat carriers can be used to directly pyrolyze low-rank coal, or gas heat carriers can be used to heat the char of solid heat carriers, and the char is used as the solid heat carrier to pyrolyze low-rank coal again.
[0007] 2. Environmental protection: This process does not produce soot and harmful gases during carbonization, has little environmental pollution, the carbon dioxide generated by gasification can be recycled, and the use of biomass for co-treatment can reduce carbon emissions, meeting the development trend of green environmental protection.
[0008] 3. High efficiency: The dry distillation process can achieve continuous production. While providing high-grade hydrocarbon gas for downstream devices, it can thermally decompose low-rank coal in a graded manner, extract high-value coal tar, improve production efficiency, and reduce production costs.
[0009] 4. Green: Combining the co-pyrolysis process of biomass and coal, desulfurizing and removing carbon dioxide from high-temperature syngas can reduce carbon emissions during the pyrolysis process, achieving zero or negative emissions, and developing a new co-production process for the green carbon utilization of biomass. Summary of the Invention
[0010] The purpose of the present invention is to provide a coupled pyrolysis process for biomass and coal. The present invention relates to a co-gasification and pyrolysis process for low-rank coal and biomass, a multi-purpose production process with a common supply. This process can adjust the raw material ratio, select a gas heat carrier or a combined gas / solid heat carrier method, adjust the gasification pressure, desulfurize, and remove carbon dioxide, and is applicable to different downstream application scenarios of coal, such as the utilization of low-rank coal in traditional thermal power plants, reducing the power generation cost, improving the power generation efficiency, emission reduction / deep peak shaving and green hydrogen production, deep processing of pyrolyzed coal tar, co-firing of upgraded semi-coke, and opening up a new co-disposal process for traditional power plants, reducing carbon emissions and increasing revenue; injecting coke in steel mills, using hydrogen extraction from syngas as a reducing agent to reduce emissions and carbon; separate utilization of different components in coal chemical industry, etc. This method not only promotes the large-scale development and conversion of low-rank coal, but also significantly improves economic benefits and reduces carbon emissions.
[0011] The purpose of the present invention can be achieved by the following technical solutions: A coupled pyrolysis process for biomass and coal includes the following steps: Step 1, pretreatment of gasification raw materials; drying and pulverizing to an appropriate particle size to meet gasification requirements. Among them, biomass is dried and baked at 250 - 300 °C and ground through a 150 - 200 mesh sieve. Step 2, obtaining high-temperature syngas after gasification; Step 3, grinding and drying low-rank coal to obtain pulverized coal; Step 4, inputting the pulverized coal in Step 3 into a entrained flow bed to mix with high-temperature syngas for flash pyrolysis; Step 5, separating the high-temperature gas-phase substances by high-temperature filtration to obtain high-temperature oil gas and semi-coke respectively. Quench and cool the high-temperature oil gas to separate it into coal tar and a mixed gas. The mixed gas is desulfurized and carbon dioxide is removed through a desulfurization tower to obtain a high-grade pyrolysis gas and a syngas mixed gas.
[0012] As a preferred technical solution of the present invention, in Step 1, after the biomass gasification raw materials are dried and baked at 250 - 300 °C, they are pulverized to less than 0.2 mm to minimize carbon deposition and gas production, thereby maximizing the effective components of biomass.
[0013] In Step 1, the gasification feedstock is low-rank coal, pyrolysis semicoke, biomass single material, or a mixed material composed of a combination of the above raw materials; As a preferred technical solution of the present invention, the biomass material undergoes skid-mounted small-scale drying and granulation. The skid-mounted small-scale pyrolysis device is convenient for decentralized layout. Granulation increases density and is easy to store, which can effectively reduce transportation costs.
[0014] As a preferred technical solution of the present invention, in Step 2, the reaction temperature of the gasification is 1150 - 1500 °C; when using the gasification synthesis gas as a heat source, the wastewater generated by pyrolysis and the coal pyrolysis semicoke can be used to prepare water coal slurry to eliminate the discharge of phenolic wastewater).
[0015] As a preferred technical solution of the present invention, in Steps 1 to 3, the mass ratio of the gasification feedstock to the low-rank coal is 0 - 100%; the gasification feedstock is a mixed material composed of any one or a combination of coal, semicoke, and biomass materials.
[0016] As a preferred technical solution of the present invention, in Step 3, the grinding is to grind to a particle size of 150 - 200 mesh; the pulverized coal of this particle size is easy to dry quickly and flash pyrolyze, so that the yield of coal tar reaches 150 - 200% of the Gray-King yield; the condensed water obtained by drying is used as industrial water. The drying of the pulverized coal adopts hot air drying while grinding and secondary drum drying, which reduces the moisture content of the pulverized coal entering the pyrolysis system, reduces the pyrolysis energy consumption, reduces the generation of phenolic water during the pyrolysis process, and flash pyrolyzes in a hydrogen-rich environment. The pyrolysis phenolic wastewater can be used to prepare the raw material of water coal slurry.
[0017] As a preferred technical solution of the present invention, in Step 4, the inlet temperature of the synthesis gas of the entrained flow bed is 1150 - 1500 °C; the inlet temperature of the low-rank coal of the entrained flow bed is 90 - 150 °C; the end temperature of the entrained flow bed is 500 - 600 °C; the synthesis gas is the synthesis gas gasified from low-rank coal, pyrolysis semicoke, biomass single material, or mixed material. The low-rank coal pyrolysis uses the above high-temperature synthesis gas as the heat source for pyrolysis, avoiding the generation of flue gas, and reducing the emission of carbon dioxide by recovering carbon dioxide; gas hot carrier high-temperature flash pyrolysis, the gas inlet temperature of the pyrolysis entrained flow bed is high, the pulverized coal inlet temperature is low, the temperature difference is large, the pulverized coal flashes pyrolyzes, and pyrolyzes in a high-temperature hydrogen-rich environment, improving the yield of pyrolysis coal tar.
[0018] As a preferred technical solution of the present invention, after the processes of desulfurization and carbon dioxide removal, a pure gas can be obtained, which can be used as a synthesis raw material gas for coal chemical industry, for deep peak shaving of traditional thermal power plants, and for other industries that require clean high-calorific value fuels.
[0019] As a preferred technical solution of the present invention, syngas is subjected to compression, purification (desulfurization and decarbonization), and separation processes to extract high-purity hydrogen (H2). By adopting a full biomass gasification solution, green hydrogen can be produced, creating favorable conditions for the distributed layout of hydrogen.
[0020] As a preferred technical solution of the present invention, the preparation method of the adsorbent activated carbon includes the following steps: S1. Grind the activated carbon, add it to a nitric acid solution after sieving, stir it while heating, filter and wash it until the washing liquid is neutral, and then vacuum dry it to constant weight to obtain pretreated activated carbon. S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate, then heat and stir, filter to obtain the solid, wash it three times with anhydrous ethanol, dry it, and then calcine it to obtain composite particles. S3. Under a nitrogen atmosphere, ultrasonically mix the composite particles, anhydrous ethanol, and fluorosalicylaldehyde, let it stand, then add dianisidine and stir at a constant temperature, filter to obtain the solid, wash it three times with anhydrous ethanol, and vacuum dry it to constant weight to obtain the product.
[0021] As a preferred technical solution of the present invention, in step S1, the sieving is through a 40-60 mesh sieve; the mass ratio of the activated carbon to the nitric acid solution is 5-7:32-40; the concentration of the nitric acid solution is 5 mol / L; the heating and stirring is carried out at a temperature of 60-75 °C and a rotation speed of 400-500 rpm for 8-10 h; the temperature of the vacuum drying is 90 °C.
[0022] As a preferred technical solution of the present invention, in step S2, the heating and stirring is carried out at a temperature of 60-68 °C for 5-6 h; the drying is carried out at a temperature of 110-120 °C for 1.5-2.0 h; the calcination is carried out at a temperature of 380-400 °C for 3-4 h; the mass ratio of the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate is 12-13:40-50:2.2-2.4.
[0023] As a preferred technical solution of the present invention, in step S3, the ultrasonic mixing is carried out at a power of 600-800 W for 10-15 min; the standing time is 2-3 h; the constant-temperature stirring is carried out at a temperature of 60-70 °C and a rotation speed of 500-800 rpm for 4-5 h; the temperature of the vacuum drying is 80 °C; the mass ratio of the composite particles, anhydrous ethanol, fluorosalicylaldehyde, and dianisidine is 13-14:40-50:2.0-2.3:1.5-1.8; the fluorosalicylaldehyde is one or more of 3-fluorosalicylaldehyde, 4-fluorosalicylaldehyde, 5-fluorosalicylaldehyde, and 6-fluorosalicylaldehyde.
[0024] The beneficial effects of the present invention: The present invention relates to a technology for gasifying a single material or a mixed material of low-rank coal, pyrolytic char, and biomass in coordination with the pyrolysis of low-rank coal. This process first extracts high-value tar components and high-grade syngas and pyrolysis gas mixture from low-rank coal through a classification method, and then reasonably applies the remaining solid char. This method not only promotes the large-scale development and conversion of low-rank coal, but also provides a collaborative flexible solution to configure a complete set of pyrolysis systems for different industrial scenarios, significantly improving the economic benefits of the entire system and reducing carbon emissions. Detailed Embodiments
[0025] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following, in combination with embodiments, details the specific embodiments, structures, features, and their effects according to the present invention as follows. Embodiment 1
[0026] A coupled pyrolysis process of biomass and coal includes the following steps: Step 1: Dry the biomass material by baking at 260°C and grind it into powder. Step 2: Gasify the powder obtained in Step 1 with a gasification medium (pure oxygen) to obtain high-temperature syngas. Embodiment 2
[0027] A coupled pyrolysis process of biomass and coal includes the following steps: Step 1: Dry the biomass material by baking at 260°C and grind it into powder. Step 2: Obtain syngas after gasification with a gasification medium. Step 3: Grind and dry the low-rank coal to obtain pulverized coal, wherein the grinding is to a particle size less than 200 mesh. Step 4: Input the syngas obtained in Step 2 and the pulverized coal into a entrained flow bed for pyrolysis treatment to obtain char and gas phase substances, wherein the inlet temperature of the syngas in the entrained flow bed is 1250°C; the inlet temperature of the low-rank coal in the entrained flow bed is 110°C; the end temperature of the entrained flow bed is 550°C. Step 5: High-temperature filter and separate the gas phase substances to obtain high-temperature oil gas and char, and quickly cool and separate the high-temperature oil gas to obtain coal tar and pyrolysis gas.
[0028]
[0029]
[0030]
[0031] Embodiment 3 A coupling pyrolysis process of biomass and coal comprises the following steps: Step 1: Prepare a mixed slurry from the fuel powder, with a slurry concentration of 60%; Step 2: Obtain synthesis gas after gasification with a gasification medium; Step 3: Grind the low-rank coal, and after drying, obtain coal powder; wherein, the grinding is to grind to a particle size of 200 mesh; Step 4: Input the synthesis gas and coal powder from Step 2 into a entrained flow bed for pyrolysis treatment to obtain semicoke and gas-phase substances; wherein, the inlet temperature of the synthesis gas in the entrained flow bed is 1350 °C; the inlet temperature of the low-rank coal in the entrained flow bed is 110 °C; the end temperature of the entrained flow bed is 550 °C; Step 5: High-temperature filter and separate the gas-phase substances to obtain high-temperature oil-gas and semicoke, and rapidly cool and separate the high-temperature oil-gas to obtain coal tar and pyrolysis gas.
[0032] Using the fuel powder to prepare the mixed slurry as the design raw material, the proximate analysis data is as follows: Raw material type: Mixed powder (200 mesh) ① Proximate analysis Moisture content: 10% (as received basis) Ash content: 13% (dry basis) Volatile matter: 80% (dry ash-free basis) Fixed carbon: 21% (dry ash-free basis) ② Ultimate analysis Carbon: 55% (dry ash-free basis) Hydrogen: 7% (dry ash-free basis) Nitrogen: 0.8% (dry ash-free basis) Sulfur: 0.07% (dry ash-free basis) Oxygen: 38% (dry ash-free basis) ③ Combustion calorific value analysis Calorific value: 17 MJ / kg
[0033] Example 4
[0034] The preparation method of the adsorbent activated carbon comprises the following steps: S1: Grind the activated carbon, add it to a nitric acid solution after passing through a 200-mesh sieve, stir at 60 °C and 400 rpm for 8 h, then filter to obtain the solid, wash until the washing liquid is neutral, and vacuum dry at 90 °C to constant weight to obtain the pretreated activated carbon; wherein, the mass ratio of the activated carbon to the nitric acid solution is 5:32; the concentration of the nitric acid solution is 5 mol / L; S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate, stir at 60 °C for 5 h, filter to obtain the solid, wash it three times with absolute ethanol, dry it at 110 °C for 1.5 h, and then calcine it at 380 °C for 3 h to obtain composite particles; wherein, the mass ratio of the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate is 12:40:2.2; S3. Under a nitrogen atmosphere, ultrasonically irradiate the composite particles, absolute ethanol, and fluorosalicylaldehyde at a power of 600 W for 10 min, let it stand for 2 h, add dianisidine, and stir at 60 °C and 500 rpm for 4 h, filter to obtain the solid, wash it three times with absolute ethanol, and vacuum dry it at 80 °C to constant weight, then it is obtained; wherein, the mass ratio of the composite particles, absolute ethanol, fluorosalicylaldehyde, and dianisidine is 13:40:2.0:1.5; the fluorosalicylaldehyde is 5-fluorosalicylaldehyde.
[0035] Example 5 The preparation method of the adsorbent activated carbon comprises the following steps: S1. Grind the activated carbon, sieve it through a 200-mesh sieve, add it to a nitric acid solution, stir at 64 °C and 425 rpm for 8.5 h, filter to obtain the solid, wash it until the washing liquid is neutral, and vacuum dry it at 90 °C to constant weight to obtain the pretreated activated carbon; wherein, the mass ratio of the activated carbon to the nitric acid solution is 5.5:34; the concentration of the nitric acid solution is 5 mol / L; S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate, stir at 62 °C for 5.2 h, filter to obtain the solid, wash it three times with absolute ethanol, dry it at 112 °C for 1.6 h, and then calcine it at 385 °C for 3.2 h to obtain composite particles; wherein, the mass ratio of the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate is 12.2:42:2.25; S3. Under a nitrogen atmosphere, ultrasonically irradiate the composite particles, absolute ethanol, and fluorosalicylaldehyde at a power of 650 W for 11 min, let it stand for 2.2 h, add dianisidine, and stir at 62 °C and 575 rpm for 4.2 h, filter to obtain the solid, wash it three times with absolute ethanol, and vacuum dry it at 80 °C to constant weight, then it is obtained; wherein, the mass ratio of the composite particles, absolute ethanol, fluorosalicylaldehyde, and dianisidine is 13.2:42:2.1:1.58; the fluorosalicylaldehyde is 5-fluorosalicylaldehyde.
[0036] Example 6 The preparation method of the adsorbent activated carbon comprises the following steps: S1. Grind the activated carbon, pass it through a 200-mesh sieve, add it to a nitric acid solution, stir at 68 °C and 450 rpm for 9 h, filter to obtain the solid, wash it until the washing liquid is neutral, and vacuum dry it at 90 °C until constant weight to obtain the pretreated activated carbon. Among them, the mass ratio of the activated carbon to the nitric acid solution is 6:36; the concentration of the nitric acid solution is 5 mol / L; S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate, stir at 64 °C for 5.5 h, filter to obtain the solid, wash it three times with absolute ethanol, dry it at 115 °C for 1.8 h, and then calcine it at 390 °C for 3.5 h to obtain the composite particles. Among them, the mass ratio of the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate is 12.5:45:2.3; S3. Under a nitrogen atmosphere, ultrasonically irradiate the composite particles, absolute ethanol and fluorosalicylaldehyde at a power of 700 W for 12 min, let it stand for 2.5 h, then add dianisidine and stir at 65 °C and 650 rpm for 4.5 h, filter to obtain the solid, wash it three times with absolute ethanol, and vacuum dry it at 80 °C until constant weight to obtain the product. Among them, the mass ratio of the composite particles, absolute ethanol, fluorosalicylaldehyde and dianisidine is 13.5:45:2.15:1.65; the fluorosalicylaldehyde is 5-fluorosalicylaldehyde.
[0037] Example 7 The preparation method of the adsorbent activated carbon comprises the following steps: S1. Grind the activated carbon, pass it through a 200-mesh sieve, add it to a nitric acid solution, stir at 71 °C and 475 rpm for 9.5 h, filter to obtain the solid, wash it until the washing liquid is neutral, and vacuum dry it at 90 °C until constant weight to obtain the pretreated activated carbon. Among them, the mass ratio of the activated carbon to the nitric acid solution is 6.5:38; the concentration of the nitric acid solution is 5 mol / L; S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate, stir at 66 °C for 5.8 h, filter to obtain the solid, wash it three times with absolute ethanol, dry it at 118 °C for 1.9 h, and then calcine it at 395 °C for 3.8 h to obtain the composite particles. Among them, the mass ratio of the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate is 12.8:48:2.35; S3. Under a nitrogen atmosphere, ultrasonic the composite particles, absolute ethanol and fluorosalicylaldehyde at a power of 750 W for 14 min. After standing for 2.8 h, add dianisidine and stir at 68 °C and 725 rpm for 4.8 h. Filter to obtain the solid, wash it three times with absolute ethanol, and vacuum dry it at 80 °C until constant weight, then it is obtained; wherein, the mass ratio of the composite particles, absolute ethanol, fluorosalicylaldehyde and dianisidine is 13.8:48:2.22:1.7; the fluorosalicylaldehyde is 5-fluorosalicylaldehyde.
[0038] Example 8 The preparation method of the adsorption activated carbon comprises the following steps: S1. Grind the activated carbon, sieve it through a 200-mesh sieve, then add nitric acid solution and stir at 75 °C and 500 rpm for 10 h. Filter to obtain the solid, wash it until the washing liquid is neutral, and vacuum dry it at 90 °C until constant weight to obtain the pretreated activated carbon; wherein, the mass ratio of the activated carbon to the nitric acid solution is 7:40; the concentration of the nitric acid solution is 5 mol / L; S2. Under a nitrogen atmosphere, mix the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate, and stir at 68 °C for 6 h. Filter to obtain the solid, wash it three times with absolute ethanol, dry it at 120 °C for 2.0 h, and then calcine it at 400 °C for 4 h to obtain the composite particles; wherein, the mass ratio of the pretreated activated carbon, propylene glycol and tetra-n-propyl zirconate is 13:50:2.4; S3. Under a nitrogen atmosphere, ultrasonic the composite particles, absolute ethanol and fluorosalicylaldehyde at a power of 800 W for 15 min. After standing for 3 h, add dianisidine and stir at 70 °C and 800 rpm for 5 h. Filter to obtain the solid, wash it three times with absolute ethanol, and vacuum dry it at 80 °C until constant weight, then it is obtained; wherein, the mass ratio of the composite particles, absolute ethanol, fluorosalicylaldehyde and dianisidine is 14:50:2.3:1.8; the fluorosalicylaldehyde is 5-fluorosalicylaldehyde.
[0039] Comparative Example 4 Compared with Example 6, the difference in Comparative Example 4 is that step S1 is not carried out, and activated carbon is used instead of pretreated activated carbon, and the other components, preparation steps and parameters are the same.
[0040] Comparative Example 5 Compared with Example 6, the difference in Comparative Example 5 is that tetra-n-propyl zirconate is not used, and the other components, preparation steps and parameters are the same.
[0041] Comparative Example 6 Compared with Example 6, the difference in Comparative Example 6 is that salicylaldehyde is used instead of fluorosalicylaldehyde, and the other components, preparation steps and parameters are the same.
[0042] Comparative Example 7 Compared with Example 6, the difference in Comparative Example 7 is that salicylaldehyde fluoride is not used, and the other components, preparation steps and parameters are the same.
[0043] Comparative Example 8 Compared with Example 6, the difference in Comparative Example 8 is that o-anisidine is used instead of dianisidine, and the other components, preparation steps and parameters are the same.
[0044] Comparative Example 9 Compared with Example 6, the difference in Comparative Example 9 is that dianisidine is not used, and the other components, preparation steps and parameters are the same.
[0045] The desulfurization rates of the adsorbent activated carbons prepared in Examples 4-8 and Comparative Examples 4-9 were tested respectively, and the test results are shown in Table 1.
[0046]
[0047] It can be seen from the test results in Table 1 that compared with Comparative Examples 4-9, the adsorbent activated carbons prepared by the present invention have excellent desulfurization effects.
[0048] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the equivalent embodiments by using the disclosed technical content within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any indirect modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.
Claims
1. Coupled pyrolysis process of biomass and coal, characterized in that, The pyrolysis process includes the following steps: Step 1, pretreatment of the gasification raw material; the pretreatment includes drying and pulverizing; Step 2, gasifying the pretreated gasification raw material to obtain high-temperature syngas; Step 3, grinding low-rank coal, and after drying, obtaining pulverized coal; Step 4, conveying the pulverized coal in Step 3 into a entrained flow bed to be mixed with the high-temperature syngas for flash pyrolysis; Step 5, filtering and separating the high-temperature gas-phase substances to obtain high-temperature oil-gas and semicoke respectively, quenching and cooling the high-temperature oil-gas for separation to obtain coal tar and a mixed gas, and subjecting the mixed gas to desulfurization and carbon dioxide removal treatment in a desulfurization tower to obtain a high-grade pyrolysis gas and a syngas mixture.
2. The coupled pyrolysis process of biomass and coal according to claim 1, wherein: In Step 2, the reaction temperature of the gasification is 1150 - 1500 °C.
3. A coupled pyrolysis process of biomass and coal according to claim 1, characterized in that: In Steps 1 to 2, the gasification raw material is a mixed material composed of any one or more combinations of coal, pyrolysis semicoke, and biomass materials.
4. A coupled pyrolysis process of biomass and coal according to claim 1, characterized in that: In Step 3, the grinding is to grind to a particle size of 150 - 200 mesh; the semicoke is used to prepare activated carbon or a gasification raw material.
5. A coupled pyrolysis process of biomass and coal according to claim 1, characterized in that: In Step 4, the inlet temperature of the syngas in the entrained flow bed is 1150 - 1500 °C; the inlet temperature of the low-rank coal in the entrained flow bed is 90 - 150 °C; the terminal temperature of the pyrolysis reaction in the entrained flow bed is 500 - 600 °C.
6. The co-pyrolysis process of biomass and coal according to claim 1, characterized in that, The preparation method of the adsorbent activated carbon includes the following steps: S1, grinding and sieving the activated carbon, adding a nitric acid solution, heating and stirring, then filtering and washing until the washing liquid is neutral, and vacuum drying to constant weight to obtain pretreated activated carbon; S2, under a nitrogen atmosphere, mixing the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate evenly, then heating and stirring, filtering to obtain solid substances, washing three times with absolute ethanol, drying, and then calcining to obtain composite particles; S3, under a nitrogen atmosphere, ultrasonically mixing the composite particles, absolute ethanol, and fluorosalicylaldehyde, standing, then adding dianisidine and stirring at a constant temperature, filtering to obtain solid substances, washing three times with absolute ethanol, and vacuum drying to constant weight to obtain the product.
7. A coupled pyrolysis process of biomass and coal according to claim 6, characterized in that: In Step S1, the sieving is through a 200-mesh sieve; the mass ratio of the activated carbon to the nitric acid solution is 5 - 7:32 - 40; the concentration of the nitric acid solution is 5 mol / L; the heating and stirring is stirring at a temperature of 60 - 75 °C and a rotation speed of 400 - 500 rpm for 8 - 10 h; the temperature of the vacuum drying is 90 °C.
8. A coupled pyrolysis process of biomass and coal according to claim 6, characterized in that: In Step S2, the heating and stirring is stirring at a temperature of 60 - 68 °C for 5 - 6 h; the drying is drying at a temperature of 110 - 120 °C for 1.5 - 2.0 h; the calcining is calcining at a temperature of 380 - 400 °C for 3 - 4 h; the mass ratio of the pretreated activated carbon, propylene glycol, and tetra-n-propyl zirconate is 12 - 13:40 - 50:2.2 - 2.
4.
9. A coupled pyrolysis process of biomass and coal according to claim 6, characterized in that: In step S3, the ultrasonic mixing is carried out at a power of 600 - 800 W for 10 - 15 min; the standing time is 2 - 3 h; the constant temperature stirring is carried out at a temperature of 60 - 70 °C and a rotation speed of 500 - 800 rpm for 4 - 5 h; the temperature of the vacuum drying is 80 °C; the mass ratio of the composite particles, absolute ethanol, fluorinated salicylaldehyde and dianisidine is 13 - 14:40 - 50:2.0 - 2.3:1.5 - 1.8; the fluorinated salicylaldehyde is one or more of 3 - fluorosalicylaldehyde, 4 - fluorosalicylaldehyde, 5 - fluorosalicylaldehyde and 6 - fluorosalicylaldehyde.