CN116286072B - Adjustable biomass and waste plastic catalytic co-pyrolysis system and method - Google Patents
Adjustable biomass and waste plastic catalytic co-pyrolysis system and method Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 69
- 239000002028 Biomass Substances 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000004321 preservation Methods 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000012075 bio-oil Substances 0.000 description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 19
- 239000003610 charcoal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000013502 plastic waste Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The application discloses an adjustable biomass and waste plastic catalytic co-pyrolysis system, and relates to the technical field of biomass energy thermal conversion and utilization. The pyrolysis unit comprises a tubular furnace, wherein sealing flanges are arranged at two ends of the tubular furnace, and telescopic components are arranged on the sealing flanges; the gas supply unit comprises a nitrogen cylinder which is communicated with the input end of the tube furnace through a gas supply pipeline; the condensing unit comprises a volatilizing pipeline, one end of the volatilizing pipeline is communicated with the output end of the tube furnace, the other end of the volatilizing pipeline is communicated with a condenser, and the output end of the condenser is connected with the air storage bag through a moisture remover. The application has the beneficial effects that: the plugging plates on two sides are driven by the telescopic components to be tightly attached to the mixed materials, so that the mixed materials can not overflow to two sides during rotary pyrolysis, and the reaction area can be adjusted for the mixed materials with different qualities to ensure the full progress of pyrolysis reaction.
Description
Technical Field
The application relates to the technical field of biomass energy thermal conversion utilization, in particular to an adjustable biomass and waste plastic catalytic co-pyrolysis system and method.
Background
At present, the resource utilization technology of organic solid waste (agriculture and forestry waste, plastic waste and the like) has become an effective means for partially replacing the use of fossil fuel resources. The co-pyrolysis technology of oxygen-enriched agricultural and forestry waste and hydrogen-enriched plastic waste is receiving attention because of the directional conversion of the oxygen-enriched agricultural and forestry waste and hydrogen-enriched plastic waste into high-quality bio-oil (hydrocarbons, saccharides, aldehydes, furans, etc.). The key point of the synergistic effect of biomass and waste plastics is that the thermal weight loss temperature ranges of different components are overlapped after mixing, primary products generated by pyrolysis can be mutually contacted, and the molecular sieve catalyst can reduce the reaction activation energy of biomass and plastic waste to different degrees, so that the waste plastics are thermally decomposed and chemically reacted in the main pyrolysis stage of the biomass, and finally, the product with high added value is obtained. The difference of pyrolysis reactor can influence the heat transfer mode between the living beings granule to influence the distribution of pyrolysis product, and the difference of raw materials kind and pyrolysis condition also can show influence the content and the product distribution of charcoal, oil, gas in the living beings pyrolysis process. The rotating bed reactor is often used in pyrolysis reaction due to the characteristics of wide raw material adaptability, simple operation, convenient control, uniform material mixing and heating, and capability of considering production of three morphological products.
The conventional rotating bed reactor is mostly provided with a rotating device based on the principle of a fixed bed reactor, the reaction space of a hearth is fixed, the rotating bed reactor is not suitable for full contact reaction of mixed materials, the mixed materials can be dispersed to two sides of the reactor in the rotating process, and the independent pyrolysis reaction of biomass and waste plastics is caused, so that the method is not beneficial to directionally preparing high-quality liquid fuel. In addition, the rotational speed, temperature, mass ratio of raw materials to catalyst and heat preservation time during pyrolysis are different, and the yield of products of pyrolysis reaction and the like are also obviously different.
Therefore, a pyrolysis reaction system with an adjustable reaction area and avoiding overflow to two sides in the rotation process of raw materials needs to be designed and prepared, and the directional pyrolysis of biomass and waste plastics can be effectively realized through proper rotation speed, temperature, mass ratio of raw materials to catalyst and heat preservation time adjustment.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the problems occurring in the prior art.
Therefore, one technical problem to be solved by the present application is how to ensure that overflow to both sides during rotation of the raw materials is avoided and that the reaction area can be adjusted.
In order to solve the technical problems, the application provides the following technical scheme: an adjustable biomass and waste plastic catalytic co-pyrolysis system comprises a pyrolysis unit, wherein the pyrolysis unit comprises a tube furnace, sealing flanges are arranged at two ends of the tube furnace, and a telescopic assembly is arranged on each sealing flange; the gas supply unit comprises a nitrogen cylinder which is communicated with the input end of the tube furnace through a gas supply pipeline; the condensing unit comprises a volatilizing pipeline, one end of the volatilizing pipeline is communicated with the output end of the tube furnace, the other end of the volatilizing pipeline is communicated with a condenser, and the output end of the condenser is connected with the air storage bag through a moisture remover.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the tubular furnace is provided with a hearth, a resistance layer, an insulating layer and a temperature controller from inside to outside along the radial direction.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: and through holes are uniformly formed in the sealing flange.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the telescopic assembly comprises a rotating piece, a telescopic shaft and a plugging plate, one end of the telescopic shaft is fixedly connected with the plugging plate, and the other end of the telescopic shaft is positioned in the rotating piece.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the rotating piece is positioned in the through hole and is of a hollow through structure, the side wall of the rotating piece is provided with a through spiral groove, and one ends of the rotating piece, which face the air supply pipeline and the volatilization pipeline, are respectively provided with an operating handle.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the telescopic shaft is of a hollow through structure, a guide rod is arranged on the side wall of one end of the telescopic shaft, which is positioned in the rotating piece, the guide rod is positioned in the spiral groove, and the inner cavity of the telescopic shaft is communicated with the air supply pipeline.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the diameter of the plugging plate is the same as the inner diameter of the hearth, and the plugging plate is provided with sieve holes which are correspondingly communicated with the inner cavity of the telescopic shaft.
As a preferred scheme of the adjustable biomass and waste plastic catalytic co-pyrolysis system, the application comprises the following steps: the air supply pipeline is provided with a pressure reducing valve and a rotameter.
The application has one beneficial effect:
the plugging plates on two sides are driven by the telescopic components to be tightly attached to the mixed materials, so that the mixed materials can not overflow to two sides during rotary pyrolysis, and the reaction area can be adjusted for the mixed materials with different qualities to ensure the full progress of pyrolysis reaction.
Another technical problem to be solved by the present application is how to ensure the reaction yield of catalytic co-pyrolysis of biomass and waste plastics to the greatest extent.
In order to solve the technical problems, the application also provides the following technical scheme: the biomass and waste plastic catalytic co-pyrolysis method is realized by the adjustable biomass and waste plastic catalytic co-pyrolysis system and comprises the following steps of crushing biomass and waste plastic to a particle size of more than 0.105m and less than 0.425mm to jointly form raw materials; mechanically stirring biomass, waste plastic and a catalyst for more than 10 minutes until the color of the mixed material is uniform, and then placing the mixed material in the middle of a tube furnace; adjusting the telescopic shaft to enable the plugging plate to be close to the sealing flange; introducing nitrogen for more than 20 minutes, and discharging air in the tubular furnace; reversely adjusting the telescopic shaft to enable the plugging plate to be close to the mixed material; regulating the rotating speed, the temperature, the mass ratio of the raw materials to the catalyst and the heat preservation time of the tubular furnace, and carrying out pyrolysis reaction and heat preservation on the mixed materials; after the reaction is finished, nitrogen is introduced into the tube furnace and the temperature is reduced to below 25 ℃.
As a preferred embodiment of the catalytic co-pyrolysis method for biomass and waste plastics according to the present application, wherein: the rotating speed of the tube furnace is 0-20 r/min, the temperature is 500-900 ℃, and the mass ratio of the catalyst to the raw materials is 0:1 to 15:1, the heat preservation time is more than 30 minutes.
The application has another beneficial effect:
according to the method, the telescopic shaft and the plugging plate are adjusted, so that the size of a reaction area is adapted to raw materials with different qualities, and the yield of an aromatic compound which is a target product of co-pyrolysis of biomass and waste plastics is improved; the rotating speed of the reaction yield, the reaction temperature and the mass ratio of raw materials to catalyst are regulated, so that the yield of the target product aromatic hydrocarbon compounds obtained by co-pyrolysis of biomass and waste plastics is effectively improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is an overall schematic diagram of an adjustable biomass and waste plastic catalytic co-pyrolysis system according to the present application;
FIG. 2 is a schematic diagram of the connection of a sealing flange and a rotating member of the adjustable biomass and waste plastic catalytic co-pyrolysis system according to the application;
FIG. 3 is a schematic view of a telescoping assembly of the adjustable biomass and waste plastic catalytic co-pyrolysis system of the present application;
FIG. 4 is an enlarged schematic view of FIG. 1 at A;
FIG. 5 is an enlarged schematic view at B in FIG. 3;
fig. 6 is a schematic flow chart of the catalytic co-pyrolysis method of biomass and waste plastics according to the application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more readily apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Referring to fig. 1 to 5, in a first embodiment of the present application, an adjustable biomass and waste plastic catalytic co-pyrolysis system is provided, and the system includes a pyrolysis unit 100, including a tube furnace 101, sealing flanges 102 are disposed at two ends of the tube furnace 101, and a telescopic assembly 103 is disposed on the sealing flanges 102; the gas supply unit 200 comprises a nitrogen bottle 201, and the nitrogen bottle 201 is communicated with the input end of the tube furnace 101 through a gas supply pipeline 202; the condensing unit 300 comprises a volatilizing pipeline 301, one end of the volatilizing pipeline 301 is communicated with the output end of the tube furnace 101, the other end of the volatilizing pipeline is communicated with a condenser 302, and the output end of the condenser 302 is connected with an air storage bag 304 through a moisture remover 303.
The tube furnace 101 is provided with a furnace chamber 101a, a resistive layer 101b, an insulating layer 101c, and a temperature controller 101d from inside to outside in the radial direction.
The sealing flange 102 is uniformly provided with through holes 102a.
The telescopic assembly 103 comprises a rotating piece 103a, a telescopic shaft 103b and a blocking plate 103c, one end of the telescopic shaft 103b is fixedly connected with the blocking plate 103c, and the other end of the telescopic shaft is located in the rotating piece 103 a.
The rotating member 103a is located in the through hole 102a, and is of a hollow through structure, the side wall of the rotating member is provided with a through spiral groove 103a-1, and one end of the rotating member, which faces the air supply pipeline 202 and the volatilization pipeline 301, is provided with an operation handle 103a-2.
The telescopic shaft 103b is of a hollow through structure, a guide rod 103b-1 is arranged on the side wall of one end of the telescopic shaft, which is positioned in the rotating piece 103a, the guide rod 103b-1 is positioned in the spiral groove 103a-1, and the inner cavity of the telescopic shaft 103b is communicated with the air supply pipeline 202.
The diameter of the plugging plate 103c is the same as the inner diameter of the hearth 101a, and is provided with a sieve opening 103c-1, and the sieve opening 103c-1 is correspondingly communicated with the inner cavity of the telescopic shaft 103 b.
The air supply line 202 is provided with a pressure reducing valve 202a and a rotameter 202b.
The rotating member 103a is located in the through hole 102a, and the operating handle 103a-2 is tightly attached to the surface of the sealing flange 102 because the maximum diameter is larger than that of the through hole 102a, so that the rotating member 103a can only rotate axially but not move axially inwards, but can be pulled outwards to be conveniently detached.
The aperture of the sieve mesh 103c-1 is smaller than 0.105mm, and the design ensures that the mixed material with the aperture larger than 0.105mm is not thrown out of the 103c-1 when rotating, or avoids that the raw material enters the inner cavity of the telescopic shaft 103b to cause the blockage of the telescopic shaft 103b, and ensures that nitrogen from the air supply pipeline 202 and the telescopic shaft 103b enters the area surrounded by the blocking plate 103c, and gas volatilized by similar pyrolysis reaction can also enter the volatilization pipeline 301 along the telescopic shaft 103b at the other side.
The telescopic assembly 103 works on the principle that: through the rotation of the rotating piece 103a by the operating handle 103a-2, the guide rod 103b-1 is guided by the spiral groove 103a-1, and then the telescopic shaft 103b is driven to spirally stretch, namely axially stretch while axially rotating, and finally the plugging plates 103c at two sides are tightly attached to the mixed materials, so that the mixed materials can not overflow to two sides when rotating and pyrolyzing, and the reaction area can be adjusted aiming at the mixed materials with different qualities, so that the full progress of the pyrolysis reaction is ensured.
The nitrogen in the gas supply line 202 first depressurizes the nitrogen in the nitrogen cylinder 201 to a normal range through the pressure reducing valve 202a, and the gas flow rate is controlled by the rotameter 202b.
Volatile components analyzed by the pyrolysis reaction are condensed in a condenser 302, and non-condensable gases enter a gas storage bag 304.
Example 2
Referring to fig. 6, a second embodiment of the present application provides a catalytic co-pyrolysis method for biomass and waste plastics, which is implemented by the adjustable biomass and waste plastics catalytic co-pyrolysis system of embodiment 1, and includes the following steps:
s1: crushing biomass and waste plastics to a particle size of more than 0.105m and less than 0.425mm to jointly form a raw material;
s2: mechanically stirring biomass, waste plastic and catalyst for more than 10 minutes until the color of the mixed material is uniform, and then placing the mixed material into the middle position of a tube furnace 101;
s3: adjusting the telescopic shaft 103b so that the blocking plate 103c is close to the sealing flange 102;
s4: introducing nitrogen for more than 20 minutes and discharging air in the tubular furnace 101;
s5: reversely adjusting the telescopic shaft 103b to enable the plugging plate 103c to be close to the mixed materials;
s6: the rotation speed, the temperature, the mass ratio of the raw materials to the catalyst and the heat preservation time of the tube furnace 101 are regulated, and the mixed materials are subjected to pyrolysis reaction and heat preservation;
s7: after the reaction was completed, nitrogen was introduced into the tube furnace 101 and the temperature was reduced to 25 ℃.
The rotating speed of the tube furnace 101 is 0-20 r/min, the temperature is 500-900 ℃, and the mass ratio of the catalyst to the raw materials is 0:1 to 15:1, the heat preservation time is more than 30 minutes.
Corresponding to the aperture of the sieve aperture 103c-1 being smaller than 0.105mm, the particle size of the raw materials is larger than 0.105mm and smaller than 0.425mm, wherein the larger than 0.105mm is used for avoiding the raw materials from entering the sieve aperture 103c-1, and the smaller than 0.425mm is used for ensuring that different materials can be fully contacted for reaction. If the particle size is too small (< 0.105 mm), the energy consumption in pulverizing the raw material is too high.
The biomass selected in the experiment is corn stalk, and the waste plastic selected in the experiment is polypropylene.
After the experiment was completed, nitrogen was continued to be introduced until the reactor temperature was lowered to room temperature. The yield of biochar is determined by the weight of biomass and waste plastics before and after the reaction, the yield of bio-oil is calculated by the weight before and after the reaction of a condenser, and the gas yield is calculated by a difference method.
Example 3
A third embodiment of the present application, which is different from the first two embodiments, is: corn stalks and polypropylene (the grain size of the raw materials is more than 0.105mm and less than 0.425 mm) with the mass ratio of 1:1 are uniformly mixed according to the mechanical mixing method, and then are placed in the middle of the tube furnace 101, and the uniformity in the length direction of the whole reactor is ensured. The telescopic shaft 103b is adjusted so that the plugging plates 103c connected to the telescopic shaft 103b are positioned at two ends of the hearth first. The gas flow rate was controlled by a rotameter 202b, and after sealing the system, nitrogen gas was introduced for 20 minutes to discharge the air in the tube furnace 101. The telescopic shaft 103b is then adjusted so that the two plugging plates 103c connected by the telescopic shaft 103b are tightly attached to the two ends of the mixed material. Setting the mass ratio of the sample to the catalyst to be 1:3, the rotating speed of the pyrolysis furnace to be 10r/min and the reaction temperature to be 500, 600, 700 and 800 ℃, the yield of the bio-oil (from 60.10 percent to 38.23 percent) and the bio-char (from 32.32 percent to 25.62 percent) gradually decreases with the increase of the temperature, and the yield of the biomass gas (from 7.58 percent to 36.15 percent) increases linearly. The biomass pyrolysis can generate three forms of products, namely gas, oil and charcoal, an experimenter can adjust the temperature according to respective needs, generally, the higher the temperature is, the lower the yield of the charcoal is, the more the yield of the biomass gas is, the higher the temperature is, the later the yield of the bio-oil is, the lower the yield of the bio-charcoal is, the more the yield of the biomass gas is, the higher the yield of the bio-oil is, the later the yield of the bio-oil is, and the co-pyrolysis of the biomass and the plastic is more preferable to examine the aromatic-rich components in the bio-oil, but the contradiction is that the higher the temperature is, the yield of the bio-oil is reduced, but the proportion of aromatic hydrocarbons in the bio-oil is increased. The respective yield of the biomass charcoal, the oil and the gas is related to the directional use aspect of the biomass, so that researches for analyzing the distribution rule of biomass products are often carried out, and the change rule of the charcoal, the oil and the gas along with the temperature is given to reference which product is specifically used in the later period. Note here that the higher the temperature, the lower the yield of bio-oil, but the higher the aromatic hydrocarbon in the bio-oil.
The ratio of aromatic hydrocarbon in the bio-oil is 10.21%, 18.63%, 46.36% and 68.23% respectively at 500-800 ℃, and when the temperature is continuously increased to 900 ℃, the ratio of aromatic hydrocarbon in the bio-oil is 72.03%, the ratio is slightly increased compared with 800 ℃, but the amplification is obviously reduced, the yield of the bio-oil is obviously reduced at 900 ℃, and more energy consumption and equipment requirements are higher than 800 ℃, so that the preferable temperature for aromatic hydrocarbon preparation of the device is 800 ℃, and specific product data are shown in table 1.
TABLE 1
It can be seen that as the temperature increases in the experimental range, the bio-oil and bio-char yields decrease and the biogas yield increases. The preferable temperature for preparing the aromatic compounds which are target products of the co-pyrolysis of biomass and waste plastics in the device is 800 ℃.
Example 4
A fourth embodiment of the present application is different from the first three embodiments in that: the mass ratio is 1:1 (the grain size of the raw materials is more than 0.105mm and less than 0.425 mm) are uniformly mixed according to the mechanical mixing method, and then are placed in the middle of the tube furnace 101, and the uniformity in the length direction of the whole reactor is ensured. The telescopic shaft 103b is adjusted so that the plugging plates 103c connected to the telescopic shaft 103b are positioned at two ends of the hearth first. The gas flow rate was controlled by a rotameter 202b, and after sealing the system, nitrogen gas was introduced for 20 minutes to discharge the air in the tube furnace 101. The telescopic shaft 103b is then adjusted so that the two plugging plates 103c connected by the telescopic shaft 103b are tightly attached to the two ends of the mixed material. The pyrolysis temperature is set to 600 ℃, and the rotating speed of the pyrolysis furnace is set to 10r/min. With increasing catalyst addition (catalyst: raw material mass ratio from 0:1 to 10:1), the yield of biomass gas (from 8.01% to 25.17%) increases monotonically, while the yield of biochar varies less, at a minimum of 30.16%. The yield of bio-oil (reduced from 60.10% to 42.19%) gradually decreased with increasing catalyst addition. When the catalyst/feedstock ratio is 0:1. 1: 1. 3: 1. 10:1. 15:1, the aromatic hydrocarbon in the biological oil accounts for 0%, 10.93%, 17.72%, 24.56% and 24.85% respectively. It can be seen that the aromatic hydrocarbon ratio gradually increases with increasing catalyst addition, but when the mass ratio of catalyst to raw material is 10:1, the aromatic hydrocarbon content is very small in amplification, and the aromatic hydrocarbon content is 10: the difference at 1 is not large, description 10:1, the raw materials fully contact with the catalyst, the reaction is complete, and under the condition of unchanged raw material quantity, the continuous increase of the catalyst has little influence on the aromatic hydrocarbon content, so that the mass ratio of the preferable catalyst to the raw materials for the aromatic hydrocarbon preparation of the device is 10:1, specific product data are shown in table 2.
TABLE 2
It can be seen that the yield of biomass gas monotonically increases with increasing catalyst addition, the yield of biochar changes less, and the yield of bio-oil gradually decreases with increasing catalyst addition with a trend of decreasing first and then increasing slightly. The preferred catalyst/raw material ratio for preparing the target product aromatic hydrocarbon compound by co-pyrolysis of biomass and waste plastics of the device is 10:1.
example 5
A fifth embodiment of the present application is different from the first four embodiments in that: corn stalks and polypropylene (the grain size of the raw materials is more than 0.105mm and less than 0.425 mm) with the mass ratio of 1:1 are uniformly mixed according to the mechanical mixing method, and then are placed in the middle of the tube furnace 101, and the uniformity in the length direction of the whole reactor is ensured. The telescopic shaft 103b is adjusted so that the plugging plates 103c connected to the telescopic shaft 103b are positioned at two ends of the hearth first. The gas flow rate was controlled by a rotameter 202b, and after sealing the system, nitrogen gas was introduced for 20 minutes to discharge the air in the tube furnace 101. The telescopic shaft 103b is then adjusted so that the two plugging plates 103c connected by the telescopic shaft 103b are tightly attached to the two ends of the mixed material. The pyrolysis temperature was set at 600℃and the ratio of raw materials/catalyst was 1:3. As the rotational speed increases from 0r/min to 20r/min, the yields of biochar and bio-oil show a tendency to decrease first and then increase, with the yields of biochar and bio-oil being lowest at 15r/min, 27.21% and 45.79%, respectively. The yield of the biomass gas is gradually increased along with the increase of the rotating speed, reaches the highest (27.00%) at 15r/min, and then is reduced along with the increase of the rotating speed. The aromatic hydrocarbon content is firstly monotonously increased and then decreased along with the increase of the rotating speed, and the aromatic hydrocarbon content is respectively 11.63%, 14.17%, 18.52%, 24.12% and 19.61% at 0, 5, 10, 15 and 20r/min, so that the phenomenon is probably caused by the fact that when the reactor rotates, the relative flow of the reactor, the materials and the materials per se is enhanced, the heat transfer is accelerated, and the contact of corn straw and polypropylene pyrolysis volatile matters is promoted, so that the possibility is provided for more conversion of olefin and oxygen-containing compounds into aromatic hydrocarbon. When the rotating speed is too high, the contact and sliding between the material and the wall surface of the reactor are weakened, which is unfavorable for obtaining heat and the sufficient contact of pyrolysis volatile matters, thereby reducing the content of aromatic hydrocarbon. Thus, the preferred rotational speed for the aromatic hydrocarbon production of the present apparatus is 15r/min (24.12%), and the specific product data are shown in Table 3.
TABLE 3 Table 3
It can be seen that the minimum value of the bio-oil and the biochar, the maximum value of the biomass gas and the maximum value of the aromatic hydrocarbon compound which is a target product of the co-pyrolysis of the biomass and the waste plastic are all obtained at 15 r/min.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (4)
1. An adjustable biomass and waste plastic catalytic co-pyrolysis system is characterized in that: comprising the steps of (a) a step of,
the pyrolysis unit (100) comprises a tube furnace (101), sealing flanges (102) are arranged at two ends of the tube furnace (101), and a telescopic assembly (103) is arranged on the sealing flanges (102);
the gas supply unit (200) comprises a nitrogen bottle (201), and the nitrogen bottle (201) is communicated with the input end of the tube furnace (101) through a gas supply pipeline (202);
the condensing unit (300) comprises a volatilizing pipeline (301), one end of the volatilizing pipeline (301) is communicated with the output end of the tube furnace (101), the other end of the volatilizing pipeline is communicated with a condenser (302), and the output end of the condenser (302) is connected with the air storage bag (304) through a moisture remover (303);
through holes (102 a) are uniformly formed in the sealing flange (102);
the telescopic assembly (103) comprises a rotating piece (103 a), a telescopic shaft (103 b) and a blocking plate (103 c), one end of the telescopic shaft (103 b) is fixedly connected with the blocking plate (103 c), and the other end of the telescopic shaft is positioned in the rotating piece (103 a);
the rotating piece (103 a) is positioned in the through hole (102 a) and is of a hollow through structure, a through spiral groove (103 a-1) is formed in the side wall of the rotating piece, and an operating handle (103 a-2) is respectively arranged at one end of the rotating piece, which faces the air supply pipeline (202) and the volatilizing pipeline (301);
the telescopic shaft (103 b) is of a hollow through structure, a guide rod (103 b-1) is arranged on the side wall of one end of the telescopic shaft, which is positioned in the rotating piece (103 a), the guide rod (103 b-1) is positioned in the spiral groove (103 a-1), and the inner cavity of the telescopic shaft (103 b) is communicated with the air supply pipeline (202);
the diameter of the plugging plate (103 c) is the same as the inner diameter of the hearth (101 a), and is provided with a sieve mesh (103 c-1), and the sieve mesh (103 c-1) is correspondingly communicated with the inner cavity of the telescopic shaft (103 b).
2. The adjustable biomass and waste plastic catalytic co-pyrolysis system of claim 1, wherein: the tubular furnace (101) is provided with a hearth (101 a), a resistor layer (101 b), an insulating layer (101 c) and a temperature controller (101 d) from inside to outside along the radial direction.
3. The adjustable biomass and waste plastic catalytic co-pyrolysis system of claim 2, wherein: the air supply pipeline (202) is provided with a pressure reducing valve (202 a) and a rotameter (202 b).
4. A catalytic co-pyrolysis method for biomass and waste plastics is characterized in that: the method is realized by the adjustable biomass and waste plastic catalytic co-pyrolysis system as claimed in any one of claims 1-3, and comprises the following steps,
crushing biomass and waste plastics to a particle size of more than 0.105mm and less than 0.425mm to jointly form a raw material;
mechanically stirring biomass, waste plastic and a catalyst for more than 10 minutes until the color of the mixed material is uniform, and then placing the mixed material into the middle part of a tube furnace (101);
adjusting the telescopic shaft (103 b) so that the blocking plate (103 c) is close to the sealing flange (102);
introducing nitrogen for more than 20 minutes and discharging air in the tubular furnace (101);
reversely adjusting the telescopic shaft (103 b) to enable the blocking plate (103 c) to be close to the mixed materials;
the rotation speed, the temperature, the mass ratio of raw materials to catalyst and the heat preservation time of the tube furnace (101) are regulated, and the mixed materials are subjected to pyrolysis reaction and heat preservation;
after the reaction is finished, introducing nitrogen into a tube furnace (101) and cooling to below 25 ℃;
the rotating speed of the tube furnace (101) is 0-20 r/min, the temperature is 500-900 ℃, and the mass ratio of the catalyst to the raw materials is 0:1 to 15:1, the heat preservation time is more than 30 minutes.
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| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
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| CN105419848A (en) * | 2015-11-18 | 2016-03-23 | 江苏大学 | Method for preparing bio-oil through co-pyrolysis catalytic hydrogenation by means of algae and waste rubber |
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