CN115962469B - Rotary catalytic pyrolysis device and method - Google Patents
Rotary catalytic pyrolysis device and method Download PDFInfo
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- CN115962469B CN115962469B CN202310024484.2A CN202310024484A CN115962469B CN 115962469 B CN115962469 B CN 115962469B CN 202310024484 A CN202310024484 A CN 202310024484A CN 115962469 B CN115962469 B CN 115962469B
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Abstract
The invention discloses a rotary catalytic pyrolysis device and a method, wherein the rotary catalytic pyrolysis device comprises a closed shell, a rotary grinding machine, a feeding mechanism and a plurality of sets of microwave generators. The small-volume grinding balls are automatically distributed below and close to the grinding wall to serve as a pyrolysis zone, and the large-volume catalytic balls are automatically distributed above the grinding ball zone to serve as a catalytic zone; the catalytic ball and the grinding ball are heated by absorbing microwaves with different frequencies, so that the wear-resistant layer and the grinding ball at the periphery of the catalytic ball reach the required pyrolysis temperature, and the catalytic layer of the catalytic ball core reaches the required catalytic temperature; after entering the device, the raw materials pass through the gaps of the catalytic balls and enter the pyrolysis zone, are heated, rubbed and crushed by the grinding balls and the grinding walls, continuously strip off the surface carbon residue, realize full pyrolysis, and then the generated pyrolysis gas passes through the catalytic layer to further perform catalytic reaction. The device can realize an efficient catalytic process while the grinding raw materials ensure full pyrolysis.
Description
Technical Field
The invention relates to the technical field of catalytic pyrolysis, in particular to a rotary catalytic pyrolysis device and method.
Background
The catalytic pyrolysis is an efficient means for treating organic solid wastes (organic solid wastes) such as biomass, household garbage, waste plastics, waste rubber and the like, has the advantages of short treatment period, high conversion efficiency, obvious volume reduction effect, high-efficiency solidification of heavy metals, avoidance of generation of harmful substances such as dioxin and the like compared with the traditional treatment mode, can obtain high-value solid-liquid-gas three products, and is a technology with great application and popularization prospects in the current harmless treatment and high-value utilization technologies of the organic solid wastes.
The most critical of the catalytic pyrolysis technology is whether the corresponding pyrolysis reactor can realize efficient heat and mass transfer. However, most organic solid wastes have poor heat conductivity, so that rapid heat absorption and temperature rise are difficult, and further heat and mass transfer can be prevented by carbon generated on the pyrolysis surface. If the solution is to prolong the stay time of the raw materials in the reactor or to use finer raw material particles, the treatment efficiency of the reactor is reduced, or the power consumption of the pulverizer is increased, without increasing the treatment cost of the organic solid waste. In the fluidized bed reactor, carbon on the surface of the raw material can be peeled off by continuous collision of particles, so that the catalyst acts on the inside of the raw material, but there are problems that pyrolysis gas condensation is difficult, condensation heat loss is large, the reactor is severely worn, equipment is huge, and the like due to large carrier gas usage amount. In some rotating fluidized bed catalytic pyrolysis reactors, the fluidization of the raw materials is achieved by the rotation of the device, so that the problem of using a large amount of carrier gas can be avoided. However, the severe collision of the feedstock, heat transfer particles and catalytic particles also accelerates catalyst attrition, greatly reducing catalyst life, and catalyst fragments also affect solid product quality, limiting the development of the technology.
The pyrolysis gas is catalyzed in an ex-situ manner, so that the catalyst can be prevented from being in direct contact with the raw materials, and the service life of the catalyst is effectively prolonged. Typically, ex situ catalysis employs primarily a separate catalytic bed or even a separate catalytic reaction chamber. For example, according to chinese patent nos. 201080010711.7 and 200810137286.2, pyrolysis of raw materials and catalytic process of pyrolysis gas are performed in two reaction chambers respectively, so that respective required working conditions can be conveniently controlled. However, fast pyrolysis liquefaction is an unstable process, and the pyrolysis and catalysis are separated, so that the retention time is prolonged, the pyrolysis gas is deteriorated due to secondary decomposition or repolymerization, and meanwhile, in order to keep temperature and provide an additional reaction area, the space utilization rate is inevitably reduced, and the running cost is increased. For the rotating bed pyrolysis reactor of the Chinese patent 201810487288.8, pyrolysis and catalysis processes are performed in the reaction chamber at the same time, and heat can be stored by heating the spherical carrier through flue gas, so that energy is provided for the reaction process, and meanwhile, the spherical carrier is utilized for catalysis, so that the space utilization rate is greatly improved. However, the optimal temperature and the pyrolysis temperature required by the catalytic process are generally different, and the rotating bed pyrolysis reactor can only gradually transfer heat inwards through an external heat source, so that the working condition cannot be flexibly changed, and the optimal pyrolysis and the catalytic process are difficult to realize simultaneously. Meanwhile, as the raw materials flow in the gaps of the spherical carrier, the effect of crushing the carbon residue on the surface of the raw materials is poor, so that the heat transfer efficiency is poor.
Therefore, the method has the important points of developing the existing organic solid waste catalytic pyrolysis reactor, and simultaneously, the service life of the catalyst is prolonged and the space utilization rate of the device is improved while the high-efficiency heat transfer is ensured.
Disclosure of Invention
The invention mainly aims to provide a rotary catalytic pyrolysis device and a rotary catalytic pyrolysis method, and aims to solve the technical problems that the conventional catalytic pyrolysis device has the defects of low heat exchange efficiency, poor catalytic effect, large space occupation, difficult flexible regulation and control of reaction conditions and the like, and cannot realize efficient heat transfer and catalyst protection at the same time.
In order to achieve the above object, the present invention provides a rotary catalytic pyrolysis device, comprising:
the device comprises a closed shell, a gas inlet and a gas outlet, wherein the closed shell is provided with a discharge hole, a gas inlet and a gas outlet;
the rotary grinding machine is of a hollow cylindrical structure and is rotatably arranged in the closed shell, two opposite bottom surfaces of the rotary grinding machine are end plates, and the circumferential side surface of the rotary grinding machine is a grinding wall which is full of sieve holes; a plurality of catalytic balls and a plurality of grinding balls are arranged in the rotary grinding machine, the diameter of each grinding ball is smaller than that of each catalytic ball, each grinding ball is arranged in the area of the lower layer close to the grinding wall, and the catalytic balls are arranged above the area where the corresponding grinding ball is arranged;
the feeding mechanism comprises a hopper and a screw feeder, wherein the feeding end of the screw feeder is provided with the hopper, the discharging end of the screw feeder penetrates through the sealed shell and stretches into the rotary grinding machine, and the screw feeder is coaxial with the rotary axis of the rotary grinding machine and is horizontally arranged; the method comprises the steps of,
the microwave generators are arranged outside the closed shell and distributed corresponding to the lower half part of the rotary grinding machine;
the catalytic ball is of a porous spherical structure, the inner core of the catalytic ball is a catalytic layer, and the periphery of the catalytic ball is wrapped with an abrasion-resistant layer; the wear-resistant layer comprises a first wave-absorbing material and a wear-resistant material, the catalytic layer comprises a catalytic active component and a second wave-absorbing material, and the microwave absorption frequencies of the first wave-absorbing material and the second wave-absorbing material are different; the grinding ball is of a solid spherical structure and comprises a first wave-absorbing material and a wear-resistant material; wherein, the first frequency microwave that the microwave generator produced can make first wave-absorbing material heat to pyrolysis temperature, the second frequency microwave that the microwave generator produced can make second wave-absorbing material heat to catalytic temperature, pyrolysis temperature is higher than catalytic temperature.
Optionally, the screw feeder comprises a cylindrical shell, a conveying screw rod rotatably supported in the cylindrical shell and a feeding motor for driving the conveying screw rod to rotate; the feeding end of the cylindrical shell is provided with the hopper, the discharging end of the cylindrical shell extends into the closed shell, and one end plate of the rotary grinder is rotatably sleeved on the cylindrical shell through a bearing;
a rotating shaft is arranged on the other end plate of the rotary grinder; the rotary shaft is supported on the closed shell through a bearing, penetrates through the closed shell and is connected with the driving system, and the driving system drives the whole rotary grinding machine to rotate.
Optionally, the space for filling the catalytic ball and the grinding ball is no more than half the volume of the rotary grinder.
Optionally, the diameter of the grinding balls is larger than the diameter of the sieve holes.
Optionally, the inner surface of the grinding wall is provided with a wear resistant coating.
Optionally, the clearance between the rotary grinder and the sealed housing is no more than 30mm.
Optionally, the gas outlet above the sealed housing is connected to a liquid collection system, the gas inlet below the sealed housing is connected to a carrier gas system, and the discharge outlet below the sealed housing is connected to a solid collection system.
Further, the invention also provides a catalytic pyrolysis method based on the rotary catalytic pyrolysis device, which comprises the following steps:
the rotary catalytic pyrolysis device is started, and the rotary grinding machine rotates; the grinding balls with smaller volume are automatically distributed at the lower part close to the grinding wall under the rotation stirring to form a pyrolysis zone, and the catalytic balls with larger volume are automatically distributed at the upper part of the area where the grinding balls are positioned to form a catalytic zone; simultaneously, the microwave generator emits first-frequency microwaves and second-frequency microwaves into the rotary grinding machine, so that the catalytic ball and the grinding ball absorb microwaves to heat up until the wear-resistant layer and the grinding ball at the periphery of the catalytic ball reach the required pyrolysis temperature and the catalytic layer of the catalytic ball core reach the required catalytic temperature;
raw materials in the hopper are sent into a rotary grinder through a screw feeder; in a rotary grinder, raw materials fall, firstly pass through gaps among catalytic balls in a catalytic zone, and start preheating;
then the raw materials enter a pyrolysis zone, are stirred and collided by grinding balls, and then are heated, and are evenly pyrolyzed to generate pyrolysis gas; simultaneously, under the continuous grinding action of the grinding ball and the grinding wall, the carbon residue generated by the pyrolysis of the surface of the raw material is continuously stripped to expose the part which is not pyrolyzed inside; under the friction and crushing action of the grinding balls and the grinding walls, the carbon residue passes through the sieve holes and is discharged through the discharge holes, and the carbon residue is collected in the solid collecting system; the raw materials are continuously ground and heated in the rotary grinder due to the obstruction of the sieve holes, and the volume is gradually reduced until pyrolysis is complete;
the pyrolysis gas moves upwards, passes through the pore canal at the periphery of the catalytic ball and enters the internal catalytic layer to further perform catalytic reaction;
the catalyzed pyrolysis gas is discharged through a gas outlet, separated by a liquid collecting system, and liquid products are collected after condensation; non-condensable gas exists in the pyrolysis gas, one part of the non-condensable gas is collected and stored in a storage tank, and the other part of the non-condensable gas is sent into the rotary catalytic pyrolysis device again through a gas inlet through a carrier gas system so as to adjust the gas flow rate.
The core in the technical scheme of the invention is a small-volume grinding ball which is automatically distributed on the lower layer and is tightly attached to the grinding wall, a large-volume double-layer porous catalytic ball which is automatically distributed on the upper layer, and a sieve pore which can screen the carbon residue to pass through. The small-volume grinding balls are automatically distributed at the position below and close to the grinding wall under the rotary stirring of the rotary grinding machine to serve as a pyrolysis zone, and the large-volume catalytic balls are automatically distributed above the grinding ball zone to serve as a catalytic zone; the catalytic ball and the grinding ball are heated by absorbing microwaves with different frequencies, so that the wear-resistant layer and the grinding ball at the periphery of the catalytic ball reach the required pyrolysis temperature, and the catalytic layer of the catalytic ball core reaches the required catalytic temperature; after the raw materials fall into the rotary grinder from the inside, the raw materials firstly pass through the gap of the catalytic ball and enter the pyrolysis zone, and the raw materials are subjected to common friction and crushing actions of the grinding ball and the grinding wall to strip off the surface carbon residue, so that rapid temperature rise and full pyrolysis are realized; fine carbon residue discharge is controlled through sieve holes on the grinding wall; and the generated pyrolysis gas passes through pore channels at the periphery of the catalytic ball and enters an internal catalytic layer to further perform catalytic reaction, and then liquid products are obtained after separation and condensation. By adopting the technical scheme, the invention has the following effects:
1. the heating rate is high, and the energy is saved and the efficiency is high: the microwave energy well penetrates through the device without the heat conduction process from outside to inside, directly acts on the catalytic ball and the grinding ball, is directly absorbed by the wave-absorbing material to raise the temperature, has high heating rate, can shorten the reaction period, has small thermal gradient and maintains the uniform distribution of the temperature; and other structures of the device can not absorb microwaves, so that the heat loss is small, and the energy consumption can be saved.
2. Good selectivity and heat concentration: the microwaves with preset frequency can only be absorbed by the special corresponding wave-absorbing materials, namely one wave-absorbing material corresponds to one microwave frequency, and the double layers of the catalytic ball can avoid the absorption of the microwaves required by the inner layer by the outer layer by using different wave-absorbing materials, so that the heating range is concentrated, the temperature is easy to be controlled in a layering manner, and the optimal working conditions of the pyrolysis zone and the catalytic zone are realized; meanwhile, the high temperature of a feeding area is avoided, the raw materials are not easy to soften and adhere during feeding, the screw feeder is allowed to directly stretch into the rotary grinding machine, and the uniform feeding from the inside is realized.
3. Small thermal inertia and quick response: the microwave can only heat the catalytic ball and the grinding ball, and the waste heat of other structures of the device is less, so that the thermal inertia is small, the thermal hysteresis effect is avoided, the temperature can be regulated and controlled in time, the rapid start and stop can be realized, and the states of the pyrolysis and catalytic processes can be flexibly changed so as to adapt to the change of the raw material components.
4. High heat transfer efficiency and automatic discharging: the raw materials are continuously ground by the grinding balls and the grinding walls, and the surface pyrolytic carbon residue is stripped to expose the internal unreacted part, so that the heat is facilitated to enter, and the heat transfer efficiency is improved; meanwhile, broken fine carbon residue can directly pass through the sieve holes to be discharged, and large-particle raw materials are continuously left in the rotary grinding machine to be pyrolyzed, so that the effective separation of the raw materials and the pyrolyzed carbon is ensured, and the automatic discharging is realized.
5. The catalyst has long service life: the catalytic ball sets up to the wearing layer of the catalytic layer and the peripheral parcel of kernel, and only outside hard wearing layer bumps in the stirring in-process, and catalytic layer only contacts with pyrolysis gas, can not influence its catalytic effect, has greatly prolonged the life of catalyst, avoids the catalyst piece to influence product quality simultaneously.
6. The reaction condition is convenient to regulate and control: parameters such as pyrolysis temperature, catalytic temperature, reaction time and the like can be flexibly adjusted by controlling the feeding speed of the device, the rotating speed of the rotary grinder, the microwave transmitting power, the sizes and the proportions of the catalytic ball and the grinding ball and the like, so that the pyrolysis and catalytic reaction process is regulated and controlled according to different raw materials and required target products, and high-efficiency conversion is realized.
7. High stability and automatic distribution of reaction areas: the catalytic ball and the grinding ball are used for heat transfer, the heat exchange between the raw materials and the wall surface is not relied on, the rotating speed is not required to be too large, and the relative stability is higher; the rotary grinding machine is used for rotating and stirring, the small-volume grinding balls can automatically move downwards to a position close to the grinding wall to serve as a pyrolysis zone, and the large-volume catalytic balls automatically move upwards to a position above the area where the grinding balls are located to serve as a catalytic zone, so that pyrolysis and catalytic processes can be automatically guaranteed not to be mutually interfered, and stable operation of the device is realized.
8. The residence time is short, and the space utilization rate is high: a plurality of pore channels are formed on the catalytic ball, pyrolysis gas generated by pyrolysis of the raw materials can directly pass through the pore channels in the catalytic ball to rapidly perform catalytic reaction with the catalytic layer, so that the residence time is short, and the catalytic effect is good; the continuous circulation of gas in the double-layer structure can be realized by utilizing the pore canal, and the efficient pyrolysis and catalysis processes are respectively realized; meanwhile, additional auxiliary equipment such as a catalytic reaction chamber and heat exchange can be omitted, and the space utilization rate is improved.
In conclusion, the device has the advantages of high-efficiency heat exchange, flexible and accurate layered temperature control, quick regulation and control response, energy conservation, high efficiency, automatic discharging, high space utilization rate, long service life of the catalyst and the like, and can realize a rapid catalytic process while grinding raw materials to ensure high-efficiency pyrolysis.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a rotary catalytic pyrolysis device according to the present invention;
fig. 2 is a schematic flow chart of the catalytic pyrolysis method provided by the invention.
Description of the reference numerals:
1-a hopper; 2-screw feeder; 3-catalytic sphere; 4-grinding balls; 5-a discharge hole; 6-a rotary grinding machine; 7-a microwave generator; 8-a closed shell; 9-gas outlet;
61-end plates; 62-sieve pores; 63-grinding the wall; 64-rotation axis.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The technical solutions of the present embodiment will be clearly and completely described below with reference to the drawings in the present embodiment, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indications (such as up, down, left, right, front, and rear...the above) in the present embodiment are merely used to explain the relative positional relationship, movement conditions, and the like between the components in a certain specific posture (as shown in the drawings), and if the specific posture is changed, the directional indication is changed accordingly.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body: can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In addition, the technical solutions of the embodiments of the present invention may be combined with each other, but it is necessary to be based on the fact that those skilled in the art can implement the technical solutions, and when the technical solutions are contradictory or cannot be implemented, the combination of the technical solutions should be considered as not existing, and not falling within the scope of protection claimed by the present invention.
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Aiming at the existing problems, the invention provides a rotary catalytic pyrolysis device and a method, which have the characteristics of high heating rate, concentrated heat, uniform heating, quick regulation and control response, flexible and accurate layered temperature control, high heat transfer efficiency, energy conservation, high efficiency, long service life of a catalyst, high stability, automatic distribution of a reaction zone, automatic screening and discharging, high space utilization rate and the like, and can realize a rapid and timely catalytic process while grinding raw materials to ensure high-efficiency pyrolysis.
In order to achieve the above technical solution, as shown in fig. 1, an embodiment of the present invention provides a rotary catalytic pyrolysis device, which includes a sealed housing 8, a rotary grinder 6, a feeding mechanism, and a plurality of microwave generators 7. The sealed shell 8 is provided with a discharge hole 5, a gas inlet and a gas outlet 9. The rotary grinding machine 6 has a hollow cylindrical structure and is rotatably disposed in the sealed housing 8, two opposite bottom surfaces of the rotary grinding machine 6 are end plates 61, and a circumferential side surface of the rotary grinding machine 6 is a grinding wall 63 full of mesh holes 62. The inner surface of the grinding wall 63 may be provided with a wear-resistant coating, for example a silicon carbide coating, to ensure service life, and also to minimize wear of the material on the rotary grinding machine 6 and to avoid mixing of the worn material into the pyrolysis products.
The feeding mechanism comprises a hopper 1 and a screw feeder 2, wherein the feeding end of the screw feeder 2 is provided with the hopper 1, the discharging end of the screw feeder 2 penetrates through a sealed shell 8 and stretches into a rotary grinding machine 6, and the screw feeder 2 is coaxial with the rotation axis of the rotary grinding machine 6 and is horizontally arranged. The screw feeder 2 directly extends into the rotary grinder 6 to achieve uniform feeding from the inside.
The microwave generators 7 are arranged outside the closed shell 8 and distributed corresponding to the lower half part (corresponding to the pyrolysis zone and the catalytic zone) of the rotary grinder 6. Microwave generators (also known as microwave oscillators) are existing instruments that use frequency synthesis techniques to generate the desired frequency or waveform signal. The frequency synthesis technology is to perform linear operation on a low-frequency standard reference signal with high spectral purity and high stability generated by a crystal oscillator in a frequency domain, and obtain signals with one or more frequencies and frequency bands meeting various index requirements, such as the same stability and low phase noise, through frequency multiplication, frequency mixing, frequency division and other technologies. From the development history of frequency synthesis, the frequency synthesis mode sequentially goes through the processes of direct analog synthesis, phase locking technology and direct digital synthesis. Wherein the microwave generator 7 can emit the first frequency microwave and the second frequency microwave at the same time; alternatively, part of the microwave generators 7 emit microwaves of a first frequency, while the remaining microwave generators 7 emit microwaves of a second frequency. The material on the closed shell 8 corresponding to the microwave emitting position or path can be non-metal materials such as quartz, ceramic and the like, so that the microwave can well penetrate the closed shell 8 to enter the interior, and the catalytic ball 3 and the grinding ball 4 are heated simultaneously inside and outside, so that the heating rate is high, the reaction period can be shortened, the thermal gradient is small, and the uniform distribution of the temperature is maintained; and the heating temperature to be achieved can be flexibly controlled by controlling the transmitting power and transmitting time of the microwaves.
A plurality of catalytic balls 3 and a plurality of grinding balls 4 are placed in the rotary grinding machine 6, the diameter of the grinding balls 4 is smaller than that of the catalytic balls 3, and the diameter of the grinding balls 4 is larger than that of the sieve holes 62, so that the catalytic balls 3 and the grinding balls 4 cannot fall out of the rotary grinding machine 6. The grinding balls 4 are arranged in the lower layer in the region close to the grinding wall 63, and the catalytic balls 3 are arranged above the region where the grinding balls 4 are located. The catalytic ball 3 and the grinding ball 4 are used for heat transfer, the heat exchange between the raw materials and the wall surface is not relied on, the rotating speed is not required to be too large, and the relative stability is higher; the small-volume grinding balls 4 can automatically move down to a position close to the grinding wall 63 to serve as a pyrolysis zone when being rotationally stirred by the rotary grinding machine 6, and the large-volume catalytic balls 3 can automatically move up to a position above the area where the grinding balls are located to serve as a catalytic zone, so that the pyrolysis and the catalytic process can be automatically ensured not to be mutually interfered, and the stable operation of the device is realized. And, the space for filling the catalytic ball 3 and the grinding ball 4 is not more than half of the volume of the rotary grinder 6, namely, the screw feeder 2 directly stretches into the rotary grinder 6 and enters the catalytic zone, so that uniform feeding from the inside is realized, and the high temperature of the feeding zone can be avoided, so that raw materials are not easy to soften and adhere during feeding.
The catalytic ball 3 is of a porous spherical structure, the inner core of the catalytic ball 3 is a catalytic layer, and the periphery of the catalytic ball is wrapped with an abrasion-resistant layer; the material of the wear-resistant layer comprises a first wave-absorbing material and a wear-resistant material, the material of the catalytic layer comprises a catalytic active component and a second wave-absorbing material, and the microwave absorption frequencies of the first wave-absorbing material and the second wave-absorbing material are different; the grinding ball 4 is of a solid spherical structure and comprises a first wave-absorbing material and a wear-resistant material; wherein the first frequency microwave generated by the microwave generator 7 can heat the first wave-absorbing material to a pyrolysis temperature, and the second frequency microwave generated by the microwave generator 7 can heat the second wave-absorbing material to a catalysis temperature, wherein the pyrolysis temperature is higher than the catalysis temperature. The first wave-absorbing material may be any one of silicon nitride, silicon carbide, boron nitride, aluminum nitride, graphene, etc., and the second wave-absorbing material may be another one of silicon nitride, silicon carbide, boron nitride, aluminum nitride, graphene, etc., or may be processed by different processing techniques and additives to make the wave-absorbing frequencies of the materials different. The wave-absorbing materials have different wave-absorbing frequencies, so long as the catalytic layer and the wear-resistant layer are ensured to adopt different wave-absorbing materials, the wave-absorbing materials are not limited to a certain type. For example, certain silicon carbide materials have a wave absorption frequency of 12-18GHz, preferably 15GHz, which may correspond to absorption of first frequency microwaves (15 GHz); the wave absorption frequency of the FeCo/graphene composite material is 7-11GHz, and the optimal wave absorption frequency is 9GHz, and the FeCo/graphene composite material can correspondingly absorb second-frequency microwaves (9 GHz). The catalytically active component may be barium oxide, magnesium oxide, solid phosphoric acid or solid potassium phosphate, etc., and is selected according to the actual catalytic reaction requirements, and any component that can be supported on the wave-absorbing material may be used. The wear resistant material may be silicon carbide or other similar material. The first wave-absorbing material and the wear-resistant material can be silicon carbide, and the silicon carbide material can stably absorb microwaves with the frequency of 15GHz and also has the characteristic of wear resistance.
The microwaves with preset frequency can only be absorbed by the special corresponding wave-absorbing materials, namely one wave-absorbing material corresponds to one microwave frequency, the double layers of the catalytic ball can avoid the absorption of the microwaves required by the inner layer by the outer layer by using different wave-absorbing materials, the heating range is concentrated, the temperature is easy to be controlled in a layering manner, and the optimal working conditions of the pyrolysis zone and the catalytic zone are realized. In addition, the microwave can directly act on the catalytic ball and the grinding ball without the heat conduction process from outside to inside, the microwave is directly absorbed by the wave-absorbing material to raise the temperature, the heating rate is high, and the reaction period can be shortened; and other structures of the device can not absorb microwaves, so that the heat loss is small, and the energy consumption can be saved. The microwave can only heat the catalytic ball and the grinding ball, and the waste heat of other structures of the device is less, so that the thermal inertia is small, the thermal hysteresis effect is avoided, the temperature can be regulated and controlled in time, the rapid start and stop can be realized, and the states of the pyrolysis and catalytic processes can be flexibly changed so as to adapt to the change of the raw material components.
The double-layer catalytic ball 3 may have only the wear-resistant layer formed with the pore canal, or may have both the wear-resistant layer and the catalytic layer formed with the pore canal, so long as the pyrolysis gas can enter the catalytic layer to react with the catalytic active component, and the pore canal may be formed in various manners, for example, the pore canal may be made of templates with different sizes like the catalyst pore canal, or the ventilation pore canal may be drilled directly on the sphere. The double-layer sphere volume is relatively large, and many methods for realizing the double-layer spherical structure exist, for example, a small sphere can be used as a core, and a separated shell is spliced outside the small sphere. The catalytic ball 3 is provided with the catalytic layer of the inner core and the wear-resistant layer wrapped by the periphery, only the wear-resistant layer on the outer side is lost in the collision process, and the catalytic layer is only contacted with pyrolysis gas, so that the catalytic effect is not influenced, the service life of the catalyst is greatly prolonged, and meanwhile, the influence of catalyst fragments on the product quality is avoided. A plurality of pore channels are formed on the catalytic ball, pyrolysis gas generated by pyrolysis of the raw materials can directly pass through the pore channels in the catalytic ball to rapidly perform catalytic reaction with the catalytic layer, so that the residence time is short, and the catalytic effect is good; the continuous circulation of gas in the double-layer structure can be realized by utilizing the pore canal, and the efficient pyrolysis and catalysis processes are respectively realized; meanwhile, additional auxiliary equipment such as a catalytic reaction chamber and heat exchange can be omitted, and the space utilization rate is improved.
The technical scheme adopts a double-layer porous catalytic ball 3 with a catalytic core wrapped by a peripheral wear-resistant layer and a solid grinding ball 4. The microwave generator 7 emits microwaves with two different frequencies into the rotary grinder 6, and the emission power of the microwaves with different frequencies is controlled respectively to enable the catalytic ball 3 and the grinding ball 4 to quickly heat up after absorbing the microwaves until the wear-resistant layer at the periphery of the catalytic ball 3 and the grinding ball 4 reach the required pyrolysis temperature and the catalytic area of the inner core of the catalytic ball 3 reaches the required catalytic temperature. The small volume of grinding balls 4 are automatically distributed below near the grinding wall 63 as pyrolysis zone and the large volume of catalytic balls 3 are automatically distributed above the grinding ball zone as catalytic zone under the rotary agitation of the rotary grinder 6. After falling into the rotary grinder 6, the raw materials firstly pass through the gap of the catalytic ball 3 and enter the pyrolysis zone, and are subjected to common friction and crushing actions of the grinding ball 4 and the grinding wall 63 to strip off surface carbon residue, expose the unreacted part in the interior, facilitate heat to enter, improve heat transfer efficiency and realize rapid temperature rise and full pyrolysis; through the sieve mesh 62 on the grinding wall 63, the discharge of the tiny pyrolysis carbon residue is controlled, and the raw materials of large particles continue to stay in the rotary grinding machine 6 for pyrolysis, so that the effective separation of the raw materials and the pyrolysis carbon is ensured, and the automatic discharge is realized. The generated pyrolysis gas passes through the pore canal at the periphery of the catalytic ball 3 and enters the internal catalytic layer to further perform catalytic reaction, and then liquid products are obtained after separation and condensation. The device has the advantages of high-efficiency heat exchange, flexible and accurate layered temperature control, quick regulation response, energy conservation, high efficiency, automatic discharging, high space utilization rate, long service life of the catalyst and the like, and can realize rapid catalytic process while grinding raw materials to ensure high-efficiency pyrolysis.
In a preferred embodiment, referring again to fig. 1, the screw feeder 2 comprises a cylindrical housing, a conveying screw (not shown) rotatably supported within the cylindrical housing, and a feed motor (not shown) for driving the conveying screw in rotation, which may be a servo motor with a decelerator. Wherein, cylindric casing and transport screw rod can all adopt wear-resisting material to reduce the wearing and tearing when carrying the screw rod rotation, increase of service life. The discharge end of the cylindrical shell may be a discharge opening formed in an end surface of the cylindrical shell, and at this time, the cylindrical shell is in frictional contact with a conveying screw rod, and the conveying screw rod is supported by the cylindrical shell; alternatively, the discharge opening may be formed on the circumferential side surface of the cylindrical housing near the bottom, and the conveying screw may be rotatably supported in the cylindrical housing by a pair of bearings.
The feeding end of the cylindrical shell is provided with a hopper 1, the discharging end of the cylindrical shell extends into the sealed shell 8, and one of end plates 61 of the rotary grinder 6 is rotatably sleeved on the cylindrical shell through a bearing. The other end plate 61 of the rotary grinder 6 is provided with a rotary shaft 64; the rotating shaft 64 is supported on the airtight housing 8 through a bearing and can be sealed by matching with a labyrinth seal, and the rotating shaft 64 passes through the airtight housing 8 to be connected with a driving system and drives the whole rotary grinding machine 6 to rotate through the driving system, wherein the driving system can comprise a motor, a speed reducer and the like for providing power. The clearance between the rotary grinder 6 and the airtight enclosure 8 is not more than 30mm. The catalytic ball 3 and the grinding ball 4 are utilized for heat transfer, the heat exchange between the raw materials and the wall surface is not relied on, the rotating speed is not required to be too large, and the relative stability is higher. Moreover, the discharge port 5 on the airtight enclosure 8 is separated from the rotary grinder 6, and the screw feeder 2 and the rotary shaft 64 cannot absorb microwaves to maintain a low temperature, so that the sealing of the apparatus is easy. Parameters such as pyrolysis temperature, catalytic temperature, reaction time and the like can be flexibly adjusted by controlling the feeding speed of the screw feeder 2, the rotating speed of the rotary grinder 6, the microwave emitting power, the sizes and the proportions of the catalytic ball 3 and the grinding ball 4 and the like, so that the pyrolysis and catalytic reaction processes are regulated and controlled according to different raw materials and required target products, and high-efficiency conversion is realized.
The technical scheme of the invention is further described based on the optimal embodiment. Specifically, the rotary grinder 6 is arranged in the airtight shell 8 and is of a horizontal hollow cylindrical structure, the diameter of the bottom surface is about 1000mm, and the height is about 500 mm; the gap between the rotary grinder 6 and the closed shell 8 is not more than 20mm; the two bottom surfaces of the rotary grinder 6 are end plates 61, the side surfaces are grinding walls 63 which are fully distributed with sieve holes 62, and the aperture of the sieve holes 62 is about 2mm; the inner surface of the grinding wall 63 is provided with a wear-resistant silicon carbide coating; the end plate 61 on one side of the rotary grinder 6 is connected with a rotary shaft 64, and the shaft diameter is about 60mm; the rotating shaft 64 is supported by a bearing arranged on the closed shell 8, matched with a labyrinth seal ring for sealing, and connected with a driving system outside the closed shell 8; and 6 sets of microwave generators 7 are uniformly arranged on the outer side of a closed shell 8 corresponding to the lower half part of the cylinder of the rotary grinder 6.
And, the rotary grinder 6 is internally filled with the catalytic ball 3 and the grinding ball 4 with the stacking volume of about 1/3 of the volume, and the number ratio of the catalytic ball 3 to the grinding ball 4 is 1:2; the diameter of the catalytic ball 3 is about 40mm, and the diameter of the grinding ball 4 is about 10mm; the grinding balls 4 are arranged in the lower layer in the region close to the grinding wall 63, and the catalytic balls 3 are arranged above the region where the grinding balls 4 are located. The catalytic ball 3 is of a double-layer porous spherical structure, the inner core is a catalytic layer, the periphery is wrapped with an abrasion-resistant layer, and the grinding ball 4 is of a solid spherical structure; the wear-resistant layer of the catalytic ball 3 and the grinding ball are both made of wear-resistant silicon carbide materials, and the catalytic layer of the catalytic ball 3 is composed of a catalytic active component and boron nitride; the screw feeder 2 is coaxially arranged with the rotary grinder 6, and the screw feeder 2 is fixed on the airtight housing 8; the feeding end of the screw feeder 2 is connected with the hopper 1, and the discharging end penetrates through the sealed shell 8 and stretches into the rotary grinder 6. The gas outlet 9 above the closed casing 8 is connected with a liquid collecting system (not shown), the discharge outlet 5 below is connected with a solid collecting system (not shown), and the gas inlet below the closed casing 8 is connected with a carrier gas system (not shown). The solid collecting system, the liquid collecting system and the carrier gas system are all known in the prior art.
In order to better realize the technical scheme, the invention also provides a catalytic pyrolysis method using the rotary catalytic pyrolysis device, which comprises the following steps:
s1, starting a rotary catalytic pyrolysis device, and driving a rotary grinding machine to rotate by a driving system through a rotary shaft; the grinding balls with smaller volume are automatically distributed at the lower part close to the grinding wall under the rotation stirring to form a pyrolysis zone, and the catalytic balls with larger volume are automatically distributed at the upper part of the area where the grinding balls are positioned to form a catalytic zone; simultaneously, the microwave generator emits first-frequency microwaves and second-frequency microwaves into the rotary grinding machine, so that the catalytic ball and the grinding ball absorb microwaves and heat up rapidly until the wear-resistant layer and the grinding ball at the periphery of the catalytic ball reach the required pyrolysis temperature and the catalytic layer of the catalytic ball core reach the required catalytic temperature;
s2, feeding raw materials in a hopper into a rotary grinder through a screw feeder; in a rotary grinder, raw materials fall, firstly pass through gaps among catalytic balls in a catalytic zone, and start preheating;
s3, the raw materials enter a pyrolysis zone, are subjected to full stirring and severe collision of grinding balls, and then are rapidly heated, and are uniformly pyrolyzed to generate pyrolysis gas; simultaneously, under the continuous grinding action of the grinding ball and the grinding wall, the carbon residue generated by the pyrolysis of the surface of the raw material is continuously stripped to expose the part which is not pyrolyzed inside; under the friction and crushing action of the grinding balls and the grinding walls, the carbon residue with smaller size passes through the sieve holes and is discharged through the discharge holes to be collected in the solid collecting system; the raw material particles with larger size are continuously ground and heated in the rotary grinder due to the obstruction of the sieve holes, and the volume is gradually reduced until pyrolysis is complete;
s4, the generated pyrolysis gas moves upwards, passes through pore channels at the periphery of the catalytic ball and enters the internal catalytic layer, and further catalytic reaction occurs;
s5, discharging the catalyzed pyrolysis gas through a gas outlet, separating and condensing the pyrolysis gas through a liquid collecting system, and collecting a liquid product; non-condensable gas exists in the pyrolysis gas, one part of the non-condensable gas is collected and stored in a storage tank, and the other part of the non-condensable gas is sent into the rotary catalytic pyrolysis device again through a gas inlet through a carrier gas system so as to adjust the gas flow rate.
The process flow of catalytic pyrolysis of the organic solid waste raw material by using the rotary catalytic pyrolysis device is described in detail below by specific examples, and devices with basically the same structure are adopted in each example.
Example 1
Continuously feeding bagasse raw materials with the average particle size of 8mm into a rotary grinding machine through a screw feeder; the surface of the catalytic ball and the grinding ball are maintained at a temperature of about 500 ℃ and the interior of the catalytic ball is maintained at a temperature of about 350 ℃ by continuously absorbing microwave energy; under the drive of the drive system, the rotating speed of the rotary grinder is about 10r/min, so that the raw materials are subjected to the common friction and crushing actions of the grinding balls and the grinding walls in the pyrolysis zone, and the surface carbon residue is stripped, so that the rapid temperature rise and the full pyrolysis are realized; the generated pyrolysis gas passes through the pore canal of the outer layer of the catalytic ball and enters the interior, and the pyrolysis gas is subjected to catalytic reaction under the action of the catalytic active ingredient barium oxide; and after separation and condensation of pyrolysis gas after final catalysis, collecting a liquid product, wherein the liquid phase yield is 51.2wt%, and the target product 4-vinyl phenol accounts for 12.1wt% in the liquid phase product, so that the high-value utilization of bagasse raw materials is realized.
Example 2
Continuously feeding waste paper raw materials with the average particle size of 10mm into a rotary grinder through a screw feeder; the surface of the catalytic ball and the grinding ball are maintained at a temperature of about 550 ℃ and the interior of the catalytic ball is maintained at a temperature of about 300 ℃ by continuously absorbing microwave energy; under the drive of the drive system, the rotating speed of the rotary grinder is about 15r/min, so that the raw materials are subjected to the common friction and crushing actions of the grinding balls and the grinding walls in the pyrolysis zone, and the surface carbon residue is stripped, so that the rapid temperature rise and the full pyrolysis are realized; the generated pyrolysis gas passes through the pore canal of the outer layer of the catalytic ball and enters the interior, and catalytic reaction occurs under the action of solid phosphoric acid serving as a catalytic active component; and after separation and condensation of pyrolysis gas after final catalysis, collecting a liquid product, wherein the liquid phase yield is 47.3wt%, and the target product of the levoglucose ketone accounts for 12.8wt% in the liquid phase product, so that the high-value utilization of waste paper raw materials is realized.
Example 3
Continuously feeding the waste rubber raw material with the average particle size of 8mm into a rotary grinding machine through a screw feeder; the surface of the catalytic ball and the grinding ball are maintained at a temperature of about 600 ℃ and the interior of the catalytic ball is maintained at a temperature of about 350 ℃ by continuously absorbing microwave energy; under the drive of the drive system, the rotating speed of the rotary grinder is about 12r/min, so that the raw materials are subjected to the common friction and crushing actions of the grinding balls and the grinding walls in the pyrolysis zone, and the surface carbon residue is stripped, so that the rapid temperature rise and the full pyrolysis are realized; the generated pyrolysis gas passes through the pore canal of the outer layer of the catalytic ball and enters the interior, and the pyrolysis gas is subjected to catalytic reaction under the action of the catalytic active ingredient magnesium oxide; and after separation and condensation of pyrolysis gas after final catalysis, collecting a liquid product, wherein the liquid phase yield is 47.5wt%, and the target product arene accounts for 48.8wt% in the liquid phase product, so that the high-value utilization of the waste rubber raw material is realized.
Example 4
Continuously feeding pine wood raw materials with the average grain diameter of 8mm into a rotary grinding machine through a screw feeder; the surface of the catalytic ball and the grinding ball are maintained at a temperature of about 500 ℃ and the interior of the catalytic ball is maintained at a temperature of about 300 ℃ by continuously absorbing microwave energy; under the drive of the drive system, the rotating speed of the rotary grinder is about 8r/min, so that the raw materials are subjected to the common friction and crushing actions of the grinding balls and the grinding walls in the pyrolysis zone, and the surface carbon residue is stripped, so that the rapid temperature rise and the full pyrolysis are realized; the generated pyrolysis gas passes through the pore canal of the outer layer of the catalytic ball and enters the interior, and the pyrolysis gas is subjected to catalytic reaction under the action of solid potassium phosphate serving as a catalytic active component; and after separation and condensation of pyrolysis gas after final catalysis, collecting a liquid product, wherein the liquid phase yield is 43.2wt%, and the ratio of a target product phenolic mixture in the liquid phase product is 30.1wt%, so that the high-value utilization of pine raw materials is realized.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures or equivalent processes disclosed herein or in the alternative, which may be employed directly or indirectly in other related arts.
Claims (8)
1. A rotary catalytic pyrolysis device, comprising:
the device comprises a closed shell (8), wherein a discharge hole (5), a gas inlet and a gas outlet (9) are formed in the closed shell (8);
the rotary grinding machine (6) is of a hollow cylindrical structure and is rotatably arranged in the closed shell (8), two opposite bottom surfaces of the rotary grinding machine (6) are end plates (61), and the circumferential side surface of the rotary grinding machine (6) is a grinding wall (63) which is full of sieve holes (62); a plurality of catalytic balls (3) and a plurality of grinding balls (4) are arranged in the rotary grinding machine (6), the diameter of each grinding ball (4) is smaller than that of each catalytic ball (3), the grinding balls (4) are arranged in the lower layer of the region close to the grinding wall (63), and the catalytic balls (3) are arranged above the region where the grinding balls (4) are arranged;
the feeding mechanism comprises a hopper (1) and a screw feeder (2), wherein the feeding end of the screw feeder (2) is provided with the hopper (1), the discharging end of the screw feeder (2) penetrates through the sealed shell (8) and stretches into the rotary grinding machine (6), and the screw feeder (2) and the rotary grinding machine (6) are coaxial and horizontally arranged; the method comprises the steps of,
the microwave generators (7) are arranged outside the closed shell (8) and distributed corresponding to the lower half part of the rotary grinding machine (6);
the catalytic ball (3) is of a porous spherical structure, the inner core of the catalytic ball (3) is a catalytic layer, and the periphery of the catalytic ball is wrapped with an abrasion-resistant layer; the wear-resistant layer comprises a first wave-absorbing material and a wear-resistant material, the catalytic layer comprises a catalytic active component and a second wave-absorbing material, and the microwave absorption frequencies of the first wave-absorbing material and the second wave-absorbing material are different; the grinding ball (4) is of a solid spherical structure and comprises a first wave-absorbing material and a wear-resistant material; wherein a first frequency of microwaves generated by the microwave generator (7) can heat a first wave-absorbing material to a pyrolysis temperature, and a second frequency of microwaves generated by the microwave generator (7) can heat a second wave-absorbing material to a catalysis temperature, and the pyrolysis temperature is higher than the catalysis temperature.
2. The rotary catalytic pyrolysis device according to claim 1, characterized in that the screw feeder (2) comprises a cylindrical housing, a conveying screw rotatably supported in the cylindrical housing and a feed motor for driving the conveying screw in rotation; the feeding end of the cylindrical shell is provided with the hopper (1) and the discharging end of the cylindrical shell extends into the closed shell (8), and one end plate (61) of the rotary grinder (6) is rotatably sleeved on the cylindrical shell through a bearing;
a rotating shaft (64) is arranged on the other end plate (61) of the rotary grinder (6); the rotary shaft (64) is supported on the closed shell (8) through a bearing, the rotary shaft (64) penetrates through the closed shell (8) to be connected with a driving system, and the driving system drives the whole rotary grinding machine (6) to rotate.
3. The rotary catalytic pyrolysis device according to claim 1 or 2, characterized in that the space for filling the catalytic balls (3) and the grinding balls (4) is not more than half the volume of the rotary grinding machine (6).
4. The rotary catalytic pyrolysis device according to claim 1 or 2, characterized in that the grinding balls (4) have a diameter larger than the pore diameter of the sieve pores (62).
5. A rotary catalytic pyrolysis device according to claim 1 or 2, characterized in that the inner surface of the grinding wall (63) is provided with a wear-resistant coating.
6. The rotary catalytic pyrolysis device according to claim 1 or 2, characterized in that the clearance between the rotary grinding machine (6) and the closed casing (8) is not more than 30mm.
7. The rotary catalytic pyrolysis device according to claim 1 or 2, characterized in that the gas outlet (9) above the closed housing (8) is connected to a liquid collection system, the gas inlet below the closed housing (8) is connected to a carrier gas system, and the discharge outlet (5) below the closed housing (8) is connected to a solids collection system.
8. A catalytic pyrolysis process based on a rotary catalytic pyrolysis unit according to any one of claims 1 to 7, comprising the steps of:
the rotary catalytic pyrolysis device is started, and the rotary grinding machine rotates; the grinding balls with smaller volume are automatically distributed at the lower part close to the grinding wall under the rotation stirring to form a pyrolysis zone, and the catalytic balls with larger volume are automatically distributed at the upper part of the area where the grinding balls are positioned to form a catalytic zone; simultaneously, the microwave generator emits first-frequency microwaves and second-frequency microwaves into the rotary grinding machine, so that the catalytic ball and the grinding ball absorb microwaves to heat up until the wear-resistant layer and the grinding ball at the periphery of the catalytic ball reach the required pyrolysis temperature and the catalytic layer of the catalytic ball core reach the required catalytic temperature;
raw materials in the hopper are sent into a rotary grinder through a screw feeder; in a rotary grinder, raw materials fall, firstly pass through gaps among catalytic balls in a catalytic zone, and start preheating;
then the raw materials enter a pyrolysis zone, are stirred and collided by grinding balls, and then are heated, and are evenly pyrolyzed to generate pyrolysis gas; simultaneously, under the continuous grinding action of the grinding ball and the grinding wall, the carbon residue generated by the pyrolysis of the surface of the raw material is continuously stripped to expose the part which is not pyrolyzed inside; under the friction and crushing action of the grinding balls and the grinding walls, the carbon residue fragments pass through the sieve holes and are discharged through the discharge holes, and are collected in the solid collecting system; the raw materials are continuously ground and heated in the rotary grinder due to the obstruction of the sieve holes, and the volume is gradually reduced until pyrolysis is complete;
the pyrolysis gas moves upwards, passes through the pore canal at the periphery of the catalytic ball and enters the internal catalytic layer to further perform catalytic reaction;
the catalyzed pyrolysis gas is discharged through a gas outlet, and liquid products are collected after separation and condensation by a liquid collecting system; non-condensable gas exists in the pyrolysis gas, one part of the non-condensable gas is collected and stored in a storage tank, and the other part of the non-condensable gas is sent into the rotary catalytic pyrolysis device again through a gas inlet through a carrier gas system so as to adjust the gas flow rate.
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