CN113322089A - Pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics - Google Patents
Pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics Download PDFInfo
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- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 55
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B23/00—Other methods of heating coke ovens
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/02—Multi-step carbonising or coking processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics. When the waste plastics are subjected to catalytic pyrolysis, the waste plastics are firstly decomposed into long-chain hydrocarbon macromolecular compounds in a pyrolysis reactor, and then the substances are subjected to reactions such as fracture, aromatization and the like under the action of a catalyst in the catalytic pyrolysis reactor, so that high-quality pyrolysis products are selectively prepared. The invention not only realizes the independent fast pyrolysis and catalytic fast pyrolysis of the waste plastics, but also realizes the separation of the pyrolysis reaction and the catalytic reaction, so that the catalytic temperature can be flexibly controlled, and the catalyst is not easy to inactivate after being separated from the plastics.
Description
Technical Field
The invention relates to the technical field of plastic energy, in particular to a pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics.
Background
With the development of economic society, plastics become main industrial wastes and municipal wastes, and recycling is the most suitable disposal mode for waste plastics at present, but different additives often exist in different waste plastics and are difficult to separate, so that recycling of the waste plastics is limited to a great extent. The pyrolysis technology is a process of decomposing thermally decomposable substances into solid, liquid and gas three-phase products under the condition of high temperature and no oxygen, and the industrial operation of preparing liquid fuel and synthesis gas by coal pyrolysis is realized.
In the traditional pyrolysis technology, research on reaction devices for pyrolyzing waste plastics is less, and most laboratories are mainly researching the pyrolysis of the waste plastics on devices such as a tube furnace, however, the heating rate of an electric heating pyrolysis device such as a tube furnace is slow, and the electric heating pyrolysis device is not beneficial to preparing high-yield liquid products; the method can avoid secondary reaction of the pyrolysis product under the rapid heating condition to cause low yield of the liquid product, and meanwhile, the long-time heating increases energy consumption, so that the pyrolysis reaction is required to be performed under the rapid heating condition as much as possible. Traditional fast pyrolysis reactor is because rate of heating is slow, and partial technique can adopt solid heat carrier or gaseous heat carrier, though can reach the purpose of quick heating material, the heat carrier technique has that tar dust smugglies seriously, heat carrier and reactor friction damage reactor and cause the reactor to block up the scheduling problem. However, for the characteristics of dust, impurities and the like of the waste plastics, the thermal infrared fast heating waste plastics pyrolysis and catalytic pyrolysis method can avoid the problems by directly and fast heating the waste plastics without using a heat carrier. In addition, the waste plastics are complex in types, such as engineering waste plastics and special waste plastics, and the structures of the waste plastics are particularly compact, so that the waste plastics are difficult to thermally decompose, the macromolecular substance content in the waste plastic pyrolysis product is high, and the quality of the liquid product is poor, so that a catalyst needs to be added in the pyrolysis process, and the catalytic pyrolysis of the waste plastics can break bonds of the macromolecular substance, so that more light products are generated. On one hand, if the waste plastics and the catalyst are mixed and pyrolyzed, the catalyst is wrapped by the softened waste plastics and is rapidly deactivated, and the purpose of catalytic pyrolysis cannot be effectively achieved, and on the other hand, the temperature at which the catalyst plays the best effect is not necessarily the same as the temperature at which the waste plastics are pyrolyzed, so that the pyrolysis reaction of the waste plastics and the catalytic reaction of the catalyst are separated and carried out more favorably.
Disclosure of Invention
The invention aims to provide a pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics, which can realize the independent pyrolysis of the waste plastics and the catalytic pyrolysis of the waste plastics, can flexibly adjust the pyrolysis temperature and the catalytic pyrolysis temperature, separate the pyrolysis reaction and the catalytic reaction of the plastics, and slow down the deactivation speed of carbon deposition of a catalyst. The problems of low heating rate, nonuniform heating of raw materials, high content of macromolecular substances of pyrolysis products and the like in the conventional pyrolysis method are solved, the quality of the pyrolysis products is improved, and high-valued utilization of waste plastics is realized.
In order to achieve the purpose, the invention provides the following technical scheme: a pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics comprises the following steps when the waste plastics are pyrolyzed independently:
(1) crushing waste plastics until the particle size is uniform, and putting the waste plastics into a pyrolysis reactor;
(2) the method comprises the following steps of sequentially connecting a gas distribution system, a pyrolysis reactor and a product recovery system, and setting the gas flow and the target temperature of the pyrolysis reactor to be 400-800 ℃;
(3) starting a temperature rise program of a pyrolysis reactor and a refrigeration pump, carrying out pyrolysis reaction on waste plastics at high temperature, and carrying out generated volatile components out by carrier gas, wherein the temperature of the refrigeration pump is-20 ℃ to-50 ℃;
(4) the volatiles carried over by the carrier gas are collected in a product recovery system.
And (3) the pyrolysis reactor in the steps (2) and (3) is an infrared heating pyrolysis reactor.
A pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics comprises the following steps:
(1) crushing waste plastics until the particle size is uniform, putting the waste plastics into a pyrolysis reactor, and putting a certain proportion of catalyst into a catalytic pyrolysis reactor;
(2) the method comprises the following steps of sequentially connecting a gas distribution system, a pyrolysis reactor, a catalytic pyrolysis reactor and a product recovery system, and setting the gas flow and the target temperatures of the pyrolysis reactor and the catalytic pyrolysis reactor to be 400-800 ℃ respectively;
(3) starting the temperature rise degree of the pyrolysis reactor and the catalytic pyrolysis reactor, starting a refrigerating pump, carrying out pyrolysis reaction on waste plastics in the pyrolysis reactor, and simultaneously generating macromolecular hydrocarbon substances, wherein the temperature of the refrigerating pump is-20 ℃ to-50 ℃;
(4) macromolecular hydrocarbon substances generated in the pyrolysis reactor are carried into the catalytic pyrolysis reactor by carrier gas, and the macromolecular organic substances are subjected to cracking and aromatization reactions under the action of a catalyst;
(5) the catalyzed waste plastic pyrolysis product is carried into a product recovery system by carrier gas for recovery, and the flow rate of the carrier gas is 50 ml/min-1L/min.
When the waste plastics are subjected to catalytic pyrolysis, the catalytic pyrolysis reactor in the steps (1), (2), (3) and (4) is an infrared heating pyrolysis reactor.
When the waste plastics are subjected to catalytic pyrolysis, the particle size of the waste plastics in the step (1) is 1-50 mm.
When the waste plastics are subjected to catalytic pyrolysis, the catalyst in the step (1) is precious metal, transition metal oxide, alkali (earth) metal oxide, molecular sieve-supported metal oxide, metal salt and ore containing metal elements.
When the waste plastics are subjected to catalytic pyrolysis, the ratio of the catalyst to the waste plastics in the step (1) is 10: 1-1: 10.
The waste plastic is one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS, nylon and polyethylene terephthalate.
When the waste plastics are pyrolyzed independently or when the waste plastics are pyrolyzed in a catalytic mode, the gas distribution system comprises a high-pressure gas cylinder, a gas pressure reducing valve and a gas mass flowmeter which are connected in sequence through a stainless steel pipe with the inner diameter of 6 mm.
When the waste plastics are pyrolyzed independently or when the waste plastics are pyrolyzed catalytically, the product recovery system comprises a product recovery system which comprises a condensation tank, a refrigerator, a liquid collecting bottle, a gas washing bottle, a gas filter and a wet flowmeter which are connected in sequence by a silica gel hose with the inner diameter of 6 mm.
The invention has the beneficial effects that:
1. solves the problems of difficult degradation and serious environmental pollution of the waste plastics, and realizes the reduction, reclamation and harmless disposal of the waste plastics.
2. The waste plastic is rapidly pyrolyzed by infrared heating, so that the waste plastic is uniformly heated.
3. The waste plastic is subjected to catalytic pyrolysis, the content of macromolecular products in pyrolysis products is reduced, and the quality of the pyrolysis products is improved.
4. The separation of the catalyst and the waste plastic is realized, the pyrolysis temperature and the catalysis temperature of the waste plastic are respectively controlled, and the catalysis efficiency is improved.
Drawings
FIG. 1 is a connection diagram of process equipment for separately pyrolyzing waste plastics according to the method for pyrolyzing and catalytically pyrolyzing waste plastics by infrared heating according to the present invention.
FIG. 2 is a connection diagram of process equipment for the catalytic pyrolysis of waste plastics in the infrared heating waste plastic pyrolysis and catalytic pyrolysis method of the invention.
Labeled as: the gas distribution system comprises a gas distribution system 1, a high-pressure steel cylinder 1-1, a gas pressure reducing valve 1-2, a high-pressure steel cylinder 1-3, a pyrolysis reactor 2, a catalytic pyrolysis reactor 3, a product recovery system 4, a refrigerator 4-1, a liquid collecting bottle 4-2, a condensation tank 4-3, a gas washing bottle 4-4, a gas filter 4-5, a wet-type flowmeter 4-6 and a gas collecting tank 4-7.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
It should be noted that, unless explicitly stated or limited otherwise, the terms "connected" and "connected" in the description of the present invention are to be construed broadly, and may be, for example, fixedly, detachably, or integrally, mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
Example 1
As shown in fig. 1, the process equipment for separately pyrolyzing waste plastics according to the method for pyrolyzing and catalytically pyrolyzing waste plastics by infrared heating according to the present invention includes a gas distribution system 1, a pyrolysis reactor 2, and a product recovery system 4. The concrete structure and the connection relation of the components are as follows:
the gas distribution system 1 comprises a high-pressure steel cylinder 1-1, a gas pressure reducing valve 1-2 and a high-pressure steel cylinder 1-3 which are connected through a stainless steel pipe or a copper pipe with the inner diameter of 3mm, wherein the high-pressure steel cylinder 1-1 is firstly connected with the gas pressure reducing valve 1-2, the gas pressure reducing valve 1-2 is then connected with the high-pressure steel cylinder 1-3, and the high-pressure steel cylinder 1-3 is connected with a pyrolysis reactor 2;
the product recovery system 4 comprises a refrigerator 4-1, a liquid collecting bottle 4-2, a condensation tank 4-3, a gas washing bottle 4-4, a gas filter 4-5, a wet type flowmeter 4-6 and a gas collecting tank 4-7, wherein the cooling liquid in the refrigerator 4-1 is ethylene glycol and can be cooled to the temperature below minus 20 ℃, the refrigerator 4-1 is communicated with the condensation tank 4-3, the liquid collecting bottle 4-2 is communicated with the pyrolysis reactor 2 and is soaked in the condensation tank 4-3 filled with condensate, the liquid collecting bottle 4-2 is also connected with the gas washing bottle 4-4, the gas washing bottle 4-4 is connected with the gas filter 4-5, the gas filter 4-5 is connected with the wet type flowmeter 4-6, the wet type flowmeter 4-6 is connected with the gas collecting tank 4-7 and a gas product analyzer, the gas washing bottle 4-4 is filled with one of acetone, dichloromethane, chloroform, methanol, ethanol and carbon disulfide solution, and the gas filter 4-5 is filled with cotton.
Example 2
As shown in fig. 2, the components of the process equipment for catalytic pyrolysis of waste plastics by using the infrared heating waste plastic pyrolysis and catalytic pyrolysis method of the present invention include a gas distribution system 1, a pyrolysis reactor 2, a catalytic pyrolysis reactor 3, and a product recovery system 4, and the specific structures and connection relations of the components are as follows:
the components and connection relationship of the gas distribution system 1 and the product recovery system 4 are the same as those in embodiment 1, and the difference is that the gas distribution system 1 is connected with the pyrolysis reactor 2, the pyrolysis reactor 2 is connected with the catalytic pyrolysis reactor 3, and the catalytic pyrolysis reactor 3 is connected with the product recovery system 4.
Example 3
A method for pyrolysis and catalytic pyrolysis of infrared rapid heating waste plastics comprises connecting a pyrolysis device in the connection manner described in embodiment 1 when the waste plastics are pyrolyzed separately, weighing 3g of plastics (polyethylene) with particle size of 10mm, loading into a pyrolysis reactor 2, connecting a pipeline, preferably nitrogen gas in a high-pressure steel cylinder 1-1, adjusting the gas flow of the high-pressure steel cylinder 1-3 to 100ml/min,
the pyrolysis reactor 2 is preferably at 400 ℃ and the heating rate is preferably 20 ℃/s, and the residence time at 400 ℃ is 30min, so that the pyrolysis product distribution is 0.9% of solid products, 92.6% of liquid products (containing wax) and 6.5% of gas products.
Example 4
A method for pyrolysis and catalytic pyrolysis of infrared rapid heating waste plastics comprises connecting a pyrolysis device in the connection manner described in embodiment 1 when the waste plastics are pyrolyzed separately, weighing 3g of plastics (polyethylene) with particle size of 20mm, loading into a pyrolysis reactor 2, connecting a pipeline, preferably nitrogen gas in a high-pressure steel cylinder 1-1, adjusting the gas flow of the high-pressure steel cylinder 1-3 to 100ml/min,
the pyrolysis reactor temperature is preferably 600 ℃, the heating rate is preferably 30 ℃/s, the residence time at 600 ℃ is 30min, and the pyrolysis product distribution obtained under the conditions is 0.51 percent of solid product, 90.32 percent of liquid product (containing wax) and 9.17 percent of gas product.
Example 5
A method for pyrolysis and catalytic pyrolysis of infrared rapid heating waste plastics comprises connecting a pyrolysis device in the connection manner described in embodiment 1 when the waste plastics are pyrolyzed separately, weighing 5g of plastics (polyethylene) with particle size of 30mm, loading into a pyrolysis reactor 2, connecting a pipeline, preferably nitrogen gas in a high-pressure steel cylinder 1-1, adjusting the gas flow of the high-pressure steel cylinder 1-3 to 100ml/min,
the pyrolysis reactor temperature is preferably 800 ℃, the heating rate is preferably 30 ℃/s, the residence time at 800 ℃ is 30min, and the pyrolysis product distribution obtained under the conditions is 0.1% of solid product, 78.37% of liquid product (containing wax) and 21.62% of gas product.
Example 6
When the waste plastic is subjected to catalytic pyrolysis, a pyrolysis device is connected according to the connection mode of embodiment 2, 3g of plastic (polyethylene) with the particle size of 10mm is weighed and is loaded into a pyrolysis reactor 2, 1.5g of iron oxide catalyst is loaded into a catalytic pyrolysis reactor 3, a pipeline is connected, the gas in a high-pressure steel cylinder 1-1 is preferably nitrogen, the gas flow of the high-pressure steel cylinder 1-3 is adjusted to be 100ml/min, the temperature of the pyrolysis reactor 2 is preferably 500 ℃, the temperature of the catalytic pyrolysis reactor 3 is preferably 400 ℃, the heating rate is preferably 30 ℃/s, the retention time at 600 ℃ is 30min, and the pyrolysis product distribution solid product obtained under the condition accounts for 0.46%, the liquid product (containing wax) accounts for 74.32%, and the gas product accounts for 25.22%.
In particular, the high-pressure steel cylinder 1-1, the gas pressure reducing valve 1-2, the high-pressure steel cylinder 1-3, the pressure gauge, the temperature controller, the refrigerator 4-1, the purge gas cylinder 4-4, the gas filter 4-5 and the wet flow meter 4-6 are all universal standard components or components known by those skilled in the art, and these components or instruments can be found by inquiring relevant manuals or standards. The invention mainly aims to provide a pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics, which can realize reduction, recycling and harmless treatment of the waste plastics, and has the advantages of high temperature rise rate and strong raw material adaptability.
The sizes of the pyrolysis reactor 2, the catalytic pyrolysis reactor 3, the condensation tank 4-3, the liquid collecting bottle 4-2 and the gas collecting tank 4-7 are not fixed values, and the sizes of the pyrolysis reactor, the catalytic pyrolysis reactor, the condensation tank, the liquid collecting bottle and the gas collecting tank can be specifically determined according to experimental conditions.
The present invention may be embodied in several forms and its modification in the shape and size of the present disclosure may be made without departing from the spirit and scope of the present invention.
Claims (10)
1. A pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics is characterized by comprising the following steps when the waste plastics are pyrolyzed independently:
(1) crushing waste plastics until the particle size is uniform, and putting the waste plastics into a pyrolysis reactor;
(2) the method comprises the following steps of sequentially connecting a gas distribution system, a pyrolysis reactor and a product recovery system, and setting the gas flow and the target temperature of the pyrolysis reactor to be 400-800 ℃;
(3) starting a temperature rise program of a pyrolysis reactor and a refrigeration pump, carrying out pyrolysis reaction on waste plastics at high temperature, and carrying out generated volatile components out by carrier gas, wherein the temperature of the refrigeration pump is-20 ℃ to-50 ℃;
(4) the volatiles carried over by the carrier gas are collected in a product recovery system.
2. The infrared fast pyrolysis and catalytic pyrolysis method for waste plastics, according to claim 1, characterized in that the pyrolysis reactor in steps (2) and (3) is an infrared heating pyrolysis reactor.
3. A pyrolysis and catalytic pyrolysis method for infrared rapid heating of waste plastics is characterized by comprising the following steps of:
(1) crushing waste plastics until the particle size is uniform, putting the waste plastics into a pyrolysis reactor, and putting a certain proportion of catalyst into a catalytic pyrolysis reactor;
(2) the method comprises the following steps of sequentially connecting a gas distribution system, a pyrolysis reactor, a catalytic pyrolysis reactor and a product recovery system, and setting the gas flow and the target temperatures of the pyrolysis reactor and the catalytic pyrolysis reactor to be 400-800 ℃ respectively;
(3) starting the temperature rise degree of the pyrolysis reactor and the catalytic pyrolysis reactor, starting a refrigerating pump, carrying out pyrolysis reaction on waste plastics in the pyrolysis reactor, and simultaneously generating macromolecular hydrocarbon substances, wherein the temperature of the refrigerating pump is-20 ℃ to-50 ℃;
(4) macromolecular hydrocarbon substances generated in the pyrolysis reactor are carried into the catalytic pyrolysis reactor by carrier gas, and the macromolecular organic substances are subjected to cracking and aromatization reactions under the action of a catalyst;
(5) the catalyzed waste plastic pyrolysis product is carried into a product recovery system by carrier gas for recovery, and the flow rate of the carrier gas is 50 ml/min-1L/min.
4. The method for pyrolyzing and catalytically pyrolyzing waste plastics by infrared rapid heating according to claim 3, wherein the catalytic pyrolysis reactor in steps (1), (2), (3) and (4) is an infrared heating pyrolysis reactor.
5. The method for pyrolyzing and catalytically pyrolyzing waste plastics by infrared rapid heating according to claim 3, wherein the particle size of the waste plastics in the step (1) is 1-50 mm.
6. The method for the pyrolysis and catalytic pyrolysis of infrared rapid heating waste plastics according to claim 3, wherein the catalyst in the step (1) is noble metal, transition metal oxide, alkali (earth) metal oxide, molecular sieve-supported metal oxide, metal salt or ore containing metal elements.
7. The method for pyrolyzing and catalytically pyrolyzing waste plastics by infrared rapid heating according to claim 3, wherein the ratio of the catalyst to the waste plastics in the step (1) is 10:1 to 1: 10.
8. The method for pyrolysis and catalytic pyrolysis of infrared rapidly heated waste plastics according to claim 1 or 3, wherein the waste plastics are one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS, nylon and polyethylene terephthalate.
9. The method for the pyrolysis and catalytic pyrolysis of the infrared rapid heating waste plastics as claimed in claim 1 or 3, wherein the gas distribution system comprises a high-pressure gas cylinder, a gas pressure reducing valve and a gas mass flow meter which are connected in sequence by a stainless steel pipe with the inner diameter of 6 mm.
10. The infrared fast pyrolysis and catalytic pyrolysis method for waste plastics, as claimed in claim 1 or 3, characterized in that the product recovery system comprises a product recovery system comprising a condensation tank, a refrigerator, a liquid collection bottle, a gas washing bottle, a gas filter, a wet flowmeter, which are connected in turn by a silica gel hose with an inner diameter of 6 mm.
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