CN114806619A - System and method for recycling all components of waste tire - Google Patents
System and method for recycling all components of waste tire Download PDFInfo
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- CN114806619A CN114806619A CN202210462711.5A CN202210462711A CN114806619A CN 114806619 A CN114806619 A CN 114806619A CN 202210462711 A CN202210462711 A CN 202210462711A CN 114806619 A CN114806619 A CN 114806619A
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- 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
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
Abstract
A full-component recycling system and method for waste tires comprises a quality-dividing treatment unit, wherein the quality-dividing treatment unit divides the waste tires into steel wires, low-ash components and high-ash components according to the ash content difference of different parts of the waste tires; the low-ash component and the high-ash component are respectively subjected to pressure pyrolysis through a pressure pyrolysis unit to obtain pyrolysis gas, pyrolysis oil and pyrolysis coke, the pyrolysis coke obtained from the low-ash component is subjected to in-situ activation through a first in-situ activation unit to obtain activated carbon, and the pyrolysis coke obtained from the high-ash component is subjected to in-situ activation through a second in-situ activation unit and then sequentially passes through an alkali washing unit and a water washing unit to obtain activated carbon and alkali liquor precipitate; introducing activated carbon into pyrolysis gas obtained from the low-ash component and the high-ash component for catalytic reforming to obtain methane-rich gas and activated carbon; and calcining the alkali liquor precipitate by a calcining unit to obtain ash, and catalytically reforming the methane-rich gas by using the ash as a catalyst to prepare the hydrogen-rich gas. The invention provides a way for recycling the waste tires.
Description
Technical Field
The invention belongs to the technical field of waste tire recycling, and particularly relates to a waste tire full-component recycling system and method.
Background
With the rapid development of industrial and agricultural industries in China, the annual output of waste tires is increased sharply. At present, due to improper disposal of the waste tires, part of the waste tires which are not recycled become black pollution. The pyrolysis oil and the pyrolysis coke are main products of the pressurization pyrolysis of the waste tires, and the recycling of the pyrolysis oil and the pyrolysis coke determines the economic feasibility of the pressurization pyrolysis process of the waste tires to a great extent. Meanwhile, the pressurized pyrolytic coke is further treated, so that the quality of the pyrolytic coke is improved, and the economic maximization of the waste tire pressurized pyrolytic process is facilitated.
Disclosure of Invention
The invention aims to provide a full-component recycling system and method for waste tires aiming at the problems in the prior art, the yield of pyrolysis oil and pyrolysis coke is high, the ash content of in-situ activated pyrolysis coke is low, the specific surface area is large, the particles are uniform and the quality is good, ash obtained by calcining alkali washing precipitates can be used as a catalyst to prepare hydrogen-rich gas, and full-component recycling treatment is realized.
In order to achieve the purpose, the invention has the following technical scheme:
a full-component recycling system for waste tires comprises a quality-dividing treatment unit, wherein the quality-dividing treatment unit divides the waste tires into steel wires, low-ash components and high-ash components according to the ash content difference of different parts of the waste tires; the low-ash component and the high-ash component are respectively subjected to pressure pyrolysis through a pressure pyrolysis unit to obtain pyrolysis gas, pyrolysis oil and pyrolysis coke, the pyrolysis coke obtained from the low-ash component is subjected to in-situ activation through a first in-situ activation unit to obtain activated carbon, the pyrolysis coke obtained from the high-ash component is subjected to in-situ activation through a second in-situ activation unit and then sequentially subjected to an alkali washing unit and a water washing unit to obtain activated carbon and alkali liquor precipitate, and water vapor is introduced into the first in-situ activation unit and the second in-situ activation unit; introducing activated carbon into the pyrolysis gas obtained from the low-ash component and the high-ash component for catalytic reforming to obtain methane-rich gas and activated carbon; and calcining the alkali liquor precipitate by a calcining unit to obtain ash, and performing catalytic reforming on the methane-rich gas by using the ash as a catalyst to obtain hydrogen-rich gas.
As a preferable scheme of the system, pyrolysis oil obtained from the low-ash component and the high-ash component is collected into the same container; and collecting activated carbon obtained by pyrolyzing coke in the low-ash component and the high-ash component into the same container.
As a preferable scheme of the system, the water washing unit washes the pyrolytic coke water after passing through the alkali washing unit to be neutral through deionized water, and activated carbon and alkali liquor precipitate are obtained.
A method for recycling all components of a waste tire comprises the following steps:
performing full-component quality-based treatment on the waste tire according to the ash content difference of different parts to obtain a steel wire, a low-ash component and a high-ash component;
respectively carrying out pressurized pyrolysis on the low ash component and the high ash component to obtain pyrolysis gas, pyrolysis oil and pyrolysis coke;
performing in-situ activation on the pyrolytic coke obtained from the low ash component to obtain activated carbon; carrying out in-situ activation on the pyrolytic coke obtained from the high ash component, and then sequentially carrying out alkali washing and water washing to obtain activated carbon and alkali liquor precipitate;
introducing activated carbon into pyrolysis gas obtained from the low ash component and the high ash component for catalytic reforming to obtain methane-rich gas and activated carbon;
calcining the alkali liquor precipitate to obtain ash;
and performing catalytic reforming on the methane-rich gas by using the ash as a catalyst to prepare a hydrogen-rich gas.
As a preferable scheme of the method, the step of respectively carrying out pressure pyrolysis on the low ash component and the high ash component has the pressure of 0.1MPa to 30MPa, the temperature of 400 ℃ to 850 ℃ and the reaction time of 0.5h to 1.5 h.
As a preferred scheme of the method, the steps of in-situ activation of the pyrolytic coke obtained from the low ash component and the steps of in-situ activation of the pyrolytic coke obtained from the high ash component are all completed by introducing steam, the temperature of in-situ activation is 600-1000 ℃, the reaction time is 0.5-2 h, and the mass ratio of the steam to the pyrolytic coke is 0.01-10.
As the inventionIn a preferred embodiment of the method, the activated carbon has an ash concentration of 0.01 wt.% to 2.00 wt.% and a specific surface area of 100m 2 /g～1000m 2 /g。
As a preferable scheme of the method, in the step of introducing activated carbon into the pyrolysis gas obtained from the low ash component and the high ash component for catalytic reforming to obtain the methane-rich gas and the activated carbon, the temperature of the catalytic reforming is 500-800 ℃, and the mass ratio of the activated carbon to the low ash component or the high ash component is 0.1-5.0.
As a preferable scheme of the method, in the step of sequentially carrying out alkali washing and water washing after in-situ activation on the pyrolytic coke obtained from the high-ash component, the concentration of the alkali liquor is 1.0-10.0 mol/L, the solid-to-liquid ratio of the pyrolytic coke to the alkali liquor is 1-10-5 g/10mL, and the alkali washing stirring time is 2-6 h.
As a preferable scheme of the method, in the step of catalytically reforming the methane-rich gas by using the ash as the catalyst to prepare the hydrogen-rich gas, the catalytic reforming temperature is 600-1000 ℃, and the mass ratio of the ash to the low ash component or the high ash component is 0.1-3.0.
Compared with the prior art, the invention has the following beneficial effects:
the method has the advantages that the waste tire is subjected to full-component quality separation and pressurized pyrolysis according to the ash content difference of different parts of the waste tire, so that steel wires, low-ash components and high-ash components of the waste tire can be effectively separated, and the quality of pyrolysis products of different components is improved. The full-component pressurized pyrolysis of the waste tire generates high-quality pyrolysis oil, pyrolysis coke and pyrolysis gas, and is a final treatment mode for efficiently treating the waste tire. The pressurized pyrolysis coke is subjected to steam in-situ activation under normal pressure to prepare the activated carbon with high specific surface area, can be widely applied to the fields of sewage treatment, catalyst carriers, energy storage materials and the like, and is a main utilization direction for improving the economic efficiency of the pyrolysis process of the organic solid waste tire. The activated carbon with high specific surface area prepared by the full-component recycling method for the waste tires has uniform particle size and good quality, has high adsorption removal rate on pollutants such as phenol, cadmium and the like in water, and selects methane-rich gas prepared by catalytic cracking of pyrolysis gasHigh in performance and the product quality meets the national industrial standard. Meanwhile, the ash slag prepared by the full component recycling method of the waste tire is rich in ZnO and SiO 2 The selectivity of preparing hydrogen-rich gas by catalytic cracking of methane-rich gas is high. The invention not only solves the problem of waste tire pollution, but also provides a way for recycling the waste tire, and has wide application prospect.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. The drawings in the following description are part of embodiments of the invention, and it will be clear to a person skilled in the art that other drawings can be derived from these drawings without inventive effort.
FIG. 1 is a schematic view of the working principle of a full-component recycling system for waste tires according to an embodiment of the present invention;
in the drawings: 1-scrap tires; 2-water vapor;
11-a quality-divided processing unit; 12-a first pressurized pyrolysis unit; 13-a second pressurized pyrolysis unit; 14-a first in situ activation unit; 15-a second in situ activation unit; 16-an alkaline washing unit; 17-a water washing unit; 18-a calcination unit;
21-steel wire; 22-low ash component; 23-high ash component; 24-low ash component pyrolysis gas; 25-high ash component pyrolysis gas; 26-pyrolysis oil; 27-low ash content pyrolysis coke; 28-high ash component pyrolytic coke; 29-lye precipitate; 30-activated carbon; 31-activated carbon; 32-methane rich gas; 33-ash; 34-hydrogen rich gas.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. The described embodiments are only some embodiments of the invention, not all embodiments.
All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, also belong to the protection scope of the present invention.
As shown in fig. 1, the full-component recycling system for waste tires according to the embodiment of the present invention includes a quality-classification processing unit 11, and the quality-classification processing unit 11 classifies the waste tires 1 into steel wires 21, low-ash components 22 and high-ash components 23 according to ash content differences at different parts of the waste tires 1. The low-ash component 22 and the high-ash component 23 are respectively subjected to pressure pyrolysis through a pressure pyrolysis unit to obtain pyrolysis gas, pyrolysis oil 26 and pyrolysis coke, the pyrolysis coke obtained from the low-ash component 22 is subjected to in-situ activation through a first in-situ activation unit 14 to obtain activated carbon 30, the pyrolysis coke obtained from the high-ash component 23 is subjected to in-situ activation through a second in-situ activation unit 15 and then sequentially passes through an alkali washing unit 16 and a water washing unit 17, the water washing unit 17 washes the pyrolysis coke after passing through the alkali washing unit 16 to be neutral through deionized water to obtain the activated carbon 30 and an alkali liquor precipitate 29, and water vapor 2 is introduced into the first in-situ activation unit 14 and the second in-situ activation unit 15; introducing activated carbon 30 into the pyrolysis gas obtained from the low ash component 22 and the high ash component 23 for catalytic reforming to obtain methane-rich gas 32 and activated carbon 31; the alkali liquor precipitate 29 and the alkali liquor discharged by the alkali washing unit 16 are calcined by the calcining unit 18 to obtain ash 33, and the ash 33 is used as a catalyst to perform catalytic reforming on the methane-rich gas 32 to obtain a hydrogen-rich gas 34.
In one possible embodiment, the pyrolysis oil 26 from the low ash component 22 and the high ash component 23 is collected in the same vessel; the low ash component 22 and the high ash component 23 are collected into the same container by the activated carbon 30 obtained by pyrolysis of coke.
The method for recycling the whole components of the waste tire comprises the following steps:
performing full-component quality-based treatment on the waste tire 1 according to the ash content difference of different parts to obtain a steel wire 21, a low ash component 22 and a high ash component 23;
respectively carrying out pressurized pyrolysis on the low ash component 22 and the high ash component 23 to obtain pyrolysis gas, pyrolysis oil 26 and pyrolysis coke;
in-situ activation is carried out on the pyrolytic coke obtained from the low ash component 22 to obtain activated carbon 30; performing in-situ activation on the pyrolytic coke obtained from the high ash component 23, and then sequentially performing alkali washing and water washing to obtain activated carbon 30 and an alkali liquor precipitate 29;
introducing activated carbon 30 into pyrolysis gas obtained from the low ash component 22 and the high ash component 23 for catalytic reforming to obtain methane-rich gas 32 and activated carbon 31;
calcining the alkali liquor precipitate 29 to obtain ash 33;
the ash 33 is used as a catalyst to perform catalytic reforming on the methane-rich gas 32 to prepare a hydrogen-rich gas 34.
In one possible embodiment, the low ash component 22 and the high ash component 23 are separately subjected to pressure pyrolysis at a pressure of 0.1MPa to 30MPa, a temperature of 400 ℃ to 850 ℃, and a reaction time of 0.5h to 1.5 h.
In a possible embodiment, the steps of in-situ activation of the pyrolytic coke obtained from the low ash component 22 and in-situ activation of the pyrolytic coke obtained from the high ash component 23 are completed by introducing water vapor 2, the temperature of in-situ activation is 600-1000 ℃, the reaction time is 0.5-2 h, and the mass ratio of the water vapor 2 to the pyrolytic coke is 0.01-10.
The obtained activated carbon 30 is activated carbon with high specific surface area, the ash concentration of the activated carbon 30 is 0.01 wt.% to 2.00 wt.%, and the specific surface area is 100m 2 /g～1000m 2 (ii) in terms of/g. And in the step of introducing activated carbon 30 into the pyrolysis gas obtained from the low ash component 22 and the high ash component 23 for catalytic reforming to obtain methane-rich gas 32 and activated carbon 31, the temperature of the catalytic reforming is 500-800 ℃, and the mass ratio of the activated carbon 30 to the low ash component 22 or the high ash component 23 is 0.1-5.0, and more preferably 0.2-2.0.
In a possible embodiment, in the step of sequentially performing alkali washing and water washing after in-situ activation on the pyrolytic coke obtained from the high ash component 23, the concentration of the alkali liquor is 1.0 mol/L-10.0 mol/L, the solid-to-liquid ratio of the pyrolytic coke to the alkali liquor is 1g/10 mL-5 g/10mL, and the alkali washing stirring time is 2 h-6 h.
The resulting ash 33 is mainly rich in ZnO and SiO 2 In the step of catalytically reforming the methane-rich gas 32 with the ash 33 as a catalyst to obtain the hydrogen-rich gas 34, the catalytic reforming temperature is 600 ℃ to 1000 ℃, and the mass ratio of the ash 33 to the low ash component 22 or the high ash component 23 is 0.1 to 3.0, more specificallyFurther preferably 0.5 to 3.0.
Example 1
Referring to fig. 1, the method for recycling the whole components of the waste tire in the embodiment of the invention comprises the following steps:
(1) according to the ash content difference of different parts of the waste tire 1, the waste tire 1 is sent to a quality separation treatment unit 11 for full-component quality separation treatment to obtain a steel wire 21, a low ash component 22 and a high ash component 23. The low ash fraction 22 and the high ash fraction 23 are cut into small pieces (less than 2mm) for convenient sample loading.
(2) The low ash component 22 and the high ash component 23 enter the first pressurized pyrolysis unit 12 and the second pressurized pyrolysis unit 13 and are charged into the pressurized pyrolysis furnace with a material height not exceeding the furnace shell 2/3. In the process of pressure pyrolysis, firstly, the low ash component 22 and the high ash component 23 are subjected to pressure pyrolysis under the pyrolysis process conditions that the nitrogen flow rate is 100mL/min, the pressure is 3.0MPa and the temperature is 500 ℃. Then, the low ash component thermal coke 27 and the high ash component thermal coke 28 of the low ash component 22 and the high ash component 23 are activated in situ under the conditions of normal pressure, the temperature of 700 ℃ and the mass ratio of the water vapor 2 to the material of 0.5.
(3) The collected high ash content pyrolysis coke activated carbon sequentially enters an alkali washing unit 16 and a water washing unit 17. Mixing the high-ash-component thermal coke activated carbon with 5mol/L NaOH solution at a solid-to-liquid ratio of 3g/10mL, and stirring at normal temperature for 4 h. And (3) carrying out suction filtration on the carbon black subjected to alkali washing, washing the carbon black to be neutral (pH 7.0) by using deionized water, and calcining the carbon black at 700 ℃ to obtain the low-ash high-specific-surface-area activated carbon.
(4) The alkali wash concentrated and precipitated enters a calcining unit 18 for calcining at the temperature of 600 ℃ to obtain the alkali wash rich in ZnO and SiO 2 33 of the ash.
(5) The activated carbon 30 obtained by activation is used as a catalyst of the low ash component pyrolysis gas 24 and the high ash component pyrolysis gas 25 under the conditions that the temperature is 600 ℃ and the mass ratio of the activated carbon 30 to the low ash component 22 or the high ash component 23 is 1.5, and the methane-rich gas 32 is prepared by catalytic reforming. The ash 33 is used as a catalyst for the methane-rich gas 32 at 700 ℃ and the mass ratio of the ash 33 to the low ash component 22 or the high ash component 3 is 0.5, and the hydrogen-rich gas 34 is produced by catalytic reforming.
Example 2
Referring to fig. 1, the method for recycling the whole components of the waste tire in the embodiment of the invention comprises the following steps:
(1) according to the ash content difference of different parts of the waste tire 1, the waste tire 1 is sent to a quality separation treatment unit 11 for full-component quality separation treatment to obtain a steel wire 21, a low ash component 22 and a high ash component 23. The low ash fraction 22 and the high ash fraction 23 are cut into small pieces (less than 2mm) for convenient sample loading.
(2) The low ash component 22 and the high ash component 23 enter the first pressurized pyrolysis unit 12 and the second pressurized pyrolysis unit 13 and are charged into the pressurized pyrolysis furnace with a material height not exceeding the furnace shell 3/5. In the process of pressure pyrolysis, firstly, the low ash component 22 and the high ash component 23 are subjected to pressure pyrolysis under the pyrolysis process conditions that the nitrogen flow rate is 150mL/min, the pressure is 10.0MPa and the temperature is 600 ℃. Then, the low ash component thermal coke 27 and the high ash component thermal coke 28 of the low ash component 22 and the high ash component 23 are activated in situ under the conditions of normal pressure, the temperature of 800 ℃ and the mass ratio of the water vapor 2 to the material of 0.8.
(3) The collected high ash content pyrolysis coke activated carbon sequentially enters an alkali washing unit 16 and a water washing unit 17. Mixing the high-ash-component thermal coke activated carbon with 10mol/L NaOH solution at a solid-to-liquid ratio of 5g/10mL, and stirring at normal temperature for 6 h. And (3) carrying out suction filtration on the carbon black subjected to alkali washing, washing the carbon black to be neutral (pH 7.0) by using deionized water, and calcining the carbon black at 800 ℃ to obtain the low-ash high-specific-surface-area activated carbon.
(4) The alkali wash concentrated and precipitated enters a calcining unit 18 for calcining at 650 ℃ to obtain the alkali wash rich in ZnO and SiO 2 33 of the ash.
(5) The activated carbon obtained by activation is used as a catalyst of the low ash component pyrolysis gas 24 and the high ash component pyrolysis gas 25 under the conditions that the temperature is 800 ℃ and the mass ratio of the activated carbon 30 to the low ash component 22 or the high ash component 23 is 3.0, and the methane-rich gas 32 is prepared by catalytic reforming. The ash 33 is used as a catalyst for the methane-rich gas 32 at 800 ℃ and a mass ratio of the ash 33 to the low ash component 22 or the high ash component 3 of 2.0, and the hydrogen-rich gas 34 is produced by catalytic reforming.
Example 3
Referring to fig. 1, the method for recycling the whole components of the waste tire in the embodiment of the invention comprises the following steps:
(1) according to the ash content difference of different parts of the waste tire 1, the waste tire 1 is sent to a quality-dividing treatment unit 11 to be subjected to full-component quality-dividing treatment to obtain a steel wire 21, a low-ash component 22 and a high-ash component 23. The low ash fraction 22 and the high ash fraction 23 are cut into small pieces (less than 2mm) for convenient sample loading.
(2) The low ash component 22 and the high ash component 23 enter the first pressurized pyrolysis unit 12 and the second pressurized pyrolysis unit 13 and are charged into the pressurized pyrolysis furnace with a material height not exceeding the furnace shell 1/2. In the process of pressure pyrolysis, firstly, the low ash component 22 and the high ash component 23 are subjected to pressure pyrolysis under the pyrolysis process conditions that the nitrogen flow rate is 100mL/min, the pressure is 15.0MPa and the temperature is 600 ℃. Then, the low ash component thermal coke 27 and the high ash component thermal coke 28 of the low ash component 22 and the high ash component 23 are activated in situ under the conditions of normal pressure, the temperature of 600 ℃ and the mass ratio of the water vapor 2 to the material of 1.0.
(3) The collected high ash content pyrolysis coke activated carbon sequentially enters an alkali washing unit 16 and a water washing unit 17. Mixing the high-ash-component thermal coke activated carbon with 8mol/L NaOH solution at a solid-to-liquid ratio of 4g/10mL, and stirring at normal temperature for 4 h. And (3) carrying out suction filtration on the carbon black subjected to alkali washing, washing the carbon black to be neutral (pH 7.0) by using deionized water, and calcining the carbon black at 600 ℃ to obtain the low-ash high-specific-surface-area activated carbon.
(4) The alkali wash concentrated and precipitated enters a calcining unit 18 for calcining at 700 ℃ to obtain the alkali wash rich in ZnO and SiO 2 33 of the ash.
(5) The activated carbon obtained by activation is used as a catalyst of the low ash component pyrolysis gas 24 and the high ash component pyrolysis gas 25 under the conditions that the temperature is 700 ℃ and the mass ratio of the activated carbon 30 to the low ash component 22 or the high ash component 23 is 5.0, and the methane-rich gas 32 is prepared by catalytic reforming. The ash 33 is used as a catalyst for the methane-rich gas 32 at 600 ℃ and the mass ratio of the ash 33 to the low ash component 22 or the high ash component 3 is 3.0, and the hydrogen-rich gas 34 is produced by catalytic reforming.
The invention not only solves the problem of waste tire pollution, but also provides an effective way for resource utilization of waste tires, and the waste tire is prepared by the inventionThe full-component recycling method for preparing the activated carbon with high specific surface area has uniform particle size, good quality, high adsorption and removal rate on pollutants such as phenol, cadmium and the like in water, high selectivity on preparing methane-rich gas by catalytic cracking of pyrolysis gas, and the product quality meets the national industrial standard. The ash slag prepared by the full component recycling method of the waste tire is rich in ZnO and SiO 2 The method has high selectivity for preparing hydrogen-rich gas by catalytic cracking of methane-rich gas, and has wide application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the technical solution of the present invention, and it should be understood by those skilled in the art that the technical solution can be modified and replaced by a plurality of simple modifications and replacements without departing from the spirit and principle of the present invention, and the modifications and replacements also fall within the protection scope defined by the claims.
Claims (10)
1. The utility model provides a full component resource system of scrap tire which characterized in that: the quality grading treatment device comprises a quality grading treatment unit (11), wherein the quality grading treatment unit (11) grades the waste tire (1) into a steel wire (21), a low-ash component (22) and a high-ash component (23) according to the ash content difference of different parts of the waste tire (1); the low-ash component (22) and the high-ash component (23) are respectively subjected to pressure pyrolysis through a pressure pyrolysis unit to obtain pyrolysis gas, pyrolysis oil (26) and pyrolysis coke, the pyrolysis coke obtained from the low-ash component (22) is subjected to in-situ activation through a first in-situ activation unit (14) to obtain activated carbon (30), the pyrolysis coke obtained from the high-ash component (23) is subjected to in-situ activation through a second in-situ activation unit (15) and then sequentially subjected to an alkali washing unit (16) and a water washing unit (17) to obtain activated carbon (30) and alkali liquor precipitate (29), and water vapor (2) is introduced into the first in-situ activation unit (14) and the second in-situ activation unit (15); the pyrolysis gas obtained from the low ash component (22) and the high ash component (23) is introduced into activated carbon (30) for catalytic reforming to obtain methane-rich gas (32) and activated carbon (31); and calcining the alkali liquor precipitate (29) by using a calcining unit (18) to obtain ash (33), and catalytically reforming the methane-rich gas (32) by using the ash (33) as a catalyst to prepare a hydrogen-rich gas (34).
2. The full component recycling system for scrap tires according to claim 1, characterized in that: the pyrolysis oil (26) obtained from the low ash component (22) and the high ash component (23) is collected into the same container; the low ash component (22) and the high ash component (23) are collected into the same container through activated carbon (30) obtained by pyrolyzing coke.
3. The full component recycling system for scrap tires according to claim 1, characterized in that: and the water washing unit (17) washes the pyrolytic coke after passing through the alkali washing unit (16) to be neutral through deionized water to obtain activated carbon (30) and alkali liquor precipitate (29).
4. A method for recycling a whole waste tire component based on the whole waste tire component recycling system according to any one of claims 1 to 3, comprising the steps of:
performing full-component quality-based treatment on the waste tire (1) according to the ash content difference of different parts to obtain a steel wire (21), a low-ash component (22) and a high-ash component (23);
respectively carrying out pressure pyrolysis on the low ash component (22) and the high ash component (23) to obtain pyrolysis gas, pyrolysis oil (26) and pyrolysis coke;
in-situ activation of the pyrolysis coke obtained from the low ash component (22) to obtain activated carbon (30); performing in-situ activation on the pyrolytic coke obtained from the high-ash component (23), and then sequentially performing alkali washing and water washing to obtain activated carbon (30) and an alkali liquor precipitate (29);
introducing activated carbon (30) into pyrolysis gas obtained from the low ash component (22) and the high ash component (23) for catalytic reforming to obtain methane-rich gas (32) and activated carbon (31);
calcining the alkali liquor precipitate (29) to obtain ash (33);
the ash residue (33) is used as a catalyst to carry out catalytic reforming on the methane-rich gas (32) to prepare hydrogen-rich gas (34).
5. The method for recycling the whole components of the waste tire as recited in claim 4, wherein the step of performing the pressure pyrolysis on the low ash component (22) and the high ash component (23) is performed at a pressure of 0.1MPa to 30MPa, a temperature of 400 ℃ to 850 ℃ and a reaction time of 0.5h to 1.5 h.
6. The method for recycling the whole components of the waste tire as claimed in claim 4, wherein the steps of in-situ activation of the pyrolytic coke obtained from the low ash component (22) and in-situ activation of the pyrolytic coke obtained from the high ash component (23) are completed by introducing steam (2), the temperature of in-situ activation is 600-1000 ℃, the reaction time is 0.5-2 h, and the mass ratio of the steam (2) to the pyrolytic coke is 0.01-10.
7. The method for recycling full components of waste tires according to claim 4, characterized in that the activated carbon (30) has an ash concentration of 0.01 wt.% to 2.00 wt.% and a specific surface area of 100m 2 /g～1000m 2 /g。
8. The method for recycling the whole components of the waste tire as claimed in claim 7, wherein in the step of introducing activated carbon (30) into the pyrolysis gas obtained from the low ash component (22) and the high ash component (23) for catalytic reforming to obtain the methane-rich gas (32) and the activated carbon (31), the temperature of the catalytic reforming is 500 ℃ to 800 ℃, and the mass ratio of the activated carbon (30) to the low ash component (22) or the high ash component (23) is 0.1 to 5.0.
9. The method for recycling the whole components of the waste tire as claimed in claim 4, wherein in the step of sequentially performing alkali washing and water washing after the pyrolysis coke obtained from the high ash component (23) is subjected to in-situ activation, the concentration of the alkali liquor is 1.0 mol/L-10.0 mol/L, the solid-to-liquid ratio of the pyrolysis coke to the alkali liquor is 1g/10 mL-5 g/10mL, and the alkali washing stirring time is 2 h-6 h.
10. The method for recycling the whole components of the waste tire as claimed in claim 4, wherein in the step of catalytically reforming the methane-rich gas (32) by using the ash (33) as the catalyst to obtain the hydrogen-rich gas (34), the temperature of the catalytic reforming is 600 ℃ to 1000 ℃, and the mass ratio of the ash (33) to the low ash component (22) or the high ash component (23) is 0.1 to 3.0.
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