CN115612518A - Treatment method for recycling waste tires - Google Patents
Treatment method for recycling waste tires Download PDFInfo
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- CN115612518A CN115612518A CN202211231152.3A CN202211231152A CN115612518A CN 115612518 A CN115612518 A CN 115612518A CN 202211231152 A CN202211231152 A CN 202211231152A CN 115612518 A CN115612518 A CN 115612518A
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- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000010920 waste tyre Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- 238000000197 pyrolysis Methods 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 23
- 239000012634 fragment Substances 0.000 claims abstract description 18
- 238000012546 transfer Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000002485 combustion reaction Methods 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 239000004615 ingredient Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 59
- 230000004580 weight loss Effects 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000000376 reactant Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 6
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 6
- 238000002411 thermogravimetry Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000006148 magnetic separator Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 3
- 238000001914 filtration Methods 0.000 claims 1
- 238000009489 vacuum treatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 239000012263 liquid product Substances 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012265 solid product Substances 0.000 description 6
- 208000005156 Dehydration Diseases 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- 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
-
- 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
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
Abstract
The invention relates to the technical field of tire recovery, and discloses a treatment method for recycling waste tires, which comprises the following steps of S1: crushing, magnetically separating and cleaning waste tires; s2, determining pyrolysis parameters: simulating the pyrolysis reaction of the waste tire, and selecting and determining pyrolysis process parameters; s3, ingredient pyrolysis: carrying out pyrolysis reaction S4 on the tire fragments, the additives and the heat transfer medium, and collecting pyrolysis products: respectively collecting pyrolytic carbon, pyrolytic oil and pyrolytic gas; s5, oil gas detection and analysis: and detecting the content of combustible gas in the pyrolysis gas. The solid decomposition product pyrolytic carbon obtained by the method has the characteristics of large gaps, light weight, less ash and high heat value, has an excellent adsorption function when being used as an adsorbent, and has a higher heating combustion effect when being used as fuel; the obtained liquid product pyrolysis oil has high light fraction content, low heavy fraction content and high quality, and has higher economic value as chemical raw oil.
Description
Technical Field
The invention relates to the technical field of tire recycling, in particular to a treatment method for recycling waste tires.
Background
With the rapid development of the automobile industry in China, waste tires are also increased at a two-digit speed every year, belong to insoluble or indissoluble high-molecular elastic materials, have high elasticity and toughness, cannot change within the range of-50-150 ℃, the decomposition of macromolecules of the waste tires to the extent of not influencing the growth of plants in soil requires hundreds of years, and is difficult to naturally degrade by organisms in the nature, so various waste tire treatment methods are provided, however, a large amount of toxic and harmful gases such as hydrogen sulfide, benzene, polycyclic aromatic hydrocarbon and the like can be generated in the treatment process, and if the treatment is improper, huge environmental pollution and ecological disasters can be easily caused.
Chinese patent discloses a method for recycling waste tires (No. CN 107699269A), which combines a supercritical ethanol method and catalytic oxidation, so that organic matters in the waste tires can be completely decomposed to obtain more fuel oil; meanwhile, carbon black doped in rubber waste tires can be completely separated, the content of the carbon black in solids is increased, but the adsorption performance and the combustion performance of the obtained carbon black are poor, and the quality of the obtained fuel is also poor.
Disclosure of Invention
The present invention is directed to a method for recycling waste tires to solve the above problems of the related art.
In order to achieve the purpose, the invention provides the following technical scheme:
a treatment method for recycling waste tires comprises the following steps:
s1, raw material treatment: crushing the waste tires into pieces of 100mm multiplied by 100mm, magnetically selecting waste steel wires, and cleaning to obtain tire pieces for later use;
s2, determining pyrolysis parameters: taking the tire fragments obtained in the step S1, carrying out a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tire, carrying out thermogravimetric analysis, and selecting appropriate pyrolysis process parameters;
s3, ingredient pyrolysis: adding the tire fragments, the additives and the heat transfer medium obtained in the step S1 into a rotary kiln of a pyrolysis reaction system through a feeding system, introducing high-purity nitrogen into the rotary kiln, vacuumizing, heating according to pyrolysis parameters determined in the step S2, driving the tire fragments and the additives in the kiln to turn and mix together through the rotary kiln, and enabling the tire fragments to generate pyrolytic carbon, pyrolytic oil and pyrolytic gas;
s4, collection of pyrolysis products: collecting pyrolysis carbon continuously discharged from a low outlet of the rotary kiln through a pyrolysis carbon collecting system, processing to obtain carbon black particles, collecting pyrolysis oil and pyrolysis gas continuously discharged from a high outlet of the rotary kiln through a cooling and separating system, and cooling to separate the pyrolysis oil and the pyrolysis gas from oil gas;
s5, oil gas detection and analysis: detect the combustible gas content in the pyrolysis gas through measurement control system, if wherein combustible gas content reaches recoverable economic condition, then save in the surge tank, carry out recycle, if can not reach the recovery condition, then introduce the pyrolysis gas into the combustion chamber through the draught fan and burn, filter the back, discharge in the atmosphere through detecting qualified.
As a still further scheme of the invention: the thermo-gravimetric analysis method in the step S2 is as follows:
s11, performing tire fragmentation on a tire at a certain heating rate, opening the tire for pyrolysis after heating to a certain temperature, recording initial weight loss temperature, increasing weight loss rate along with the rise of the temperature, decreasing weight loss rate after reaching the highest point, and recording the maximum weight loss rate at the heating rate and the characteristic temperature at the maximum weight loss rate;
s12, adjusting the temperature rise speed, repeating the process in the step S1, and recording the maximum weight loss rate and the characteristic temperature at the maximum weight loss rate at different temperature rise speeds;
s13, drawing a curve chart by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at the heating speed of each group with the characteristic temperature at the maximum weight loss rate; and comprehensively selecting the states with lower characteristic temperature, higher heating speed and larger maximum weight loss rate as subsequent pyrolysis process parameters.
As a still further scheme of the invention: the calculation formula of the pyrolysis reaction rate in the step S2 is as follows:
in the formula (1), A is a frequency factor, E is reaction activation energy, R is a gas constant, 8.314J/mol · k is taken, T is reaction temperature, n is reaction order, a is conversion rate of a reactant, wherein the calculation formula of the conversion rate a of the reactant is as follows:
in the above formula (2), w t Mass of reactant at time t, w c Mass of reactant in initial state of reaction, w z Is the mass of the reactants at the end of the reaction.
As a still further scheme of the invention: the catalyst in the step S3 is made of FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Composition of powder, feCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 The mass ratio of the powder is (2-3): (5-6): (3-4).
As a still further scheme of the invention: the heat transfer medium consists of potassium oxide and lithium oxide, and the mass ratio of the potassium oxide to the lithium oxide is 1: 1.
As a still further scheme of the invention: the mass ratio of the catalyst to the heat transfer medium to the tire fragments in the step S3 is 1: 100-120; and the turning speed of the rotary kiln in the step S3 is adjusted within the range of 0.5-4.5 rpm.
As a still further scheme of the invention: and after the vacuumizing treatment in the step S3, keeping the vacuum degree in the rotary kiln between 20 and 100 pa.
As a still further scheme of the invention: the method for oil-gas separation in the step S4 comprises the following steps: introducing pyrolysis oil and pyrolysis gas into a flash tower, carrying out quenching flash separation, and cooling oil gas from the top of the flash tower through a condenser again to realize separation of the pyrolysis oil and the pyrolysis gas; and then, detecting the moisture content in the pyrolysis oil and the pyrolysis gas, wherein after the moisture content is detected to be qualified, the pyrolysis oil flows into a collecting box, and the pyrolysis gas flows into a pressure stabilizing tank.
As a still further scheme of the invention: the above-mentionedThe method for preparing the carbon black particles by the pyrolytic carbon in the step S4 comprises the following steps: cooling pyrolytic carbon, feeding into magnetic separator, separating steel wire and other ferromagnetic substances, pulverizing into desired particle size, and feeding into H under the action of induced draft fan 2 SO 4 And cleaning the solution and NaOH solution, removing ash, and feeding the separated carbon black into a granulator for granulation treatment.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, waste tires are recycled through raw material treatment, pyrolysis parameter determination, ingredient pyrolysis, pyrolysis product collection and oil gas detection and analysis, and the obtained solid decomposition product pyrolytic carbon has the characteristics of large gap, light weight, less ash content and high heat value, and has an excellent adsorption function when being used as an adsorbent and a higher heating combustion effect when being used as a fuel; the obtained liquid product pyrolysis oil has high light fraction content, low heavy fraction content and high quality, and has higher economic value as chemical raw oil.
Detailed Description
In the embodiment of the invention, a treatment method for recycling waste tires comprises the following steps:
s1, raw material treatment: crushing the waste tires into pieces of 100mm multiplied by 100mm, magnetically selecting waste steel wires, and cleaning to obtain tire pieces for later use;
s2, determining pyrolysis parameters: because the tires of different brands and different purposes have different formulas and components and different technological parameters required by the pyrolysis process, before pyrolysis of the waste tires, a pyrolysis test is required to select the technological parameters suitable for the tires; taking the tire fragments obtained in the step S1, carrying out a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tire, carrying out thermogravimetric analysis, and selecting appropriate pyrolysis process parameters;
s3, ingredient pyrolysis: adding the tire fragments, the additives and the heat transfer medium obtained in the step S1 into a rotary kiln of a pyrolysis reaction system through a feeding system, introducing high-purity nitrogen into the rotary kiln to discharge air in the kiln, ensuring that pyrolysis is performed in an oxygen-free environment, reducing secondary reaction of tar steam to ensure yield of pyrolysis oil, vacuumizing, heating according to pyrolysis parameters determined in the step S2, driving the tire fragments and the additives in the kiln to turn and mix together through the rotary kiln, and enabling the tire fragments to generate pyrolytic carbon, pyrolysis oil and pyrolysis gas;
s4, collection of pyrolysis products: collecting pyrolysis carbon continuously discharged from a low outlet of the rotary kiln through a pyrolysis carbon collecting system, processing to obtain carbon black particles, collecting pyrolysis oil and pyrolysis gas continuously discharged from a high outlet of the rotary kiln through a cooling and separating system, and cooling to separate the pyrolysis oil and the pyrolysis gas from oil gas;
s5, oil gas detection and analysis: detect the combustible gas content in the pyrolysis gas through measurement control system, if wherein combustible gas content reaches recoverable economic conditions, then the storage is in the surge tank, carries out recycle, after the steady voltage, can regard as the fuel, if can not reach the recovery conditions, then introduces the pyrolysis gas into the combustion chamber through the draught fan and burns, filters the back, discharges in the atmosphere through detecting qualified.
Preferably, the thermo-gravimetric analysis method in the step S2 is as follows:
s11, performing tire fragmentation on a tire at a certain heating rate, opening the tire for pyrolysis after heating to a certain temperature, recording initial weight loss temperature, increasing weight loss rate along with the rise of the temperature, decreasing weight loss rate after reaching the highest point, and recording the maximum weight loss rate at the heating rate and the characteristic temperature at the maximum weight loss rate;
s12, adjusting the temperature rise speed, repeating the process in the step S1, and recording the maximum weight loss rate and the characteristic temperature at the maximum weight loss rate at different temperature rise speeds;
s13, drawing a curve chart by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at the heating speed of each group with the characteristic temperature at the maximum weight loss rate; and comprehensively selecting the states with lower characteristic temperature, higher heating speed and larger maximum weight loss rate as subsequent pyrolysis process parameters.
Preferably, the calculation formula of the pyrolysis reaction rate in the S2 step is as follows:
in the formula (1), A is a frequency factor, E is reaction activation energy, R is a gas constant, 8.314J/mol · k is taken, T is reaction temperature, n is reaction order, a is conversion rate of a reactant, wherein the calculation formula of the conversion rate a of the reactant is as follows:
in the above formula (2), w t Mass of reactant at time t, w c Mass of reactant in initial state of reaction, w z Is the mass of the reactants at the end of the reaction.
Preferably, the catalyst in the S3 step is made of FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Composition of powder, feCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 The mass ratio of the powder is (2-3) to (5-6) to (3-4), and the reaction activation energy of the tire fragments is improved through the catalyst, so that the micromolecule gas products are increased, and the macromolecule gas products are reduced.
Preferably, the heat transfer medium is composed of potassium oxide and lithium oxide, the mass ratio of the potassium oxide to the lithium oxide is 1: 1, and the pyrolysis speed can be increased by fully contacting the heat transfer medium with the tire fragments.
Preferably, the mass ratio of the catalyst to the heat transfer medium to the tire fragments in the step S3 is 1: 100-120; and (3) adjusting the overturning speed of the rotary kiln in the step (S3) within the range of 0.5-4.5 rpm, so as to adjust the retention time of the tire in the rotary kiln.
Preferably, after the vacuum pumping treatment in the step S3, the vacuum degree in the rotary kiln is kept between 20 and 100pa, so that pyrolysis gas and pyrolysis oil can be quickly separated from the rotary kiln, and the recovery treatment is facilitated.
Preferably, the oil-gas separation method in the step S4 comprises the following steps: introducing pyrolysis oil and pyrolysis gas into a flash tower, carrying out quenching flash separation, and cooling oil gas from the top of the flash tower through a condenser again to realize separation of the pyrolysis oil and the pyrolysis gas; then, detecting the moisture content in the pyrolysis oil and the pyrolysis gas, after the moisture content is detected to be qualified, enabling the pyrolysis oil to flow into a collection box, enabling the pyrolysis gas to flow into a pressure stabilizing tank, and if the moisture content exceeds a set value, performing dehydration treatment, wherein for example, the set value of the moisture in the pyrolysis oil is 4%, the set value of the moisture in the pyrolysis gas is 2%, and when the moisture in the pyrolysis oil exceeds 4%, performing dehydration treatment, and if the moisture in the pyrolysis oil does not exceed 4%, not performing the dehydration treatment; when the water content in the pyrolysis gas exceeds 2%, performing dehydration treatment, and when the water content in the pyrolysis gas does not exceed 2%, not performing the dehydration treatment.
Preferably, the method for preparing carbon black granules by using the pyrolytic carbon in the S4 step comprises the following steps: the pyrolytic carbon is cooled and then sent into a magnetic separator, steel wires and other ferromagnetic substances are separated, and the pyrolytic carbon is crushed into particles with the required particle size (such as 300 meshes) by a crusher and then is sequentially sent into H under the action of an induced draft fan 2 SO 4 Cleaning the solution and NaOH solution to remove ash, feeding the separated carbon black into a granulator for granulation treatment, and drying for storage and sale.
To better illustrate the technical effects of the present invention, the following examples are given:
the method is adopted as an embodiment, a waste tire recycling method (publication number: CN108249873A, publication date: 2018-07-06) disclosed by a patent network is adopted as a first comparative example, and a waste tire recycling method (publication number: CN107699269A, publication date: 2018-02-16) disclosed by the patent network is adopted as a second comparative example;
selecting a certain waste truck tire, removing steel wires in the tire, and detecting the following components in percentage by mass: elemental analysis: c:87.23%, H:6.93%, N:0.64%, S:3.37%, 0:1.83 percent; and (3) component analysis: moisture content: 1.53%, volatile: 59.48%, ash: 4.62%, fixed carbon: 34.37 percent; the pyrolysis test determines the pyrolysis process parameters of the invention as follows: the temperature rise speed is 4.5 ℃/min, the maximum weight loss rate is 0.42%/s, and the characteristic temperature at the maximum weight loss rate is 458 ℃.
1. The pyrolytic carbons in examples, comparative examples one and two were qualitatively analyzed to determine the pore diameter (unit: nm), particle density (unit: g/cm) of the pyrolytic carbon 3 ) Porosity (unit: 100%), ash (unit: 100%) and calorific value (unit: MJ/kg), see in particular table 1 below,
TABLE 1 comparative analysis of various parameters of pyrolytic carbon
From table 1 it can be analytically derived: the pore diameter and the porosity of the solid product pyrolytic carbon obtained by adopting the method of the embodiment are obviously larger than those of the solid product pyrolytic carbon obtained by the methods of the comparative example one and the comparative example two; the particle density of the solid product pyrolytic carbon obtained by adopting the method of the embodiment is obviously less than that of the pyrolytic carbon obtained by the methods of the comparative examples I and II; the ash content of the solid product pyrolytic carbon obtained by adopting the method of the embodiment is obviously less than that of the pyrolytic carbon obtained by the methods of the comparative examples one and two; the calorific value of the solid product pyrolytic carbon obtained by adopting the method of the embodiment is obviously higher than that of the solid product pyrolytic carbon obtained by the methods of the comparative examples I and II; further, it is found that: the solid decomposition product pyrolytic carbon obtained by the method has the characteristics of large gaps, light weight, less ash content and high heat value, has an excellent adsorption function when being used as an adsorbent, and has a higher heating combustion effect when being used as a fuel.
2. The pyrolysis oils of the examples, comparative examples I and comparative examples II were qualitatively analyzed to determine the mass ratio of the light fraction, middle fraction and heavy fraction in the pyrolysis oils, as shown in Table 1 below,
TABLE 2 comparative analysis of pyrolysis oil components
From table 2, it can be analyzed that: the light fraction in the liquid product pyrolysis oil obtained by the method of the example is significantly higher than the light fraction in the liquid product pyrolysis oil obtained by the methods of the comparative examples one and two; the heavy fraction in the liquid product pyrolysis oil obtained using the example process is significantly lower than the heavy fraction in the liquid product pyrolysis oil obtained using the comparative example one and comparative example two processes; further, it can be derived that: the liquid product pyrolysis oil obtained by the method has high light fraction content, low heavy fraction content and high quality, and has higher economic value as chemical raw oil.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (9)
1. A treatment method for recycling waste tires is characterized by comprising the following steps:
s1, raw material treatment: crushing the waste tires into pieces of 100mm multiplied by 100mm, magnetically selecting waste steel wires, and cleaning to obtain tire pieces for later use;
s2, determining pyrolysis parameters: taking the tire fragments obtained in the step S1, carrying out a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tire, carrying out thermogravimetric analysis, and selecting appropriate pyrolysis process parameters;
s3, ingredient pyrolysis: adding the tire fragments, the additives and the heat transfer medium obtained in the step S1 into a rotary kiln of a pyrolysis reaction system through a feeding system, introducing high-purity nitrogen into the rotary kiln, vacuumizing, heating according to pyrolysis parameters determined in the step S2, driving the tire fragments and the additives in the kiln to turn and mix together through the rotary kiln, and generating pyrolysis carbon, pyrolysis oil and pyrolysis gas from the tire fragments;
s4, collection of pyrolysis products: collecting pyrolysis carbon continuously discharged from a low outlet of the rotary kiln through a pyrolysis carbon collecting system, processing to obtain carbon black particles, collecting pyrolysis oil and pyrolysis gas continuously discharged from a high outlet of the rotary kiln through a cooling and separating system, and cooling to separate the pyrolysis oil and the pyrolysis gas from oil gas;
s5, oil gas detection and analysis: the content of combustible gas in the pyrolysis gas is detected through a measurement control system, if the content of the combustible gas reaches a recoverable economic condition, the combustible gas is stored in a pressure stabilizing tank and recycled, if the content of the combustible gas does not reach the recovery condition, the pyrolysis gas is introduced into a combustion chamber through an induced draft fan to be combusted, and after filtration, the pyrolysis gas is detected to be qualified and is discharged into the atmosphere.
2. The processing method for recycling waste tires according to claim 1, characterized in that, the thermo-gravimetric analysis method in the step S2 is as follows:
s11, performing tire fragmentation on a tire at a certain heating rate, opening the tire for pyrolysis after heating to a certain temperature, recording initial weight loss temperature, increasing weight loss rate along with the rise of the temperature, decreasing weight loss rate after reaching the highest point, and recording the maximum weight loss rate at the heating rate and the characteristic temperature at the maximum weight loss rate;
s12, adjusting the heating speed, repeating the process in the step S1, and recording the maximum weight loss rate at different heating speeds and the characteristic temperature at the maximum weight loss rate;
s13, drawing a curve chart by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at the heating speed of each group with the characteristic temperature at the maximum weight loss rate; and comprehensively selecting the states with lower characteristic temperature, higher heating speed and larger maximum weight loss rate as subsequent pyrolysis process parameters.
3. The processing method for recycling waste tires according to claim 1, characterized in that, the pyrolysis reaction rate in the step S2 is calculated by the following formula:
in the formula (1), A is a frequency factor, E is reaction activation energy, R is a gas constant, 8.314j/mol · k is taken, T is reaction temperature, n is reaction order, a is conversion rate of a reactant, wherein the calculation formula of the conversion rate a of the reactant is as follows:
in the above formula (2), w t Mass of reactant at time t, w c Mass of reactant in initial state of reaction, w z Is the mass of the reactants at the end of the reaction.
4. The method as claimed in claim 1, wherein the catalyst in the step S3 is FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Composition of powder, feCl 3 、NiCl 2 、Ti0 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 The mass ratio of the powder is (2-3) to (5-6) to (3-4).
5. The method as claimed in claim 1, wherein the heat transfer medium is composed of potassium oxide and lithium oxide, and the mass ratio of potassium oxide to lithium oxide is 1: 1.
6. The method for recycling and treating the waste tires according to claim 1, wherein the mass ratio of the catalyst, the heat transfer medium and the tire fragments in the step S3 is 1: 100-120; and the turning speed of the rotary kiln in the step S3 is adjusted within the range of 0.5-4.5 rpm.
7. The method as claimed in claim 1, wherein the vacuum degree in the rotary kiln is maintained between 20 pa and 100pa after the vacuum treatment in the step S3.
8. The method for processing the recycled waste tires according to claim 1, wherein the method for separating oil and gas in the step S4 comprises the following steps: introducing pyrolysis oil and pyrolysis gas into a flash tower, carrying out quenching flash separation, and cooling oil gas from the top of the flash tower through a condenser again to realize separation of the pyrolysis oil and the pyrolysis gas; and then, detecting the moisture content in the pyrolysis oil and the pyrolysis gas, wherein after the moisture content is detected to be qualified, the pyrolysis oil flows into a collecting box, and the pyrolysis gas flows into a pressure stabilizing tank.
9. The processing method for recycling waste tires according to claim 1, characterized in that the method for preparing carbon black particles by pyrolysis carbon in the step S4 is as follows: cooling pyrolytic carbon, feeding into magnetic separator, separating steel wire and other ferromagnetic substances, pulverizing into desired particle size, and feeding into H under the action of induced draft fan 2 SO 4 Cleaning the solution and Na0H solution, removing ash, and feeding the separated carbon black into a granulator for granulation treatment.
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| CN109609171A (en) * | 2018-12-24 | 2019-04-12 | 大连理工大学 | A kind of waste tire catalytic pyrolysis method |
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