CN115612518B - Treatment method for recycling waste tires - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000010920 waste tyre Substances 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 238000000197 pyrolysis Methods 0.000 claims abstract description 107
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000012634 fragment Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 238000012546 transfer Methods 0.000 claims abstract description 11
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 65
- 230000004580 weight loss Effects 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000006229 carbon black Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 229910000831 Steel Inorganic materials 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
- 229910010413 TiO 2 Inorganic materials 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
- 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
- 238000012360 testing method Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000006148 magnetic separator Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 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 6
- 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
- 239000013064 chemical raw material Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 14
- 239000012265 solid product Substances 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 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
- 238000004451 qualitative analysis Methods 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
- 230000008859 change Effects 0.000 description 1
- 238000011161 development 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of tire recycling, and discloses a treatment method for recycling waste tires, which comprises the following steps of S1, raw material treatment: crushing, magnetically separating and cleaning waste tires; s2, determining pyrolysis parameters: simulating pyrolysis reaction of waste tires, and selecting and determining pyrolysis process parameters; s3, batching pyrolysis: subjecting the tire fragments, additives and heat transfer medium to a pyrolysis reaction S4, and collecting pyrolysis products: respectively collecting pyrolytic carbon, pyrolytic oil and pyrolysis gas; s5, oil gas detection and analysis: and detecting the content of combustible gas in the pyrolysis gas. The pyrolysis carbon of the solid decomposition product obtained by the invention has the characteristics of large gap, light weight, less ash content and high heat value, has excellent adsorption function when being used as an adsorbent, and has 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 material 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, the waste tires are also grown at a speed of two digits each year, the waste tires are insoluble or indissolvable high polymer elastic materials, have higher elasticity and toughness, and cannot change within the range of-50-150 ℃, and the macromolecules of the waste tires are decomposed to the extent that the growth of plants in soil is not affected, so that the waste tires are difficult to degrade naturally by organisms in the nature, and various waste tire treatment methods are presented, however, a large amount of toxic and harmful gases such as hydrogen sulfide, benzene, polycyclic aromatic hydrocarbon and the like are generated in the treatment process, and if the waste tires are improperly treated, huge environmental pollution and ecological disaster are easily caused.
The Chinese patent discloses a recycling method of junked tires (grant publication No. CN 107699269A), which combines a supercritical ethanol method with catalytic oxidation to completely decompose organic matters in the junked tires and obtain more fuel; meanwhile, carbon black doped in the rubber junked tires can be completely separated, the carbon black content in solid matters is increased, but the obtained carbon black has poor adsorption performance and combustion performance, and the obtained fuel oil has poor quality.
Disclosure of Invention
The invention aims to provide a treatment method for recycling waste tires, so as to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the treatment method for recycling the junked tires comprises the following steps:
s1, raw material treatment: crushing the waste tires into fragments of 100mm multiplied by 100mm, magnetically separating out waste steel wires, and cleaning to obtain tire fragments for later use;
s2, determining pyrolysis parameters: taking the tire fragments obtained in the step S1, performing a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tires, performing thermogravimetric analysis, and selecting proper pyrolysis process parameters;
s3, batching pyrolysis: adding the tire fragments, the additive 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 the pyrolysis parameters determined in the step S2, and simultaneously driving the tire fragments and the additive in the kiln to be overturned and mixed together through the rotary kiln, wherein the tire fragments generate pyrolytic carbon, pyrolytic oil and pyrolysis gas;
s4, collecting pyrolysis products: continuously discharging pyrolytic carbon from a low outlet of the rotary kiln through a pyrolytic carbon collecting system, treating to obtain carbon black particles, continuously discharging pyrolytic oil and pyrolytic gas from a high outlet of the rotary kiln through a cooling separation system, and separating the pyrolytic oil and the pyrolytic gas oil and gas through cooling treatment;
s5, oil gas detection and analysis: and detecting the content of the combustible gas in the pyrolysis gas through a measurement control system, storing the combustible gas in a surge tank for recycling if the content of the combustible gas reaches a recoverable economic condition, introducing the pyrolysis gas into a combustion chamber through a draught fan for combustion if the content of the combustible gas does not reach the recoverable condition, filtering, and discharging the filtered pyrolysis gas into the atmosphere after detection.
As still further aspects of the invention: the thermogravimetric analysis method in the step S2 is as follows:
s11, heating the tire at a certain heating rate, after heating to a certain temperature, starting pyrolysis of the tire, recording initial weight loss temperature, increasing the weight loss rate along with the increase of the temperature, decreasing the 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 weightlessness speed at different temperature rise speeds and the characteristic temperature at the maximum weightlessness speed;
s13, drawing a graph by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at each group of heating speeds with the characteristic temperature at the maximum weight loss rate; comprehensively selecting the state with lower characteristic temperature, higher heating speed and higher maximum weight loss rate as the subsequent pyrolysis process parameters.
As still further aspects of the invention: the calculation formula of the pyrolysis reaction rate in the step S2 is as follows:
in the above-mentioned (1),as a factor of the frequency of the signal,in order to react the activation energy of the reaction,is a gas constant, 8.314J/mol.k is taken,in order to achieve the reaction temperature, the reaction mixture,for the number of reaction stages,is the conversion rate of the reactant, whereinThe calculation formula of (2) is as follows:
in the above-mentioned (2),is thatThe mass of the reactant at the moment,for the mass of the reactants at the initial state of the reaction,the mass of the reaction mass at the end of the reaction.
As still further aspects of the invention: the additive in the step S3 is formed by FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Powder composition, 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 still further aspects 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 still further aspects of the invention: the mass ratio of the additive, the heat transfer medium and the tire fragments in the step S3 is 1:1: (100-120); the overturning speed of the rotary kiln in the step S3 is regulated within the range of 0.5-4.5 rpm.
As still further aspects of the invention: and (3) after the vacuumizing treatment in the step S3, the vacuum degree in the rotary kiln is kept between 20 and 100 Pa.
As still further aspects of the invention: the oil-gas separation method in the step S4 comprises the following steps: introducing pyrolysis oil and pyrolysis gas into a flash evaporation tower for quenching, flash evaporation and separation, and cooling oil gas discharged from the top of the flash evaporation tower through a condenser again to realize separation of pyrolysis oil and pyrolysis gas; then, the moisture content in the pyrolysis oil and the pyrolysis gas is detected, and after the moisture detection is qualified, the pyrolysis oil flows into a collecting tank, and the pyrolysis gas flows into a pressure stabilizing tank.
As still further aspects of the invention: the method for preparing carbon black particles by pyrolyzing carbon in the step S4 comprises the following steps: cooling pyrolytic carbon, feeding the pyrolytic carbon into a magnetic separator, separating steel wires and other ferromagnetic substances, crushing the pyrolytic carbon into required particle size by a crusher, and sequentially feeding the pyrolytic carbon into H under the action of an induced draft fan 2 SO 4 Cleaning the solution and NaOH solution to remove ash, and delivering the separated carbon black into a granulator for granulation.
Compared with the prior art, the invention has the beneficial effects that:
the invention sequentially carries out raw material treatment, pyrolysis parameter determination, batching pyrolysis, pyrolysis product collection and oil gas detection analysis, and recycles the waste tires, and the obtained solid decomposition product pyrolysis carbon has the characteristics of large gap, light weight, less ash content and high heat value, has excellent adsorption function when being used as an adsorbent, and has 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 material oil.
Description of the embodiments
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 fragments of 100mm multiplied by 100mm, magnetically separating out waste steel wires, and cleaning to obtain tire fragments for later use;
s2, determining pyrolysis parameters: because the tires with different brands and different purposes have different formulas and components, the process parameters required by the pyrolysis process are different, and therefore, before the waste tires are pyrolyzed, a pyrolysis test is required to be carried out so as to select the process parameters which are suitable for the tires; taking the tire fragments obtained in the step S1, performing a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tires, performing thermogravimetric analysis, and selecting proper pyrolysis process parameters;
s3, batching 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 anaerobic environment so as to reduce secondary reactions of tar steam, ensuring the yield of pyrolysis oil, vacuumizing, heating according to the pyrolysis parameters determined in the step S2, and simultaneously driving the tire fragments and the additives in the kiln to be overturned and mixed through the rotary kiln, wherein the tire fragments generate pyrolytic carbon, pyrolytic oil and pyrolysis gas;
s4, collecting pyrolysis products: continuously discharging pyrolytic carbon from a low outlet of the rotary kiln through a pyrolytic carbon collecting system, treating to obtain carbon black particles, continuously discharging pyrolytic oil and pyrolytic gas from a high outlet of the rotary kiln through a cooling separation system, and separating the pyrolytic oil and the pyrolytic gas oil and gas through cooling treatment;
s5, oil gas detection and analysis: the content of combustible gas in the pyrolysis gas is detected by a measurement control system, if the content of the combustible gas reaches the recoverable economic condition, the combustible gas is stored in a pressure stabilizing tank for recycling, the fuel can be used as fuel after pressure stabilization, if the content of the combustible gas does not reach the recoverable condition, the pyrolysis gas is introduced into a combustion chamber by an induced draft fan for combustion, and after filtration, the pyrolysis gas is discharged into the atmosphere after being detected to be qualified.
Preferably, the thermogravimetric analysis method in step S2 is as follows:
s11, heating the tire at a certain heating rate, after heating to a certain temperature, starting pyrolysis of the tire, recording initial weight loss temperature, increasing the weight loss rate along with the increase of the temperature, decreasing the 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 weightlessness speed at different temperature rise speeds and the characteristic temperature at the maximum weightlessness speed;
s13, drawing a graph by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at each group of heating speeds with the characteristic temperature at the maximum weight loss rate; comprehensively selecting the state with lower characteristic temperature, higher heating speed and higher maximum weight loss rate as the subsequent pyrolysis process parameters.
Preferably, the calculation formula of the pyrolysis reaction rate in step S2 is as follows:
in the above-mentioned (1),as a factor of the frequency of the signal,in order to react the activation energy of the reaction,is a gas constant, 8.314J/mol.k is taken,in order to achieve the reaction temperature, the reaction mixture,for the number of reaction stages,is the conversion rate of the reactant, whereinThe calculation formula of (2) is as follows:
in the above-mentioned (2),is thatThe mass of the reactant at the moment,for the mass of the reactants at the initial state of the reaction,the mass of the reaction mass at the end of the reaction.
Preferably, the additive in step S3 is composed of FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Powder composition, 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), and the reaction activation energy of the tire fragments is improved by the additive, so that the micromolecular gas products are increased, and the macromolecule gas products are reduced.
Preferably, 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, and the pyrolysis speed can be improved by fully contacting the heat transfer medium with the tire fragments.
Preferably, the mass ratio of the additive, the heat transfer medium and the tire fragments in the step S3 is 1:1: (100-120); the overturning speed of the rotary kiln in the step S3 is regulated within the range of 0.5-4.5 rpm, so that the residence time of the tire in the rotary kiln is regulated.
Preferably, after the vacuumizing 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 recovery treatment is facilitated.
Preferably, the method for oil-gas separation in the step S4 is as follows: introducing pyrolysis oil and pyrolysis gas into a flash evaporation tower for quenching, flash evaporation and separation, and cooling oil gas discharged from the top of the flash evaporation tower through a condenser again to realize separation of pyrolysis oil and pyrolysis gas; then, detecting the moisture content in the pyrolysis oil and the pyrolysis gas, after the moisture is detected to be qualified, enabling the pyrolysis oil to flow into a collecting tank, enabling the pyrolysis gas to flow into a pressure stabilizing tank, if the moisture content exceeds a set value, performing dehydration treatment, for example, setting the moisture content in the pyrolysis oil to be 4%, setting the moisture content in the pyrolysis gas to be 2%, performing dehydration treatment when the moisture content in the pyrolysis oil exceeds 4%, and not exceeding 4%, otherwise, performing no treatment; when the moisture in the pyrolysis gas exceeds 2%, dehydration treatment is carried out, and when the moisture in the pyrolysis gas does not exceed 2%, the dehydration treatment is not carried out.
Preferably, the method for preparing carbon black particles by pyrolyzing carbon in the step S4 is as follows: cooling pyrolytic carbon, separating steel wire and other ferromagnetic matters, crushing into 300 mesh particle size, and feeding into H under the action of induced draft fan 2 SO 4 The solution and NaOH solution are cleaned to remove ash, and the separated carbon black is sent into a granulator for granulation treatment and then dried for storage and sale.
In order to better illustrate the technical effects of the present invention, the following examples are set forth:
by adopting the invention as an embodiment, a method for recycling waste tires disclosed by a patent net (publication number: CN108249873A, publication date: 2018-07-06) is adopted as a first comparison example, and a method for recycling waste tires disclosed by a patent net (publication number: CN107699269A, publication date: 2018-02-16) is adopted as a second comparison example;
selecting a certain waste truck tire, removing steel wires in the waste truck tire, and detecting the mass fractions of the components as follows: elemental analysis: c:87.23%, H:6.93%, N:0.64%, S:3.37%, O:1.83%; component analysis, moisture: 1.53%, volatile: 59.48%, ash: 4.62%, fixed carbon: 34.37%; the pyrolysis process parameters of the invention are determined by pyrolysis tests as follows: the temperature rising 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 carbon in examples, comparative examples one and two was subjected to qualitative analysis to determine pore diameter (unit: nm) and particle density (unit: g/cm) 3 ) Porosity (unit: 100%), ash (unit: 100%) and heat value (unit: MJ/kg), in particular table 1 below,
table 1 comparative analysis of various parameters of pyrolytic carbon
| Name item | Pore diameter | Particle density | Porosity of the porous body | Ash content | Heating value |
| Examples | 0.45 | 0.34 | 0.46% | 11.6% | 32.4 |
| Comparative example one | 0.37 | 0.39 | 0.41% | 12.9% | 24.7 |
| Comparative example two | 0.34 | 0.41 | 0.36% | 13.6% | 24.5 |
From table 1, it can be analyzed that: 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 first comparison example and the second comparison example; the particle density of the solid product pyrolytic carbon obtained by adopting the method of the embodiment is obviously smaller than that of the solid product pyrolytic carbon obtained by the methods of the comparative example I and the comparative example II; the ash content of the solid product pyrolytic carbon obtained by adopting the method of the embodiment is obviously smaller than that of the solid product pyrolytic carbon obtained by adopting the methods of the comparative example I and the comparative example II; the heat 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 adopting the methods of the comparative example I and the comparative example II; and then, the following steps are obtained: the pyrolysis carbon of the solid decomposition product obtained by the invention has the characteristics of large gap, light weight, less ash content and high heat value, and has excellent adsorption function when being used as an adsorbent and higher heating and burning effects when being used as fuel.
2. The pyrolysis oil in the examples, the comparative example one and the comparative example two were subjected to qualitative analysis, and the mass ratios of the light fraction, the middle fraction and the heavy fraction in the pyrolysis oil were determined, specifically as shown in table 2 below,
table 2 comparative analysis of pyrolysis oil components
| Name item | Light fraction | Middle distillate | Heavy fraction |
| Examples | 42.3% | 44.6% | 13.1% |
| ComparisonExample 1 | 40.4% | 41.8% | 17.8% |
| Comparative example two | 38.7% | 45.9% | 15.4% |
From table 2, it can be analyzed that: the light fraction in the liquid product pyrolysis oil obtained by adopting the method of the example is obviously higher than that in the liquid product pyrolysis oil obtained by adopting the methods of the first comparison example and the second comparison example; the heavy fraction in the liquid product pyrolysis oil obtained by the method of the example is significantly lower than the heavy fraction in the liquid product pyrolysis oil obtained by the methods of the comparative example one and the comparative example two; and then can be derived: the liquid product pyrolysis oil obtained by the invention has high light fraction content, low heavy fraction content and high quality, and has higher economic value as chemical raw material oil.
The foregoing description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The treatment method for recycling the junked tires is characterized by comprising the following steps of:
s1, raw material treatment: crushing the waste tires into fragments of 100mm multiplied by 100mm, magnetically separating out waste steel wires, and cleaning to obtain tire fragments for later use;
s2, determining pyrolysis parameters: taking the tire fragments obtained in the step S1, performing a pyrolysis test in a laboratory, simulating a pyrolysis reaction of the waste tires, performing thermogravimetric analysis, and selecting proper pyrolysis process parameters; the thermogravimetric analysis method comprises the following steps:
s11, heating the tire at a certain heating rate, after heating to a certain temperature, starting pyrolysis of the tire, recording initial weight loss temperature, increasing the weight loss rate along with the increase of the temperature, decreasing the 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 weightlessness speed at different temperature rise speeds and the characteristic temperature at the maximum weightlessness speed;
s13, drawing a graph by taking the heating temperature as an abscissa and the weight loss rate as an ordinate, and comparing the maximum weight loss rate at each group of heating speeds with the characteristic temperature at the maximum weight loss rate; comprehensively selecting the state with lower characteristic temperature, higher heating speed and higher maximum weight loss rate as the subsequent pyrolysis process parameter; wherein the pyrolysis reaction rate is calculated as follows:
in the above-mentioned (1),as a factor of the frequency of the signal,in order to react the activation energy of the reaction,is a gas constant, 8.314J/mol.k is taken,in order to achieve the reaction temperature, the reaction mixture,for the number of reaction stages,is the conversion rate of the reactant, whereinThe calculation formula of (2) is as follows:
in the above-mentioned (2),is thatThe mass of the reactant at the moment,for the mass of the reactants at the initial state of the reaction,the mass of the reactants at the end of the reaction;
s3, batching pyrolysis: adding the tire fragments, the additive 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 the pyrolysis parameters determined in the step S2, and simultaneously driving the tire fragments and the additive in the kiln to be overturned and mixed together through the rotary kiln, wherein the tire fragments generate pyrolytic carbon, pyrolytic oil and pyrolysis gas; wherein the additive is FeCl 3 、NiCl 2 、TiO 2 、Cr 2 O 3 NaOH powder and Na 2 CO 3 Powder composition, 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); 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;
s4, collecting pyrolysis products: continuously discharging pyrolytic carbon from a low outlet of the rotary kiln through a pyrolytic carbon collecting system, treating to obtain carbon black particles, continuously discharging pyrolytic oil and pyrolytic gas from a high outlet of the rotary kiln through a cooling separation system, and separating the pyrolytic oil and the pyrolytic gas oil and gas through cooling treatment;
s5, oil gas detection and analysis: and detecting the content of the combustible gas in the pyrolysis gas through a measurement control system, storing the combustible gas in a surge tank for recycling if the content of the combustible gas reaches a recoverable economic condition, introducing the pyrolysis gas into a combustion chamber through a draught fan for combustion if the content of the combustible gas does not reach the recoverable condition, filtering, and discharging the filtered pyrolysis gas into the atmosphere after detection.
2. The treatment method for recycling waste tires according to claim 1, wherein the mass ratio of the additive, the heat transfer medium and the tire fragments in the step S3 is 1:1: (100-120); the overturning speed of the rotary kiln in the step S3 is regulated within the range of 0.5-4.5 rpm.
3. The method for recycling waste tires according to 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.
4. The method for recycling waste tires according to claim 1, wherein the method for separating oil from gas in the step S4 is as follows: introducing pyrolysis oil and pyrolysis gas into a flash evaporation tower for quenching, flash evaporation and separation, and cooling oil gas discharged from the top of the flash evaporation tower through a condenser again to realize separation of pyrolysis oil and pyrolysis gas; then, the moisture content in the pyrolysis oil and the pyrolysis gas is detected, and after the moisture detection is qualified, the pyrolysis oil flows into a collecting tank, and the pyrolysis gas flows into a pressure stabilizing tank.
5. A method for recycling scrap tires according to claim 1The recycling treatment method is characterized in that the method for preparing carbon black particles by pyrolyzing carbon in the step S4 comprises the following steps: cooling pyrolytic carbon, feeding the pyrolytic carbon into a magnetic separator, separating steel wires and other ferromagnetic substances, crushing the pyrolytic carbon into required particle size by a crusher, and sequentially feeding the pyrolytic carbon into H under the action of an induced draft fan 2 SO 4 Cleaning the solution and NaOH solution to remove ash, and delivering the separated carbon black into a granulator for granulation.
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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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Effective date of registration: 20231208 Address after: Room 1621, 16th Floor, Entrepreneurship and Innovation Building, High tech Zone, Huaihua City, Hunan Province, 418000 Applicant after: Huaihua Baohui Scrap Automobile Recycling and Disassembly Co.,Ltd. Address before: Building A3, New Era Gongrong Industrial Park, No. 2, Shilong Community, Shiyan Street, Bao'an District, Shenzhen, Guangdong 518000 Applicant before: Guan Yezhen |
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