CN107488455A - A kind of method that thermal decomposing waste tire residue is upgraded to tire carbon black - Google Patents
A kind of method that thermal decomposing waste tire residue is upgraded to tire carbon black Download PDFInfo
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- CN107488455A CN107488455A CN201710707989.3A CN201710707989A CN107488455A CN 107488455 A CN107488455 A CN 107488455A CN 201710707989 A CN201710707989 A CN 201710707989A CN 107488455 A CN107488455 A CN 107488455A
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- Prior art keywords
- tire
- carbon black
- residue
- decomposing waste
- acid
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Classifications
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
It is a kind of to upgrade the method that thermal decomposing waste tire residue is tire carbon black, belong to chemical industry and energy technology field.It is characterized in that solid residue that 2 5hs obtain is handled damaged tire under the conditions of 550 800 DEG C pyrolysis temperature, under ultrasonic assistant, impregnated successively with watery hydrochloric acid/dilute sulfuric acid+polyacrylic acid, 4 8h further are impregnated with hydrofluoric acid under ultrasonic assistant to obtained solid after centrifugation, centrifuge again, and scrubbed and drying solid, obtain tire carbon black.Carbon black produced by the present invention, its property is suitable with carbon black N300 mass with commercial tire, and its dispersiveness is better than commercial tire carbon black N300, have the characteristics that raw material sources are extensive, price is low, process route is simple, easily operated and environmentally friendly, be a kind of science selection that thermal decomposing waste tire residue recycles.
Description
Technical field
The invention belongs to derived energy chemical field, specially a kind of side that thermal decomposing waste tire residue is upgraded to tire carbon black
Method, by technical transform of the present invention can be tire carbon black by solid residue that thermal decomposing waste tire obtains, significant increase
Its added value, the cost of junked tire disposal is reduced, is that environmental administration preferentially supports and encourages development to disposal of solid discarded object
An intermediate item.
Background technology
Shown according to the numeral that Traffic Administration Bureau of the Ministry of Public Security counts, by 2016 end of the year China's vehicle guaranteeding organic quantities up to 2.9 hundred million
, and the speed to be often close on 7% or so is continuing to increase.The operation of a large amount of motor vehicles, certainly will produce substantial amounts of damaged tire,
Thus will be prominent on influenceing also day caused by environment.Even if new-energy automobile is transformed into the future, but the influence to tire quantity is
The same.
Under natural conditions, the speed of damaged tire degraded is very slow, at least decades, at most upper century-old even more long.Mesh
Before, damaged tire is main or by pyrolysis way treatment and use, because by pyrolysis, gas, liquid, solid three-phase product can be sharp again
With.As gas and solid residue can be directly as fuel, liquid can upgrade to power fuel or the important chemicals of extraction
Such as limonene, benzene material.Other manner is such as burned, builds the road, filled, and is difficult to large-scale promotion because of various reasons, and dispose
Ratio it is very small.
The solid residue that waste tyre pyrolytic obtains, in addition to as fuel, activated carbon, but adsorption effect can also be converted into
It is unsatisfactory.There are some researches show wear-resistant to improve, it is necessary to add nearly 1/3rd carbon black during tire is manufactured
Performance.The reactivity of carbon black is actually very low.Therefore, secondary response occurs for this moieties during converting
Possibility is also very low.If unwanted composition in thermal decomposing waste tire residue can be removed, then, solid residue it is main into
Divide the carbon black that theoretically analysis is exactly manufacturing process addition, after a series of processing, it is possible to meet tire carbon black
Requirement, realize the cycling and reutilization of resource, greatly reduce disposal damaged tire cost, lift its added value.
The content of the invention
The technical problem to be solved in the present invention is on the one hand how to realize thermal decomposing waste tire residue through processing, its solid property
It is the same with carbon black property with commercial tire, so as to be used as tire additive, recycle；On the other hand, process route will letter
It is single, it is easy to popularization and large-scale production.Therefore, the present invention uses the approach for being totally different from open source literature report at it
Reason and upgrading.
Regarding to the issue above and purpose, the present invention select gentle treatment conditions to thermal decomposing waste tire solid residue at it
Reason, keep the property of carbon in pyrolysis residue not to be corrupted or altered, keep the original property of addition carbon, and can remove carbon black it
Outer other materials.The technical solution used in the present invention is：First it is 10-60 DEG C/min, is connected with nitrogen or two in heating rate
Damaged tire is heated to 600-800 DEG C of temperature range under conditions of carbon oxide gas and keeps 2-5h, nitrogen or carbon dioxide gas
The flow velocity of body is 100-200 ml/min, is cooled down afterwards, takes the solid residue after cooling, and it is 2-6mol/L to add sulfuric acid or concentration
Hydrochloric acid or the mixture of the two, polyacrylic acid, under ul-trasonic irradiation, residue 6-8h is impregnated under the conditions of 40-80 DEG C of temperature,
Then with 1500-4000 revs/min of centrifugation 15-30 minute, solution is discarded, obtained solid is continued in ul-trasonic irradiation
Under, temperature is to add the hydrofluoric acid that volumetric concentration is 20-40% in the environment of room temperature, impregnates 4-9h, centrifugation, discards supernatant liquid,
Solid is washed to neutrality, through drying, obtains tire carbon black, quality reaches N330 tires carbon black rank.Useless wheel of the present invention
Tire, it can be various automobile-used junked tires, not limited by species.
The route feature that the present invention uses is：Pyrolysis is handled under sour and ultrasonic combined effect with gentle reaction temperature
Damaged tire residue, unwanted material in residue was both eliminated, and do not destroyed the surface nature of wanted material, so as to pass through this
The technology path that invention provides is made tire carbon black, its property for example element composition, surface topography, surface functional group, surface area,
Internal permeability, iodine and oil factor etc. are inhaled, it is completely the same with carbon black N330 with commercial tire, realize the recycling of waste, product tool
There is wide application market.
Embodiment
Embodiment 1
Take 500g damaged tires to be placed in tube furnace, nitrogen protection gas is passed through in stove after sealing 2 minutes, control the flow to be
100ml/min, heating rate are 50 DEG C/min, are heated to 600 DEG C and keep this temperature 2h；The residual 100g of solid after cooling is taken,
It is placed in modeling container, addition concentration is 2mol/L watery hydrochloric acid 200ml, 30ml polyacrylic acid (MW ~ 3000), Ran Hou
Temperature is 80 DEG C, ultrasonic wave handles 6h in the environment of existing, and afterwards, said mixture is centrifuged with 1500 revs/min of speed
0.5h, solution being discarded, obtained solid is again transferred to plastic containers, adds the hydrofluoric acid 200ml that volumetric concentration is 20%,
In the presence of ultrasonic wave, after handling 9h, then centrifuge, speed is still 1500 revs/min, discards supernatant liquid, distillation water washing is into
Property, dry, obtain product, its performance is the same as N330 tires carbon black rank.
Embodiment 2
Take 500g damaged tires to be placed in tube furnace, nitrogen protection gas is passed through in stove after sealing 2 minutes, control the flow to be
150ml/min, heating rate are 10 DEG C/min, are heated to 800 DEG C and keep this temperature 2h；The residual 100g of solid after cooling is taken,
It is placed in modeling container, addition concentration is 2mol/L dilute sulfuric acids 300ml, 60ml polyacrylic acid (MW ~ 3000), Ran Hou
Temperature is 40 DEG C, ultrasonic wave handles 8h in the environment of existing, afterwards, with 1500 revs/min of speed to said mixture centrifugation 15
Minute, liquid is discarded, obtained solid is again transferred to plastic containers, adds the hydrofluoric acid 300ml that volumetric concentration is 40%,
In the presence of ultrasonic wave, after handling 5h, then centrifuge, speed is still 1500 revs/min, discards supernatant liquid, distillation water washing is into
Property, dry, obtain product, its performance is the same as N330 tires carbon black rank.
Embodiment 3
Take 500g damaged tires to be placed in tube furnace, nitrogen protection gas is passed through in stove after sealing 2 minutes, control the flow to be
200ml/min, heating rate are 60 DEG C/min, are heated to 700 DEG C and keep this temperature 2h；The residual 100g of solid after cooling is taken,
It is placed in modeling container, addition concentration is 3mol/L watery hydrochloric acid 400ml, 50ml polyacrylic acid (MW ~ 3000), Ran Hou
Temperature is 60 DEG C, ultrasonic wave handles 7h in the environment of existing, and afterwards, said mixture is centrifuged with 1500 revs/min of speed
0.5h, liquid being discarded, obtained solid is again transferred to plastic containers, adds the hydrofluoric acid 400ml that volumetric concentration is 30%,
In the presence of ultrasonic wave, after handling 4h, then centrifuge, speed is still 1500 revs/min, discards supernatant liquid, distillation water washing is into
Property, dry, obtain product, its performance is the same as N330 tires carbon black rank.
Embodiment 4
Take 500g damaged tires to be placed in tube furnace, nitrogen protection gas is passed through in stove after sealing 2 minutes, control the flow to be
150ml/min, heating rate are 30 DEG C/min, are heated to 650 DEG C and keep this temperature 2h；The residual 100g of solid after cooling is taken,
It is placed in modeling container, addition concentration is 2mol/L dilute sulfuric acids 300ml, 40ml polyacrylic acid (MW ~ 3000), Ran Hou
Temperature is 60 DEG C, ultrasonic wave handles 6h in the environment of existing, afterwards, with 1500 revs/min of speed to said mixture centrifugation 20
Minute, liquid is discarded, obtained solid is again transferred to plastic containers, adds the hydrofluoric acid 250ml that volumetric concentration is 30%,
In the presence of ultrasonic wave, after handling 4h, then centrifuge 20 minutes, speed is still 1500 revs/min, discards supernatant liquid, distillation washing
Wash to neutrality, dry, obtain product, its performance is the same as N330 tires carbon black rank.
Embodiment 5
Take 500g damaged tires to be placed in tube furnace, carbon-dioxide protecting gas is passed through in stove after sealing 2 minutes, control flow
For 150ml/ min, heating rate is 20 DEG C/min, is heated to 750 DEG C and keeps this temperature 2h.Take the solid after cooling residual
100g, it is placed in modeling container, adds the sulfuric acid 100ml that concentration is 5mol/L watery hydrochloric acid 100ml, 1mol/L, 20ml gathers
Acrylic acid (MW ~ 3000), 6h then is handled in the environment of temperature is 60 DEG C, ultrasonic wave is present, afterwards, with 1500 revs/min
Clock rate degree centrifuges 25 minutes to said mixture, discards liquid, and obtained solid is again transferred to plastic containers, and it is dense to add volume
The hydrofluoric acid 200ml for 20% is spent, in the presence of ultrasonic wave, after handling 4h, then is centrifuged 25 minutes, speed is still 1500 revs/min
Clock, supernatant liquid is discarded, distillation water washing to neutrality, dries, obtains product, its performance is the same as N330 tires carbon black rank.
Claims (2)
1. a kind of upgrade the method that thermal decomposing waste tire residue is tire carbon black, it is characterised in that comprises the following steps：First rising
Warm speed is 10-60 DEG C/min, is connected with conditions of nitrogen or carbon dioxide damaged tire being heated to 600-800 DEG C of temperature
Scope simultaneously keeps 2-5h, and the flow velocity of nitrogen or carbon dioxide is 100-200 ml/min, is cooled down afterwards, takes consolidating after cooling
Body residue, it is 2-6mol/L hydrochloric acid or the mixture of the two, polyacrylic acid to add sulfuric acid or concentration, under ul-trasonic irradiation,
Residue 6-8h is impregnated under the conditions of 40-80 DEG C of temperature, then with 1500-4000 revs/min of centrifugation 15-30 minute, is discarded molten
Liquid, obtained solid is continued under ul-trasonic irradiation, temperature is to add the hydrogen that volumetric concentration is 20-40% in the environment of room temperature
Fluoric acid, 4-9h is impregnated, centrifugation discards supernatant liquid, and washing solid through drying, obtains tire carbon black, quality reaches N33 to neutrality
0 tire carbon black rank.
2. a kind of upgrading thermal decomposing waste tire residue according to claim 1 is the method for tire carbon black, it is characterised in that
Damaged tire is not limited by species, can be various automobile-used junked tires.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707989.3A CN107488455A (en) | 2017-08-17 | 2017-08-17 | A kind of method that thermal decomposing waste tire residue is upgraded to tire carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710707989.3A CN107488455A (en) | 2017-08-17 | 2017-08-17 | A kind of method that thermal decomposing waste tire residue is upgraded to tire carbon black |
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| Publication Number | Publication Date |
|---|---|
| CN107488455A true CN107488455A (en) | 2017-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710707989.3A Pending CN107488455A (en) | 2017-08-17 | 2017-08-17 | A kind of method that thermal decomposing waste tire residue is upgraded to tire carbon black |
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| CN (1) | CN107488455A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938450A (en) * | 2019-12-16 | 2020-03-31 | 华中科技大学 | Method for preparing pyrolysis oil and limonene by utilizing waste tires through pressurization and pyrolysis |
| CN114436236A (en) * | 2020-11-06 | 2022-05-06 | 中国化学工业桂林工程有限公司 | Method for purifying cracking carbon black and by-producing fluosilicic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696210A (en) * | 2005-05-24 | 2005-11-16 | 太原理工大学 | Method for preparing acetylene black from waste plastics, tire |
| CN101164876A (en) * | 2007-09-30 | 2008-04-23 | 南开大学 | Method for preparing carbon black and active carbon from waste tyre pyrolytic carbon |
| CN101254922A (en) * | 2008-04-01 | 2008-09-03 | 大连理工大学 | Method for preparing modified white carbon black by using oil shale oil-making residual |
| CN103540172A (en) * | 2013-10-31 | 2014-01-29 | 王兢 | Method and system for preparing regenerative carbon black by deashing and modifying pyrolytic carbon of waste rubber and plastic products |
-
2017
- 2017-08-17 CN CN201710707989.3A patent/CN107488455A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696210A (en) * | 2005-05-24 | 2005-11-16 | 太原理工大学 | Method for preparing acetylene black from waste plastics, tire |
| CN101164876A (en) * | 2007-09-30 | 2008-04-23 | 南开大学 | Method for preparing carbon black and active carbon from waste tyre pyrolytic carbon |
| CN101254922A (en) * | 2008-04-01 | 2008-09-03 | 大连理工大学 | Method for preparing modified white carbon black by using oil shale oil-making residual |
| CN103540172A (en) * | 2013-10-31 | 2014-01-29 | 王兢 | Method and system for preparing regenerative carbon black by deashing and modifying pyrolytic carbon of waste rubber and plastic products |
Non-Patent Citations (1)
| Title |
|---|
| 刘汉湖等: "《固体废物处理与处置》", 31 August 2009, 中国矿业大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938450A (en) * | 2019-12-16 | 2020-03-31 | 华中科技大学 | Method for preparing pyrolysis oil and limonene by utilizing waste tires through pressurization and pyrolysis |
| CN110938450B (en) * | 2019-12-16 | 2020-10-09 | 华中科技大学 | Method for preparing pyrolysis oil and limonene by utilizing waste tires through pressurization and pyrolysis |
| CN114436236A (en) * | 2020-11-06 | 2022-05-06 | 中国化学工业桂林工程有限公司 | Method for purifying cracking carbon black and by-producing fluosilicic acid |
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Application publication date: 20171219 |
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| RJ01 | Rejection of invention patent application after publication |