CN104830076B - A kind of preparation method of scrap rubber cracking conversion modified pitch - Google Patents
A kind of preparation method of scrap rubber cracking conversion modified pitch Download PDFInfo
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- CN104830076B CN104830076B CN201510179870.4A CN201510179870A CN104830076B CN 104830076 B CN104830076 B CN 104830076B CN 201510179870 A CN201510179870 A CN 201510179870A CN 104830076 B CN104830076 B CN 104830076B
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The present invention relates to a kind of preparation method of scrap rubber cracking conversion modified pitch.Mainly comprise the following steps：Waste Crumb rubber is passed through into normal pressure twice-coiled devices, scrap rubber cracking is converted into thick class asphalt material after 260 360 °C of 30min of high temperature process 10, it is added to after stirring in heavy traffic paving asphalt and obtains scrap rubber cracking conversion asphalt mother liquid, is subsequently adding weight and carries out shearing than the SBS for 1 6% and disperse to prepare high performance modified pitch.The device that the present invention prepares cracking conversion rubber has low cost, transformation efficiency high, environmentally friendly, safe the features such as, be modified the modified pitch for preparing with SBS again after being mixed with heavy traffic paving asphalt with cracking conversion rubber, with steady heat storage, high temperature performance is excellent, the characteristics of UV resistant performance is excellent, makes scrap rubber have good economic benefit and environmental benefit.
Description
Technical field
The present invention relates to modifying road asphalt field, more particularly, to a kind of preparation of scrap rubber cracking conversion modified pitch
Method.
Background technology
Pitch has the advantages that waterproof, insulation, corrosion-resistant, and have good bonding with stone ore material as a kind of cementitious matter
Effect, is used as pavement construction material extensively for a long time.In recent years, with the increase of the volume of traffic and traffic load, people couple
Urban road laying asphalt material proposes harsher requirement, but plain asphalt high temperature is also easy to produce rut, and low temperature is easy to crack, holds
Easy aging, short life, can not fully meet and be actually needed.Generally polymer addition is distributed in pitch, polymerization is prepared
Thing modified pitch, can be effectively improved the high temperature performance of pitch.
In polymer used by modified pitch, that the most frequently used is styrene-butadiene-styrene (SBS).So
And, SBS prices are higher, and due to molecular backbone structure unsaturation be susceptible to it is aging, it is necessary to select the material that cost performance is higher
Material.Additionally, China's junked tire amount increases year by year, substantial amounts of solid waste is produced every year.If waste-tyre rubber-powder used
In modified pitch, the process problem of solid waste can be solved；Part SBS can be replaced and imitated with economic benefit and environmental protection
Benefit.But current shoddy is cross-linked structure, it is difficult to be distributed in pitch, the heat of the SBS/ shoddy composite modified asphalts of preparation
Storage stability is not enough, and isolation lamination is also easy to produce in storage and transportation process, and SBS occurs floating rubber powder and sinks, shadow
Ring the performance of modified pitch.
The stabilization of SBS/ rubber powder composite modified asphalts is always problem in the industry.Chinese patent CN103146206A passes through will
SBS improves stability by the method for Screw Extrusion with rubber powder, but the method processing cost is higher, and practice have shown that, still have
A large amount of rubber powder granules can be precipitated in there is pitch.
To improve dispersiveness of the rubber powder in pitch, CN102601975A is a kind of continuously to prepare liquid using screw extruder
The method of reclaimed rubber, the method that the invention continuously prepares liquid reclaimed rubber using screw extruder, the method is squeezed using screw rod
Go out machine, the method linked using physical chemistry, by pretreated shoddy, in extrusion built-in temperature, pressure, shearing, desulfurization
Under the comprehensive function of agent, the three-dimensional crosslinked network of scrap rubber is crushed, obtain the reclaimed rubber of liquid, the liquid regeneration glue for obtaining can be with
Pitch is simultaneously used or replacing asphalt is used to pave the way, with pure glue and with making water-proof and anti-corrosive material etc..Though the method technological process is simple, tool
Have desulphurization, disaggregation degree high, energy-saving and environmental protection, a continuous advantage, but exist yield poorly, high processing costs, screw rod has pressure, holds
The shortcoming for easily making screw rod wear and tear.By in liquid regeneration glue addition pitch, also have the shortcomings that high-temperature behavior is not enough.
The desulfurization of constant-pressure and high-temperature double helix equipment be to overcome conventional high-tension dynamic devulcanizer high pressure dangerous, waste gas discharge without
The problems such as sequence, difficult control and the environmental protection desulphurization plant without pressure, non-exhaust emission that grows up are big etc. with automatic control and yield
Feature.But the device is generally for as described in CN200810238546.5, being prepared in the 200-280 DEG C of range of work
Reclaimed rubber (sol content 30% or so), is used to manufacture rubber, if reason is at higher temperature for use as part instead of rubber
The lower processing rubber of degree, the rubber meeting colloidal sol amount of extrusion is (being more than 60%) higher, causes its mechanical strength relatively low, is directly made for rubber
Low intensity during product, therefore the device one kind is used in 200-280 DEG C of range of work processing rubber.Use it for cracking system at higher temperature
Do asphaltogenic again for deep regenerative rubber, have not been reported.
CN103194072A, CN103980723A and CN102181163A etc. are being dripped using SBS and activated rubber powder or rubber powder
The method of the composite modified asphalt sheared for a long time in green grass or young crops, and then prepare the composite modified asphalt of steady heat storage.Single technique
Process is more long, relatively costly, and pollution is big, and is limited by mixing temperature, and the addition of rubber powder is also restricted.
The content of the invention
The present invention is in order to overcome above-mentioned deficiency of the prior art, there is provided a kind of technical process it is succinct it is easy, can add
The preparation method of the ageing-resistant scrap rubber cracking conversion modified pitch of a large amount of scrap rubbers.
Inventor reaches above-mentioned purpose, with reference to problem to be solved by this invention, by studying for a long period of time, finds scrap rubber
The violent fracture of strand is being susceptible to higher than 260 DEG C, particularly 300 DEG C or so, liquid rubber is now being readily obtained, should
Rubber is different from a large amount of reclaimed rubbers for using of in the market, and its sol content is (being more than 60%) high, but just because of this point so that
Its mechanical strength is relatively low, for rubber low intensity, so not being taken seriously.Because its viscosity is low and with caking property, therefore
The characteristics of with class asphalt material.Again because discharge with endless screw function is equipped in the desulfurization of constant-pressure and high-temperature double helix, it is adapted to prepare class pitch
Material, such asphalt material is not only easily distributed in pitch, and addition content in pitch is big, pitch is converted, so as to solve
Certainly rubber powder is difficult in pitch disperses and settlement issues.Therefore, inventor is determined constant-pressure and high-temperature double helix desulfurization equipment and scrap rubber
Pintsch process performance be combined together, while coordinating the technology effect that other rational methods reach to reach the present invention to want
Really.
The technical solution used in the present invention is：
A kind of preparation method of scrap rubber cracking conversion modified pitch, it is characterised in that comprise the following steps：
(1) scrap rubber cracking conversion is obtained into cracking conversion rubber；
(2) weight is converted into rubber in the feelings that temperature is 150~180 DEG C than the heavy traffic paving asphalt for 60/40~95/5/cracking
Under condition, it is well mixed, obtains scrap rubber conversion asphalt mother liquid；
(3) by mass ratio is above-mentioned scrap rubber conversion asphalt mother liquid, 1~6% SBS is added to 170~190 DEG C and turns
Change in asphalt mother liquid, using high shearing mixing emulsor or colloid mill, temperature is maintained at 170~190 DEG C, and shearing disperses, then
Development is stirred on high speed dispersor, and during the stirring is developed, puts into co-crosslinker, finally prepared high performance useless
Rubber cracking converts modified pitch.
It is by the detailed process that scrap rubber cracking conversion obtains cracking conversion rubber in the step (1)：By waste Crumb rubber
By normal pressure double helix cracker, 10-30min is processed at a temperature of 260-360 DEG C, be converted into scrap rubber cracking thick
Class asphalt material, i.e. cracking conversion rubber；
Preferably, in step (3), the co-crosslinker quality put into during development is stirred is converted for the scrap rubber
The 0.1~1% of asphalt mother liquid gross mass.
Preferably, in step (3), during development is stirred, controlling speed of agitator for 300~1000r/min, stirring
60~150min of reaction.
Preferably, the rubber powder that the scrap rubber in the step (1) grinds after being crushed for junked tire, mesh number is 15-60
Mesh.
Preferably, the step (2) be first will cracking conversion rubber add heating asphalt tank in, with pitch 150~180
Mixing is reacted at DEG C, scrap rubber conversion asphalt mother liquid is prepared.
Preferably, the heavy traffic paving asphalt described in the step (2) meets Ministry of Communications's JTG F40-2004 requirements.
Preferably, the SBS is line style styrene-butadiene-styrene, wherein styrene and butadiene
Mass ratio is 3/7, and molecular weight is 60,000~300,000.
Preferably, the cracking conversion rubbery collosol content obtained in the step (1) is more than 60%, Mooney viscosity is less than
40。
Preferably, in step (3), the crosslinking agent of the addition is sulphur.
Present invention also offers rubber of being given up obtained in a kind of preparation method that conversion modified pitch is cracked with above-mentioned scrap rubber
Glue cracking conversion modified pitch.
The method that the present invention uses normal pressure double helix Pintsch process, the fume emission that process is produced in order, can pass through
Cooling pipe is collected.Because degradation temperature is up to 300 DEG C or so, the main chain and crosslinking sidechain for being crosslinked rubber are easy to chemical bond
Destruction, makes the cross-linked structure of rubber disintegrate, and scrap rubber is cracked into liquid type bituminous material, because cross-bond is largely broken, rubber
Xanthan molecule amount is less than 10,000 g/mol, and now sol content is drastically raised to, and more than 60%, with high fluidity and adhesive property, becomes
Class sapropelitic is obtained, it is uniform and stable so as to be reached in pitch so as to reduce lamination tendency of the scrap rubber in matrix pitch
Dispersion.In the preparation process of modified pitch, the SBS for preparing of addition, high shearing mixing emulsor intensive shear and
In the presence of high temperature, with the rubber for cracking under crosslinking agent effect, the interaction for further occurring improves SBS/ and gives up SBS
Compatibility between rubber asphalt, so as to improve the hot storage stability of modified pitch, SBS also considerably improves scrap rubber
Convert the performance of pitch.
Compared with prior art, the modified scrap rubber cracking conversion pitches of the obtained SBS of the present invention, isolation test is according to GB/
T0661-2011 standards are performed, and as a result show that its hot storage stability is excellent.135 DEG C of viscosity are according to GB/T0625-2011 standards
Perform, as a result show that it has preferable construction workability.The needle penetration of modified pitch, ductility, the test of softening point are pressed respectively
Performed according to GB/T0604-2011, GB/T0605-2011, GB/T0606-2011 standard, as a result show the high/low temperature of modified pitch
Function admirable, physical properties meet the bitumen for road use performance indications that China specifies, are adapted to large-scale production and use, and take
Obtained significant technique effect：
1. by the method for double helix Pintsch process, scrap rubber is changed into class bituminous material, significantly improve it in pitch
In dispersiveness.
2. the use of SBS is modifying agent, sulphur is used as crosslinking agent.So, the rubber of cracking is crosslinked combination, cooperate with
SBS further increases the performance of modified pitch.
3., because scrap rubber cracking rubber powder disperses fine in pitch, there is substantial amounts of carbon black to discharge, therefore it is conducive to protection
SBS's is aging.Puzzlement problem in the industry for a long time is solved, the durability of modified pitch is expanded.
4. dexterously be combined together for the scrap rubber after Pintsch process and pitch by present invention innovation, then in conjunction with SBS,
Process is simple, substantially, environmental protection is easy to control, and cost performance is high, is worthy to be popularized for effect.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Step 1：In terms of mass fraction, during 4 parts of SBS added into 96 parts of 70#SK pitches, under the conditions of 170~190 DEG C
High speed shear 45min, shearing rotating speed is 3000r/min.
Step 2：The SBS modified pitch that will have been sheared is transferred on high speed dispersor and stirs development 150min, speed of agitator
Be 800~900r/min, during add amount to 0.15 part of sulphur several times, modified pitch is obtained.
Obtained modified pitch numbering is 1, and performance is shown in Table 1.
Embodiment 2
Step 1：It is added in constant-pressure and high-temperature double helix desulfurization equipment, the full rubber powder of the junked tire of 20 mesh at 300 DEG C
Under, after 20min by scrap rubber Pintsch process be class asphalt material, in terms of mass fraction, by 30 parts of scrap rubber Pintsch process class
Asphalt material, 70 parts of SK heavy traffic paving asphalts, are mixed with scrap rubber cracking conversion asphalt mother liquid in asphalt tank, and mixing temperature is
160 DEG C, rotating speed is 50r/min, and the time is 10min.
Step 2：Above-mentioned mother liquor is added 0.2% sulphur, 170~190℃Under the conditions of high speed shear 60min, shearing
Rotating speed is 4000r/min.The modified pitch that will have been sheared is transferred on high speed dispersor and stirs development 120min, and speed of agitator is
800~900r/min, is obtained 40% scrap rubber cracking conversion pitch.
Obtained modified pitch numbering is 2, and performance is shown in Table 1.
Embodiment 3
Step 1：It is added in constant-pressure and high-temperature double helix cracking equipment, the full rubber powder of the junked tire of 20 mesh at 300 DEG C
Under, after 20min by scrap rubber Pintsch process be class asphalt material.In terms of mass fraction, 30 parts of scrap rubber Pintsch process is produced
Thing, 70 parts of heavy traffic paving asphalt, are mixed with scrap rubber cracking conversion asphalt mother liquid in asphalt tank, and mixing temperature is 160 DEG C, is turned
Speed is 50r/min, and the time is 10min.
Step 2：In terms of weight/mass percentage composition, above-mentioned mother liquor is added 0.2% sulphur, add 4% SBS, 170~
High speed shear 60min under the conditions of 190 DEG C, shearing rotating speed is 4000r/min.The modified pitch that will have been sheared is transferred to dispersion at a high speed
Development 120min is stirred on machine, speed of agitator is 800~900r/min, the modified scrap rubber cracking conversion pitches of SBS are obtained.
Obtained modified pitch numbering is 3, and performance is shown in Table 1.
Embodiment 4
Step 1：It is added in constant-pressure and high-temperature double helix cracking equipment, the full rubber powder of the junked tire of 20 mesh at 300 DEG C
Under, after 20min by scrap rubber Pintsch process be class asphalt material.In terms of mass fraction, 30 parts of scrap rubber Pintsch process is produced
Thing, 70 parts of heavy traffic paving asphalt, are mixed with scrap rubber cracking conversion asphalt mother liquid in asphalt tank, and mixing temperature is 160 DEG C, is turned
Speed is 50r/min, and the time is 10min.
Step 2：In terms of weight/mass percentage composition, above-mentioned mother liquor is added 0.2% sulphur, add 2% SBS, 170~
High speed shear 60min under the conditions of 190 DEG C, shearing rotating speed is 4000r/min.The modified pitch that will have been sheared is transferred to dispersion at a high speed
Development 120min is stirred on machine, speed of agitator is 800~900r/min, the modified scrap rubber cracking conversion pitches of SBS are obtained.
Obtained modified pitch numbering is 4, and performance is shown in Table 1.
Embodiment 5
Step 1：It is added in constant-pressure and high-temperature double helix cracking equipment, the full rubber powder of the junked tire of 20 mesh at 300 DEG C
Under, after 20min by scrap rubber Pintsch process be class asphalt material.In terms of mass fraction, 20 parts of scrap rubber Pintsch process is produced
Thing, 80 parts of heavy traffic paving asphalt, are mixed with scrap rubber cracking conversion asphalt mother liquid in asphalt tank, and mixing temperature is 160 DEG C, is turned
Speed is 50r/min, and the time is 10min.
Step 2：In terms of weight/mass percentage composition, above-mentioned mother liquor is added 0.2% sulphur, add 4% SBS, 170~
High speed shear 60min under the conditions of 190 DEG C, shearing rotating speed is 4000r/min.The modified pitch that will have been sheared is transferred to dispersion at a high speed
Development 120min is stirred on machine, speed of agitator is 800~900r/min, the modified scrap rubber cracking conversion pitches of SBS are obtained.
Obtained modified pitch numbering is 5, and performance is shown in Table 1.
Embodiment 6
Step 1：It is added in constant-pressure and high-temperature double helix cracking equipment, the full rubber powder of the junked tire of 60 mesh at 260 DEG C
Under, after 20min by scrap rubber Pintsch process be class asphalt material.In terms of mass fraction, 10 parts of scrap rubber Pintsch process is produced
Thing, 90 parts of heavy traffic paving asphalt, are mixed with scrap rubber cracking conversion asphalt mother liquid in asphalt tank, and mixing temperature is 160 DEG C, is turned
Speed is 50r/min, and the time is 10min.
Step 2：In terms of weight/mass percentage composition, above-mentioned mother liquor is added 0.2% sulphur, add 4% SBS, 170~
High speed shear 60min under the conditions of 190 DEG C, shearing rotating speed is 4000r/min.The modified pitch that will have been sheared is transferred to dispersion at a high speed
Development 120min is stirred on machine, speed of agitator is 800~900r/min, the modified scrap rubber cracking conversion pitches of SBS are obtained.
Obtained modified pitch numbering is 6, and performance is shown in Table 1.
The performance of modified bitumen that the embodiment 1~6 of table 1 is obtained
Embodiment 2,3 contrast it is visible, scrap rubber cracking conversion pitch stability preferably, but the performance such as softening point compared with
Low, after SBS is added, performance is significantly improved, and illustrates that modified pitch has good performance and heat endurance；5 DEG C of ductilities are mostly
More than 30cm, with good cryogenic property；Isolation test softening point difference within 2 DEG C, with good hot storage stability；
135 DEG C of nearly 3Pas (ibid) of bonding, it may have preferable construction workability.Contrast 1 and 5 is visible, under equal SBS consumptions, gives up
The performance of rubber cracking conversion pitch more preferably, shows there is cost performance higher.
The invention is not limited in foregoing specific embodiment.The present invention is expanded to and any in this manual disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (7)
1. a kind of scrap rubber cracking converts the preparation method of modified pitch, it is characterised in that comprise the following steps：
(1) scrap rubber cracking conversion is obtained into cracking conversion rubber；
(2) weight is converted into rubber in the situation that temperature is 150~180 DEG C than the heavy traffic paving asphalt for 60/40~95/5/cracking
Under, it is well mixed, obtain scrap rubber conversion asphalt mother liquid；
(3) by mass ratio is above-mentioned scrap rubber conversion asphalt mother liquid, 1~6% SBS is added to 170~190 DEG C of conversion drip
In blue or green mother liquor, using high shearing mixing emulsor or colloid mill, temperature is maintained at 170~190 DEG C, shearing dispersion, then in height
Development is stirred on fast dispersion machine, and during the stirring is developed, puts into co-crosslinker, finally prepare high performance scrap rubber
Cracking conversion modified pitch,
It is by the detailed process that scrap rubber cracking conversion obtains cracking conversion rubber in the step (1)：Waste Crumb rubber is passed through
Normal pressure double helix cracker, processes 10-30min at a temperature of 260-360 DEG C, cracks scrap rubber and is converted into thick class drip
Green material, i.e. cracking conversion rubber.
2. scrap rubber cracking according to claim 1 converts the preparation method of modified pitch, it is characterised in that in step
(3) in, during development is stirred, it is 300~1000r/min, 60~150min of stirring reaction to control speed of agitator.
3. scrap rubber cracking according to claim 1 converts the preparation method of modified pitch, it is characterised in that the step
(1) rubber powder that the scrap rubber in grinds after being crushed for junked tire, mesh number is 15-60 mesh.
4. scrap rubber cracking according to claim 1 converts the preparation method of modified pitch, it is characterised in that in step
(3) in, the SBS is line style styrene-butadiene-styrene, and wherein styrene and the mass ratio of butadiene is 3/
7, molecular weight is 60,000~300,000.
5. scrap rubber cracking according to claim 1 converts the preparation method of modified pitch, it is characterised in that the step
(1) more than 60%, Mooney viscosity is less than 40 to the cracking conversion rubbery collosol content obtained in.
6. scrap rubber cracking according to claim 1 converts the preparation method of modified pitch, it is characterised in that in step
(3) in, the crosslinking agent of the addition is sulphur.
7. given up obtained in the preparation method of the scrap rubber cracking conversion modified pitch according to claim 1~6 any one
Rubber cracking converts modified pitch.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105331330B (en) * | 2015-12-16 | 2016-08-24 | 甘肃恒达路桥工程集团有限公司中心试验室 | The asphalt pavement crack sealing of resistance to ultraviolet glue and preparation method thereof |
| CN105778530B (en) * | 2016-03-14 | 2019-01-29 | 中交益通（北京）科技有限公司 | A kind of SBS- rubber composite modified pitch and preparation method thereof |
| CN106009720A (en) * | 2016-05-23 | 2016-10-12 | 江苏天诺道路材料科技有限公司 | Composite modified asphalt with stable thermal storage performance and preparation method thereof |
| CN109705365B (en) * | 2018-12-29 | 2021-12-07 | 江苏宝利国际投资股份有限公司 | Preparation method of environment-friendly composite modified asphalt |
| CN109678399B (en) * | 2019-02-25 | 2019-09-20 | 内蒙古高等级公路建设开发有限责任公司 | A kind of Warm-Mix Bitumen Mixture and preparation method thereof |
| CN111925659A (en) * | 2020-07-30 | 2020-11-13 | 江苏宝利国际投资股份有限公司 | Self-healing modified asphalt and preparation method and application thereof |
| CN114316357A (en) * | 2021-12-29 | 2022-04-12 | 江苏宝利国际投资股份有限公司 | Preparation method of reactive rubber for modified asphalt |
| CN114752108B (en) * | 2022-05-13 | 2023-07-25 | 长沙理工大学 | Method for degrading waste tire rubber into asphalt |
| CN115160806B (en) * | 2022-07-18 | 2023-07-25 | 甘肃公航旅低碳科技有限公司 | Preparation method and application of low-carbon asphalt based on recycled resources |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1201389B1 (en) * | 1999-06-08 | 2009-07-29 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Method of reclaiming crosslinked rubber |
| CN101434710B (en) * | 2008-12-18 | 2010-07-14 | 泰安市金山橡胶工业有限公司 | Automatic rubber powder plasticizing process and apparatus thereof |
| CN102601975B (en) * | 2012-03-15 | 2014-12-10 | 北京化工大学 | Method for continuously preparing liquid reclaimed rubber by aid of screw extruder |
| CN102660125B (en) * | 2012-05-16 | 2014-04-16 | 中胶橡胶资源再生（青岛）有限公司 | Preparation method of waste rubber modified emulsified asphalt |
| CN103146206B (en) * | 2013-03-19 | 2015-06-10 | 湖北国创高新材料股份有限公司 | Preparation method of storage-stable compound modified asphalt |
| CN103819918A (en) * | 2014-03-18 | 2014-05-28 | 上海交通大学 | Composite high-viscosity modified asphalt and preparation method thereof |
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