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CN100567399C - A kind of rubber powder modified asphalt and its processing method - Google Patents

A kind of rubber powder modified asphalt and its processing method Download PDF

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CN100567399C
CN100567399C CNB2007101180266A CN200710118026A CN100567399C CN 100567399 C CN100567399 C CN 100567399C CN B2007101180266 A CNB2007101180266 A CN B2007101180266A CN 200710118026 A CN200710118026 A CN 200710118026A CN 100567399 C CN100567399 C CN 100567399C
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rubber powder
asphalt
modified asphalt
crosslinking agent
processing method
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CN101104739A (en
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张玉贞
刘延军
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Oil and Gas Development and Utilization Corp
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Abstract

本发明公开了改性沥青及其加工方法。本发明所提供的改性沥青,含有如下重量份的组分:基质沥青50-92,橡胶粉8-50,第一交联剂0.1-5,稀释剂0-12,第二交联剂0-6。本发明通过对废胶粉在沥青中的选择性降解工艺条件分析、降解废胶粉在沥青中大分子性能的恢复及废胶粉改性沥青的制备技术研究,开发出一种通过脱硫降解和再交联的改性沥青及其加工生产方法,所得改性沥青能够形成均相混合体系,降低了改性沥青的粘度,并提高了产品的贮存稳定性。The invention discloses modified asphalt and a processing method thereof. The modified asphalt provided by the present invention contains the following components in parts by weight: base asphalt 50-92, rubber powder 8-50, first crosslinking agent 0.1-5, diluent 0-12, second crosslinking agent 0 -6. The present invention develops a method of desulfurization, degradation and The re-crosslinked modified asphalt and its processing and production method, the obtained modified asphalt can form a homogeneous mixed system, reduce the viscosity of the modified asphalt, and improve the storage stability of the product.

Description

A kind of rubber powder modified asphalt and working method thereof
Technical field
The present invention relates to a kind of rubber powder modified asphalt and working method thereof.
Background technology
Along with the development of communications and transportation cause, the performance of plain asphalt can not satisfy the requirement of high-grade highway.In order to improve asphalt quality, strengthen the use properties of road bitumen, various countries have developed the modifying asphalt production technology in succession.So-called modifying asphalt is meant " admixture rubber, resin, high molecular polymer, levigated rubber powder or other filler additives (properties-correcting agent), or take measures such as pitch mild oxidation processing are improved the bituminous performance and the asphalt mixture made ".Different properties-correcting agent can be in the use properties of improving pitch or asphalt in varying degrees.Waste Crumb rubber not only can reduce the bituminous temperature sensitivity, increases bituminous elasticity, and the be full of cracks of minimizing bituminous pavement and aging improves the driving safety and the service life of road surface of vehicle, and the cost of modifying asphalt is reduced significantly.Waste Crumb rubber is used for the best method that asphalt modification is internationally recognized innoxious, recycling treatment waste rubber.
Waste Crumb rubber modified asphalt mainly contains two kinds of production methods at present: wet method and dry method.Wet method is earlier waste Crumb rubber to be mixed with pitch, and the formation rubber powder modified asphalt is then rubber powder modified asphalt and gather materials and carry out heat and mix and stir and make compound.Dry method is earlier rubber powder to be joined to gather materials, and the mixing of formation is gathered materials and to be carried out heat with pitch and mix and stir and make compound.Because do not need special equipment, the expense of dry way process is low, and production result's consistence is poor, and the road of building with dry method needs often to repair.Main in the last few years abroad employing is wet-process modified, though this method of modifying makes the elasticity of rubber powder obtain application, but rubber powder is that swelling is not dissolved in the pitch at pitch in the course of processing, chemical reaction does not take place in rubber powder and pitch, the rubber powder modified asphalt that forms is heterogeneous, asphalt viscosity is higher, and the formed asphalt compound can produce the problem that is difficult to compacting.
In recent years, aspect rubber powder degraded and the vulcanized rubber powder chemical treatment some new technical study were being arranged also.CN1441005A discloses a kind of production technology of desulfurization glue powder-modified asphalt, promoted the consistency of each component in the rubber powder modified asphalt, but handle owing to need carry out pre-desulfurization to rubber powder, and then be that raw material carries out asphalt modification with the desulfurization rubber powder, the cost of raw material is higher, and its additive cross-linking effect that adopts is limited.
Summary of the invention
The purpose of this invention is to provide a kind of rubber powder modified asphalt and working method thereof with superperformance.
Rubber powder modified asphalt provided by the present invention, contain the component of following weight part:
Matrix pitch 50-92,
Rubber powder 8-50,
The first linking agent 0.1-5,
Thinner 0-12,
The second linking agent 0-6;
Described first linking agent is the mixture of sulphur and rock asphalt;
Described thinner is selected from one or more in solvent oil, furfural extract oil and the vacuum distillate;
Second linking agent is the SBS resin.
Wherein, the penetration degree of matrix pitch is 30~300dmm, and softening temperature is 30 ℃~62 ℃.The particle diameter of rubber powder is the 40-200 order.Sulphur and rock asphalt quality are not particularly limited than weight ratio in first linking agent, and weight ratio can not reach effect of the present invention by regulating addition simultaneously, is preferably 1: 0.1-10.
The working method of this modifying asphalt is heated to 185 ℃~250 ℃ with matrix pitch earlier, slowly adds rubber powder, shear agitation; Then, add first linking agent, shear agitation or colloidal mill grind once more, obtain described modifying asphalt.
Wherein, add that the temperature of described shear agitation is 165 ℃-245 ℃ before first linking agent, the time is no more than 8 hours, when adding first linking agent, can also add the thinner and/or second linking agent.
Pitch has certain desulfurization Degradation to common vulcanized rubber powder, but the desulfurization degradation effect is limited under the common process condition.In the present invention, by under the effect of mechanical forces such as 185 ℃~250 ℃ high temperature, shear agitation, having realized preferably rubber powder is carried out desulfurization.Be pointed out that be meant the some keys that cut off cross-link bond and the depolymerization reaction that produces in this said desulfurization, purpose is the state that makes elastomeric cross-linked rubber plasticization and return to original processing.And the desulfurization rubber powder so be easy to further be desulfurized degraded in pitch, is shown very high solubleness because its part macromolecular chain has interrupted.Under the linking agent effect, the rubber powder of degraded desulfurization can form reticulated structure once more in pitch.Wherein, the desulfurization rubber powder is because by partial desulfurization, and it has in pitch and distributes preferably and easily by the pitch swelling, when being used linking agent, linking agent can make desulfurization rubber powder recuperation section crosslinked, has formed reticulated structure uniformly in pitch, has improved the bituminous performance well.
The present invention passes through selectivity degradation technique condition analysis, the recovery of degraded shoddy in pitch macromole performance and the Study on Preparation Technology of waste rubber powder modified asphalt of shoddy in pitch, develop a kind of by desulfurization degraded and crosslinked again modifying asphalt and method for producing thereof, the gained modifying asphalt can form homogeneous mixture system, reduce the viscosity of modifying asphalt, and improved the package stability of product.
Compared with prior art, the present invention has following technical superiority and characteristics:
1, employing is carried out the appropriately crosslinked again chemical modifying process of desulfurization degraded earlier to rubber powder, is guaranteeing to have improved the stability of modified bitumen product than under the lower production cost.
2, adopt new linking agent prescription, improved rubber powder and bituminous consistency, significantly improved the performance of modifying asphalt.
3, the rubber powder modified asphalt of being produced is having tangible lifting aspect ductility index and the stability in storage index.
Description of drawings
Fig. 1 is the fluorescence micrograph (Figure 1A is 180 ℃, and Figure 1B is 230 ℃) of modifying asphalt under the different modification temperatures.
Embodiment
Deficiency in view of present waste rubber powder modified asphalt production, the invention provides a kind of is main properties-correcting agent with shoddy, in the modification course of processing, by adjusting process parameter and use linking agent shoddy is realized desulfurization degraded and crosslinked again, produced the modified bitumen product of excellent property.
Modifying asphalt of the present invention contains the component of following weight part:
Matrix pitch 50-92,
Rubber powder 8-50,
The first linking agent 0.1-5,
Thinner 0-12,
The second linking agent 0-6;
Wherein, matrix pitch can be vacuum residuum, straight-run pitch, also can be the various pitches such as mediation pitch that mediation technology obtains, and penetration degree (25 ℃, 0.1mm): 30~300, softening temperature is 30 ℃~62 ℃.
Rubber powder: can select commercially available various waste Crumb rubbers for use, granular size is 40 orders-200 orders.
Thinner: can be one or more of solvent oil, furfural extract oil or reduced pressure distillate wet goods.These thinners are the effect basically identical that rises in the modifying asphalt production process, and visual matrix pitch penetration degree size selectivity is added.
First linking agent: the mixture of sulphur and rock asphalt, sulphur and rock asphalt weight ratio are not particularly limited in this mixture, and its scope can be 1: 0.1-10, weight ratio can not reach effect of the present invention by regulating addition simultaneously.
Second linking agent: SBS resin (styrene/butadiene/styrene block copolymers).
Complete processing:
Earlier matrix pitch is heated to 185 ℃~more than 250 ℃, slowly add rubber powder, at high temperature shear agitation adds linking agent after for some time, stirs or colloidal mill grinds and makes modifying asphalt through high speed shear once more.Wherein the gradation of can classifying of two kinds of linking agents adds, and whole course of processing temperature of reaction is controlled between 165 ℃~250 ℃.
In the above-mentioned course of processing, the temperature of shear agitation is 165 ℃-245 ℃, and shear time is no more than 8 hours.Used shears performance is similar substantially in the modifying asphalt production process, and significant parameter is a velocity of shear, and velocity of shear is slow, and shear time can correspondingly increase, and when speed was fast, shear time can shorten, as long as make various materials energy thorough mixing evenly.
The present invention is further illustrated by means of embodiment below, and processing condition that adopt among the embodiment and proportioning only are used for summary of the invention is described further, and these technological parameters of non-limiting use.Per-cent related in the content all refers to mass percent.
Embodiment 1
(penetration degree (25 ℃ is 88 0.1mm), and softening temperature is 47) is heated to 210 ℃ (modification temperatures) earlier with 400 gram matrix pitches; Slowly add 40 order waste Crumb rubbers (100g), shear agitation 30 minutes (velocity of shear 2500rpm) through screening; Cool to 180 ℃, add first linking agent (2.5g, wherein the weight ratio of sulphur and rock asphalt is 1: 1) then, second linking agent (5g), controlled temperature is constant, and high speed shear stirred 2 hours, got modifying asphalt after the cooling.
Adopt common rubber powder modified asphalt in contrast, this modifying asphalt by comparison, softening temperature is brought up to 58 ℃ from 57 ℃, 5 ℃ of ductilities are brought up to 31.0cm from 14.5cm; Behind RTFOT (test of rotating thin film oven ageing), more common rubber powder modified asphalt is compared, and the softening temperature of this modifying asphalt changes by 4 ℃ and is reduced to 3 ℃, illustrate rubber powder modified asphalt desulfurization at high temperature degrade crosslinked again after, stability obviously improves.
The dispersion state of rubber powder in pitch relatively under embodiment 2, the different modification temperature
Different modification temperatures have bigger influence to performance of modified bitumen, adopt the proportioning of embodiment 1, select two different modification temperatures to compare: A) earlier matrix pitch is heated to 180 ℃, and then carries out ensuing modification processing; B) earlier matrix pitch is heated to 230 ℃, carries out ensuing modification processing again.
Adopt the microtexture (Figure 1A is 180 ℃ of modification temperature gained modifying asphalts, and Figure 1B is 230 ℃ of modification temperature gained modifying asphalts) of fluorescence microscope modifying asphalt.From Fig. 1 as seen, under 180 ℃ of modification temperatures, rubber is to exist with bigger bulk, and pitch is very poor to its swelling property; And under 230 ℃ of modification temperatures, because the effect of desulfurization degraded, rubber grain diminishes, and pitch is to the swelling property of rubber be improved (because the light constituent in the pitch penetrates in the rubber grain, showing as the rubber grain colour-darkening).This observations can illustrate the raising along with modification temperature, and rubber powder-asphalt system desulfurization degradation effect is obvious, helps modifying asphalt to form homogeneous mixture system preferably.
Embodiment 3
(penetration degree (25 ℃ is 68 0.1mm), and softening temperature is 49) is heated to 220 ℃ earlier with 400 gram matrix pitches; Slowly add 60 order waste Crumb rubbers (95g) then, shear agitation 30 minutes (velocity of shear 2500rpm) through screening; Cool to 185 ℃, add first linking agent (2.6g, wherein the weight ratio of sulphur and rock asphalt is 1: 0.5) then, 2% the second linking agents (10g), controlled temperature is constant, high speed shear stirred 2 hours, after the cooling modifying asphalt.
Experimental result records (25 ℃ of this modifying asphalt penetration degrees, 0.1mm) be 70, softening temperature is 58 ℃, 5 ℃ of ductilities are 34cm, place and after 30 days sample is remeasured the result and be: (25 ℃ is 75 0.1mm) to penetration degree, and softening temperature is 55 ℃, 5 ℃ of ductilities are 50cm, and product shows good preservation stability.
Embodiment 4
(penetration degree (25 ℃ is 88 0.1mm), and softening temperature is 47) is heated to 210 ℃ earlier with 400 gram matrix pitches; Slowly add 40 order waste Crumb rubbers (98g), shear agitation 30 minutes (velocity of shear 2500rpm) through screening; Cool to 180 ℃, add first linking agent (6g, wherein the weight ratio of sulphur and rock asphalt is 1: 3) then, high speed shear stirred 2 hours, got modifying asphalt after the cooling.
Gained modifying asphalt softening temperature is 57 ℃, 5 ℃ of ductility 17cm; Behind RTFOT (test of rotating thin film oven ageing), the softening temperature of modifying asphalt is 44.

Claims (5)

1、一种胶粉改性沥青,含有如下重量份的组分:1. A rubber powder modified asphalt containing the following components in parts by weight: 基质沥青        50-92,Base bitumen 50-92, 橡胶粉          8-50,Rubber powder 8-50, 第一交联剂      0.1-5,The first crosslinking agent 0.1-5, 第二交联剂      0-6;The second crosslinking agent 0-6; 稀释剂          0-12,Thinner 0-12, 所述基质沥青的针入度为30~300dmm,软化点为30℃~62℃;The penetration of the base pitch is 30-300dmm, and the softening point is 30°C-62°C; 所述橡胶粉的粒径为40-200目;The particle diameter of described rubber powder is 40-200 order; 所述第一交联剂为硫磺和天然沥青的混合物;The first crosslinking agent is a mixture of sulfur and natural asphalt; 第二交联剂为SBS树脂;The second crosslinking agent is SBS resin; 所述稀释剂选自溶剂油、糠醛抽出油和减压馏分油中的一种或几种。The diluent is selected from one or more of solvent oil, furfural extracted oil and vacuum distillate oil. 2、根据权利要求1所述的胶粉改性沥青,其特征在于:所述第一交联剂中硫磺和天然沥青的质量比是1∶0.1-10。2. The rubber powder modified asphalt according to claim 1, characterized in that the mass ratio of sulfur to natural asphalt in the first crosslinking agent is 1:0.1-10. 3、权利要求1所述胶粉改性沥青的加工方法,先将基质沥青加热到185℃~250℃,缓慢加入橡胶粉,剪切搅拌30分钟,剪切速度为2500rpm;然后,降温到180℃或185℃,加入第一交联剂,再次剪切搅拌或胶体磨研磨,得到所述胶粉改性沥青。3. The processing method of rubber powder modified asphalt according to claim 1, first heating the base asphalt to 185°C-250°C, slowly adding rubber powder, shearing and stirring for 30 minutes, the shearing speed is 2500rpm; then, cooling down to 180°C ℃ or 185 ℃, add the first crosslinking agent, and then shear and stir or colloid mill grinding to obtain the rubber powder modified asphalt. 4、根据权利要求3所述的加工方法,其特征在于:所述剪切搅拌的温度为165℃-245℃。4. The processing method according to claim 3, characterized in that: the temperature of the shearing and stirring is 165°C-245°C. 5、根据权利要求3或4所述的加工方法,其特征在于:在加入第一交联剂时,加入稀释剂和/或第二交联剂。5. The processing method according to claim 3 or 4, characterized in that: when adding the first cross-linking agent, diluent and/or the second cross-linking agent are added.
CNB2007101180266A 2007-06-27 2007-06-27 A kind of rubber powder modified asphalt and its processing method Active CN100567399C (en)

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Families Citing this family (16)

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CN101565286B (en) * 2008-04-25 2011-08-10 北京化工大学 Method for preparing rubber powder masterbatch capable of quickly dispersing modified asphalt
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CN102391612B (en) * 2011-10-20 2013-03-13 许昌金欧特沥青股份有限公司 Anionic aqueous colorized road surface crack sealing material and preparation process thereof
CN102433008A (en) * 2011-11-03 2012-05-02 黑龙江长和化工股份有限公司 Pavement crack pouring adhesive and preparation method thereof
CN102964854B (en) * 2012-11-23 2015-02-11 山东泰德新能源有限公司 Road asphalt modifier
CN102966018B (en) * 2012-12-04 2015-07-29 山东交通学院 A kind of preparation method of controllable temperature paveio(u)r
CN104402311B (en) * 2014-10-20 2016-11-30 山西省交通科学研究院 A kind of rubber powder modified asphalt compound and preparation method thereof
CN105985531B (en) * 2015-02-03 2018-12-04 吕刚 The method for preparing various temperature condition asphalt modifier and modified pitch using waste rubber oil
CN104693824B (en) * 2015-03-18 2016-10-12 中国海洋石油总公司 A kind of cable asphalt and preparation method thereof
CN106633964B (en) * 2016-12-22 2020-03-13 上海群康沥青科技股份有限公司 Modified asphalt composition
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