CN105542495A - Modified carbon black, modified asphalt and preparation method of modified carbon black and modified asphalt - Google Patents
Modified carbon black, modified asphalt and preparation method of modified carbon black and modified asphalt Download PDFInfo
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- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
- C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K2201/011—Nanostructured additives
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Abstract
The invention provides modified carbon black capable of being taken as an asphalt additive. The modified carbon black is prepared by performing anaerobic high-temperature pyrolysis on waste rubber, washing with a washing agent, oxidizing with an oxidizing agent and activating with a surface active agent in sequence. The invention further provides a preparation method and application of the modified carbon black. The modified carbon black provided by the invention is much higher in aging resistance than that of ordinary carbon black, good in dispersity and difficult to aggregate; therefore, compared with the ordinary carbon black, the modified carbon black can more efficiently improve the thermal-oxidative aging and ultraviolet aging resistance of the asphalt.
Description
Technical field
The present invention relates to the preparation method of a kind of modified carbon black, modifying asphalt and modified carbon black and modifying asphalt.
Background technology
Ageing of asphalt is the important factor affecting bituminous pavement functional quality and performance, pitch aging typically refer to pitch storing, transport, the mixing and stirring of compound, pave, in roller compaction process and the series of physical occurred in life-time service process and chemical transformation, cause the process of its performance degradation.The aging major way of pitch is ultraviolet light and aging and thermo-oxidative ageing.In bituminous pavement life-time service process, can slowly be oxidized when pitch contacts with air, the micelle that the polarity oxy radical of formation is coupled to high molecular gradually impels that the viscosity of pitch improves, ductility reduces.Therefore, bituminous pavement very easily occurs aging under solar radiation and in hot environment, and there will be the breakoff phenomenons such as hardening, cracking, these all greatly compromise the use properties of bituminous pavement, shorten its work-ing life.
With carbon black, modification is carried out to pitch, at home and abroad carry out comparatively early.Mix carbon black in pitch after, residual penetration degree and residual ductility raise, and the resistance of aging of pitch is greatly improved.Carbon black belongs to inorganic UV absorption agent, can by reflecting and reflecting the object that ultraviolet reaches protectiving ultraviolet.Ordinary carbon black, as a kind of common antiaging agent, can slow down the solarization of UV-light to pitch, can improve the performance of pitch thermo oxidative aging simultaneously.Because carbon black is cheap, and can obtain regenerating carbon black by means such as damaged tire cracking, therefore can save great amount of cost compared to conventional polymer modifiers SBS, SBR etc., have very large potentiality to be exploited.But the bad dispersibility of ordinary carbon black in pitch, very easily agglomeration occurs, and mix the ductility of pitch too much can be caused to decline, the decline of ductility can make bituminous pavement in the winter time low temperature time ftracture, and the very few raising to asphalt performance of incorporation is very unobvious.
For the modification of carbon black, existing many research both at home and abroad.The bright international monopoly 200780053081.X of people's application that waits of the wild will of paulownia of Japan proposes a kind of dispersible surface-modified carbon black, the surface functional group of described carbon black and the terminal isocyanate groups bonding had in the tri-isocyanate compound of three terminal isocyanate groups, and all the other two terminal isocyanate groups respectively with the hydroxyl bonding of polymkeric substance with glycol modification end group.The modified carbon black of this invention has superior dispersibility in non-polar solvent, low polar solvent, is mainly used in the black pigment used in liquid-crystal display black matix or electronic console.Japanese Patent JP-A-8-337624 discloses a kind of reactive Grafting Polymerization of Carbon Black thing of favorable dispersity in the media such as ink, ink powder, coating and coloring resin agent, it, by adding the polymer chain of silicone component in Grafting Polymerization of Carbon Black thing, makes carbon black in low polar solvent, have good dispersiveness.
But the current application for modified carbon black both at home and abroad mainly concentrates on the aspect such as pigment, tinting material, and the applied research for asphalt modification aspect is but in blank substantially.
Summary of the invention
In order to solve the problem, the invention provides modified carbon black of a kind of waste rubber cracking and preparation method thereof, and the application method in modifying asphalt.
The invention provides a kind of modified carbon black that can be used as asphalt additive, described modified carbon black by waste rubber through anaerobic high temperature pyrolysis, and successively through detergent washing, oxidizing and surfactant activation is obtained.
Preferably, described modified carbon black is the globe of diameter 30nm ~ 100nm.
Present invention also offers the preparation method of this modified carbon black, specifically carry out as follows:
S1: take waste rubber as raw material, under anaerobic, through 500 DEG C ~ 600 DEG C high temperature pyrolysis, then granulates and forms the microspheroidal carbon black that diameter is 30nm ~ 100nm;
S2: employing washing composition repeatedly washs the carbon black obtained by S1, and by Büchner funnel filtration under diminished pressure, the organic impurity in removing carbon black;
S3: by the carbon black after S2 process and oxygenant with mass percent concentration be 0.5-2: 10 ratio mix, 2h ~ 3h is stirred at 70 DEG C ~ 90 DEG C temperature, filter after being cooled to room temperature, wash described carbon black to neutral, at 100 DEG C, carry out drying until constant weight;
S4: the carbon black after S3 process, phenol and strong base solution are mixed with the ratio that mass percent is 1: 10: 1, stir and be heated to 50 DEG C, stir speed (S.S.) is 300r/min ~ 400r/min, 2h ~ 4h is reacted under the environment of nitrogen, reaction terminates rear filtration, washing carbon black, to neutral, carry out drying until constant weight, obtains modified carbon black at 50 DEG C.
Preferably, described washing composition is selected from least one in benzene,toluene,xylene, ethanol, acetone, chloroform, tetracol phenixin.
Preferably, described oxygenant is selected from hydrogen peroxide, potassium bichromate solution, concentration are not less than at least one in the nitric acid of 60%.
Preferably, the concentration of described strong base solution is 20% ~ 40%.
Present invention also offers a kind of modifying asphalt, be prepared from by melt blending by pitch, stablizer and above-mentioned arbitrary described modified carbon black, shared by each raw material, mass percent is: pitch 86% ~ 96%, modified carbon black 2% ~ 7%, stablizer 2% ~ 7%.
Preferably, described pitch is the one in road bitumen, and 25 DEG C of penetration degrees are 50dmm ~ 110dmm, and softening temperature is 42 DEG C ~ 54 DEG C.
Preferably, described stablizer be selected from that sodium metnylene bis-naphthalene sulfonate, SMA are copolymerized amine salt used, one in polyvinylpyrrolidone.
Present invention also offers a kind of preparation method of modifying asphalt:
S11: take pitch, the modified carbon black of 2% ~ 7%, the stablizer of 2% ~ 7% that mass percent is 86% ~ 96% in proportion;
S12: by the asphalt heating to 120 in S11 DEG C ~ 140 DEG C, then add stablizer and modified carbon black, start shear mixer, at the rotating speed down cut 30min ~ 60min of 3000 ~ 6000rpm, make described modified carbon black be dispersed in pitch;
S13: S12 products therefrom is kept temperature 140 DEG C ~ 160 DEG C, reduces rotating speed to 500rpm ~ 1000rpm stirring reaction 30min ~ 45min, obtained modifying asphalt.
The modified carbon black obtained through anaerobic high temperature pyrolysis by waste rubber provided by the present invention, ageing-resistant ability will far away higher than ordinary carbon black, good dispersity simultaneously, not easily reunite, the ageing-resistant performance of pitch can be improved by mixing appropriate modified carbon black provided by the present invention further in pitch, therefore more efficiently can improve the performance of pitch thermo oxidative aging and ageing resistance by ultraviolet light relative to ordinary carbon black.
Compared with prior art, tool of the present invention has the following advantages:
1) the present invention adopts waste rubber Pintsch process to produce modified carbon black, and cost is very cheap;
2) add in pitch by modified carbon black provided by the invention, when volume is higher than certain value, modified carbon black provided by the present invention is compared with ordinary carbon black, and the detrimentally affect produced pitch low-temperature performance is less;
3) dispersiveness of modified carbon black provided by the invention is better than ordinary carbon black, can improve the resistance of aging of pitch by adding appropriate modified carbon black volume provided by the invention;
4) through the pitch of modified carbon black modification provided by the invention, ageing resistance by ultraviolet light ability significantly improves, and substantially increases the ageing resistance of pitch.
Embodiment
Understand technical scheme of the present invention better to make those skilled in the art can be implemented, below in conjunction with specific embodiment, the invention will be further described, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 510 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, toluene is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add the nitric acid 500ml that product that 50g is washed and concentration are 68%, by magnetic stirring apparatus, mixture is stirred 2h at 90 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the bitumen A of 86 mass parts, (described bitumen A is bi tumenf orr oad, 25 DEG C of penetration degrees are 72dmm, softening temperature is 50.3 DEG C) be heated to 140 DEG C, add the sodium metnylene bis-naphthalene sulfonate of 7 mass parts and the modified carbon black of 7 mass parts, under the rotating speed of 6000rpm, stir 30min, maintain the temperature at 150 DEG C, reduce rotating speed to 800rpm stirring reaction 30min, obtain by the bitumen A of above-mentioned modified carbon black modification.
Comparative example 1:
The bitumen A of 86 mass parts is heated to 140 DEG C, add the sodium metnylene bis-naphthalene sulfonate of 7 mass parts and the ordinary carbon black of 7 mass parts, stir 30min with the rotating speed of 6000rpm, maintain the temperature at 150 DEG C, reduce rotating speed to 800rpm stirring reaction 30min, obtain by the bitumen A of ordinary carbon black modification.
Comparative example 1 ':
Bitumen A is first heated to 140 DEG C, stirs 30min with the rotating speed of 6000rpm, then be warming up to 150 DEG C, stir 30min with the rotating speed of 800rpm.
The contrast sample that the modifying asphalt provide embodiment 1 and comparative example 1, comparative example 1 ' provide, has carried out Thin Film Oven Test TFOT (TFOT) respectively, pressure aging vessel PAV (PAV) test and natural climate weathering test.Obtain correlation data as following table 1:
The aging resistance of table 1 modified carbon black and ordinary carbon black modifying asphalt
Compare with comparative example 1 ' with comparative example 1, after indoor are aging, adding of modified carbon black prepared by the embodiment of the present invention 1 makes the residual penetration ratio of pitch and residual Ductility ratio greatly increase, and softening temperature increment and viscosity aging index obviously reduce, show that the heatproof air aging performance of the modified carbon black prepared by the embodiment of the present invention 1 to pitch has comparatively significant improvement result.
As can also be seen from Table 1, after natural climate aging (heavy natural sunning is about 35h+ rainwater effect and is about 10h), the modifying asphalt that embodiment 1 modified carbon black obtains is same with the modifying asphalt that comparative example 1 ordinary carbon black obtains shows larger residual penetration ratio and residual Ductility ratio, and less softening temperature increment and viscosity aging index.In addition, comparative example 1 is compared with the modifying asphalt of embodiment 1, and the residual penetration ratio of the modifying asphalt that modified carbon black obtains and residual Ductility ratio are larger, and softening temperature increment and viscosity aging index less.This shows that 2 kinds of carbon blacks all improve the aging resistance of resistance to natural climate of pitch, wherein more obvious with the improvement effect of modified carbon black.
Embodiment 2:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 510 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 50nm, use ethanol repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity.In the Erlenmeyer flask connecting spherical condensating tube, add the concentrated nitric acid 500ml that carbon black that 50g is washed and concentration are 60%, by magnetic stirring apparatus, mixture is stirred 3h at 70 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight.
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the potassium hydroxide solution of 40%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 5h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.When obtained modified carbon black is carried out asphalt modification as additive, by the bitumen A of 96 mass parts, (described pitch is bi tumenf orr oad, 25 DEG C of penetration degrees are 72dmm, softening temperature is 50.3 DEG C) be heated to 140 DEG C, add the modified carbon black of copolymerized amine salt used and 2 mass parts of the SMA of 2 mass parts, under the rotating speed of 3000rpm, stir 60min, maintain the temperature at 150 DEG C, reduce rotating speed and obtain modifying asphalt A to 800rpm stirring reaction 45min.
Comparative example 2:
The bitumen A of 86 mass parts is heated to 140 DEG C, add the ordinary carbon black of copolymerized amine salt used and 2 mass parts of the SMA of 2 mass parts, 60min is stirred with the rotating speed of 3000rpm, maintain the temperature at 150 DEG C, reduce rotating speed to 800rpm stirring reaction 30min, obtain by the bitumen A of ordinary carbon black modification.
Comparative example 2 '
Bitumen A is first heated to 140 DEG C, stirs 60min with the rotating speed of 3000rpm, then be warming up to 150 DEG C, stir 30min with the rotating speed of 800rpm.
The contrast sample that the modifying asphalt provide embodiment 2 and comparative example 2, comparative example 2 ' provide, has carried out Thin Film Oven Test TFOT (TFOT) respectively, pressure aging vessel PAV (PAV) test and natural climate weathering test.Obtain correlation data as following table 2:
The aging resistance of table 2 modified carbon black and ordinary carbon black modifying asphalt
Compare with comparative example 2 ' with comparative example 2, after indoor are aging, adding of modified carbon black prepared by the embodiment of the present invention 2 makes the residual penetration ratio of pitch and residual Ductility ratio greatly increase, and softening temperature increment and viscosity aging index obviously reduce, show that the heatproof air aging performance of the modified carbon black prepared by the embodiment of the present invention 2 to pitch has comparatively significant improvement result.
As can also be seen from Table 2, after natural climate aging (heavy natural sunning is about 35h+ rainwater effect and is about 10h), the obtained modifying asphalt of embodiment 2 is same with the modifying asphalt that comparative example 2 ordinary carbon black obtains shows larger residual penetration ratio and residual Ductility ratio, and less softening temperature increment and viscosity aging index.In addition, comparative example 2 is compared with the modifying asphalt of embodiment 2, and the residual penetration ratio of modified carbon black modifying asphalt and residual Ductility ratio are larger, and softening temperature increment and viscosity aging index less.This shows that 2 kinds of carbon blacks all improve the aging resistance of resistance to natural climate of pitch, wherein more obvious with the improvement effect of modified carbon black.
Embodiment 3:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 510 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 40nm, use benzene repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity.In the Erlenmeyer flask connecting spherical condensating tube, add the nitric acid 500ml that the carbon black of 50g process and concentration are 65%, by magnetic stirring apparatus, it is stirred 3h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight.
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50m1 phenol and 5ml concentration be the aqua calcis of 30%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer; Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch B of 93 mass parts, (described pitch is bi tumenf orr oad, 25 DEG C of penetration degrees are 91dmm, softening temperature is 45.5 DEG C) be heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the modified carbon black of 3.5 mass parts, under the rotating speed of 4500rpm, stir 45min, maintain the temperature at 160 DEG C, reduce rotating speed and obtain modifying asphalt B to 700rpm stirring reaction 40min.
Comparative example 3:
The pitch B of 93 mass parts is heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the ordinary carbon black of 3.5 mass parts, stir 45min with the rotating speed of 4500rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 700rpm stirring reaction 40min, obtain by the pitch B of ordinary carbon black modification.
Comparative example 3 '
Pitch B is first heated to 120 DEG C, stirs 45min with the rotating speed of 4500rpm, then be warming up to 160 DEG C, stir 40min with the rotating speed of 700rpm.
The contrast sample that the modifying asphalt provide embodiment 3 and comparative example 3, comparative example 3 ' provide, has carried out Thin Film Oven Test TFOT (TFOT) respectively, pressure aging vessel PAV (PAV) test and natural climate weathering test.Obtain correlation data as following table 3:
The aging resistance of table 3 modified carbon black and ordinary carbon black modifying asphalt
Compare with comparative example 3 ' with comparative example 3, after indoor are aging, adding of modified carbon black prepared by the embodiment of the present invention 3 makes the residual penetration ratio of pitch and residual Ductility ratio greatly increase, and softening temperature increment and viscosity aging index obviously reduce, show that the heatproof air aging performance of the modified carbon black prepared by the embodiment of the present invention 3 to pitch has comparatively significant improvement result.
As can also be seen from Table 3, after natural climate aging (heavy natural sunning is about 35h+ rainwater effect and is about 10h), the modifying asphalt that embodiment 3 modified carbon black obtains is same with the modifying asphalt that comparative example 3 ordinary carbon black obtains shows larger residual penetration ratio and residual Ductility ratio, and less softening temperature increment and viscosity aging index.In addition, comparative example 3 is compared with the modifying asphalt of embodiment 3, and the residual penetration ratio of the modifying asphalt that modified carbon black obtains and residual Ductility ratio are larger, and softening temperature increment and viscosity aging index less.This shows that 2 kinds of carbon blacks all improve the aging resistance of resistance to natural climate of pitch, wherein more obvious with the improvement effect of modified carbon black.
Embodiment 4:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 530 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 100nm, use benzene repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity.In the Erlenmeyer flask connecting spherical condensating tube, add the potassium bichromate solution 500ml that the carbon black of 50g process and concentration are 65%, by magnetic stirring apparatus, it is stirred 3h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight.
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, the phenol of 50ml and 5ml concentration be the aqua calcis of 30%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer; Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch B of 93 mass parts, (described pitch is bi tumenf orr oad, 25 DEG C of penetration degrees are 91dmm, softening temperature is 45.5 DEG C) be heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the modified carbon black of 3.5 mass parts, under the rotating speed of 4500rpm, stir 45min, maintain the temperature at 160 DEG C, reduce rotating speed and obtain modifying asphalt B to 700rpm stirring reaction 40min.
Comparative example 4:
The pitch B of 93 mass parts is heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the ordinary carbon black of 3.5 mass parts, stir 45min with the rotating speed of 4500rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 700rpm stirring reaction 40min, obtain by the pitch B of ordinary carbon black modification.
Comparative example 4 '
Pitch B is first heated to 120 DEG C, stirs 45min with the rotating speed of 4500rpm, then be warming up to 160 DEG C, stir 40min with the rotating speed of 700rpm.
The contrast sample that the modifying asphalt provide embodiment 4 and comparative example 4, comparative example 4 ' provide, has carried out Thin Film Oven Test TFOT (TFOT) respectively, pressure aging vessel PAV (PAV) test and natural climate weathering test.Obtain correlation data as following table 4:
The aging resistance of table 4 modified carbon black and ordinary carbon black modifying asphalt
Compare with comparative example 4 ' with comparative example 4, after indoor are aging, adding of modified carbon black prepared by the embodiment of the present invention 4 makes the residual penetration ratio of pitch and residual Ductility ratio greatly increase, and softening temperature increment and viscosity aging index obviously reduce, show that the heatproof air aging performance of the modified carbon black prepared by the embodiment of the present invention 4 to pitch has comparatively significant improvement result.
As can also be seen from Table 4, after natural climate aging (heavy natural sunning is about 35h+ rainwater effect and is about 10h), the modifying asphalt that embodiment 4 modified carbon black obtains is same with the modifying asphalt that comparative example 4 ordinary carbon black obtains shows larger residual penetration ratio and residual Ductility ratio, and less softening temperature increment and viscosity aging index.In addition, comparative example 4 is compared with the modifying asphalt of embodiment 4, and the residual penetration ratio of the modifying asphalt that modified carbon black obtains and residual Ductility ratio are larger, and softening temperature increment and viscosity aging index less.This shows that 2 kinds of carbon blacks all improve the aging resistance of resistance to natural climate of pitch, wherein more obvious with the improvement effect of modified carbon black.
Embodiment 5:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 600 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, use volume ratio be 1: 1 ethanol and tetracol phenixin mixed solution the product obtained repeatedly is washed, and by Büchner funnel filtration under diminished pressure, remove its organic impurity.In the Erlenmeyer flask connecting spherical condensating tube, add the potassium bichromate solution 500ml that the carbon black of 50g process and concentration are 65%, by magnetic stirring apparatus, it is stirred 3h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight.
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, the phenol of 50ml and 5ml concentration be the aqua calcis of 30%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer; Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch B of 93 mass parts, (described pitch is bi tumenf orr oad, 25 DEG C of penetration degrees are 91dmm, softening temperature is 45.5 DEG C) be heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the modified carbon black of 3.5 mass parts, under the rotating speed of 4500rpm, stir 45min, maintain the temperature at 160 DEG C, reduce rotating speed and obtain modifying asphalt B to 700rpm stirring reaction 40min.
Comparative example 5:
The pitch B of 93 mass parts is heated to 120 DEG C, add the polyvinylpyrrolidone of 3.5 mass parts and the ordinary carbon black of 3.5 mass parts, stir 45min with the rotating speed of 4500rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 700rpm stirring reaction 40min, obtain by the pitch B of ordinary carbon black modification.
Comparative example 5 '
Pitch B is first heated to 120 DEG C, stirs 45min with the rotating speed of 4500rpm, then be warming up to 160 DEG C, stir 40min with the rotating speed of 700rpm.
The contrast sample that the modifying asphalt provide embodiment 5 and comparative example 5, comparative example 5 ' provide, has carried out Thin Film Oven Test TFOT (TFOT) respectively, pressure aging vessel PAV (PAV) test and natural climate weathering test.Obtain correlation data as following table 5:
The aging resistance of table 5 modified carbon black and the carbon black modified pitch of universality
Compare with comparative example 5 ' with comparative example 5, after indoor are aging, adding of modified carbon black prepared by the embodiment of the present invention 5 makes the residual penetration ratio of pitch and residual Ductility ratio greatly increase, and softening temperature increment and viscosity aging index obviously reduce, show that the heatproof air aging performance of the modified carbon black prepared by the embodiment of the present invention 5 to pitch has comparatively significant improvement result.
As can also be seen from Table 5, after natural climate aging (heavy natural sunning is about 35h+ rainwater effect and is about 10h), the modifying asphalt that embodiment 5 modified carbon black obtains is same with the modifying asphalt that comparative example 5 ordinary carbon black obtains shows larger residual penetration ratio and residual Ductility ratio, and less softening temperature increment and viscosity aging index.In addition, comparative example 5 is compared with the modifying asphalt of embodiment 5, and the residual penetration ratio of the modifying asphalt that modified carbon black obtains and residual Ductility ratio are larger, and softening temperature increment and viscosity aging index less.This shows that 2 kinds of carbon blacks all improve the aging resistance of resistance to natural climate of pitch, wherein more obvious with the improvement effect of modified carbon black.
Embodiment 6:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 510 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, acetone is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add the nitric acid 500ml that carbon black that 50g is washed and concentration are 68%, by magnetic stirring apparatus, mixture is stirred 3h at 70 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch C of 90 mass parts, (25 DEG C of penetration degrees are 87dmm, softening temperature is 47.2 DEG C) be heated to 140 DEG C, add the sodium metnylene bis-naphthalene sulfonate of 5 mass parts and the modified carbon black of 5 mass parts, 35min is stirred under the rotating speed of 5000rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 700rpm stirring reaction 30min, obtain by the pitch C of above-mentioned modified carbon black modification.
Embodiment 7:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 550 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 80nm, tetracol phenixin is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add the nitric acid 500ml that carbon black that 50g is washed and concentration are 68%, by magnetic stirring apparatus, mixture is stirred 2h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 40%, is heated to 50 DEG C, stir speed (S.S.) 300r/min, under the environment of nitrogen, reacts 5h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch C of 92 mass parts, (25 DEG C of penetration degrees are 87dmm, softening temperature is 47.2 DEG C) be heated to 140 DEG C, add the sodium metnylene bis-naphthalene sulfonate of 4 mass parts and the modified carbon black of 4 mass parts, 40min is stirred under the rotating speed of 4000rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 600rpm stirring reaction 35min, obtain by the pitch C of above-mentioned modified carbon black modification.
Embodiment 8:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 500 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 100nm, chloroform is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add carbon black and hydrogen peroxide that 50g is washed, by magnetic stirring apparatus, mixture is stirred 3h at 70 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the potassium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 300r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
When obtained modified carbon black is carried out asphalt modification as additive, by the pitch D of 88 mass parts, (25 DEG C of penetration degrees are 79dmm, softening temperature is 49.3 DEG C) be heated to 120 DEG C, add the sodium metnylene bis-naphthalene sulfonate of 6 mass parts and the modified carbon black of 6 mass parts, 60min is stirred under the rotating speed of 6000rpm, maintain the temperature at 160 DEG C, reduce rotating speed to 500rpm stirring reaction 45min, obtain by the pitch D of above-mentioned modified carbon black modification.
Embodiment 9:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 550 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, use dimethylbenzene difference repeatedly regenerated from washing carbon black, and by Büchner funnel filtration under diminished pressure, remove its organic impurity.In the Erlenmeyer flask connecting spherical condensating tube, add the 5g processed and regenerate carbon black and 50ml potassium bichromate solution, by magnetic stirring apparatus, it is stirred 3h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash carbon black to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight.
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the potassium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 300r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
By the pitch D of 94 mass parts, (25 DEG C of penetration degrees are 79dmm, softening temperature is 49.3 DEG C) be heated to 120 DEG C, add the modified carbon black of copolymerized amine salt used and 3 mass parts of the SMA of 3 mass parts, 60min is stirred under the rotating speed of 3000rpm, maintain the temperature at 140 DEG C, reduce rotating speed and obtain modifying asphalt D to 800rpm stirring reaction 45min.
Embodiment 10:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 600 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, tetracol phenixin is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add carbon black and hydrogen peroxide that 50g is washed, by magnetic stirring apparatus, mixture is stirred 2h at 80 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 5h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
By the pitch E of 92 mass parts, (25 DEG C of penetration degrees are 65dmm, softening temperature is 53.1 DEG C) be heated to 120 DEG C, add the modified carbon black of copolymerized amine salt used and 4 mass parts of the SMA of 4 mass parts, 60min is stirred under the rotating speed of 3000rpm, maintain the temperature at 150 DEG C, reduce rotating speed and obtain modifying asphalt E to 800rpm stirring reaction 45min.
Embodiment 11:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 510 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 30nm, chloroform is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add carbon black and hydrogen peroxide that 50g is washed, by magnetic stirring apparatus, mixture is stirred 2h at 90 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
By the pitch E of 86 mass parts, (25 DEG C of penetration degrees are 65dmm, softening temperature is 53.1 DEG C) be heated to 130 DEG C, add the polyvinylpyrrolidone of 7 mass parts and the modified carbon black of 7 mass parts, 30min is stirred under the rotating speed of 3000rpm, maintain the temperature at 180 DEG C, reduce rotating speed and obtain modifying asphalt E to 800rpm stirring reaction 45min.
Embodiment 12:
Can be used as a modified carbon black for asphalt additive, obtained through anaerobic high temperature pyrolysis by waste rubber, and form through detergent washing, the activation of oxidizing and surfactant.The preparation method of this modified carbon black is specific as follows:
Take waste rubber as raw material, under anaerobic, through 600 DEG C of high temperature pyrolysis, then granulate and form the microspheroidal carbon black that diameter is 40nm, acetone is used repeatedly to wash obtained product, and by Büchner funnel filtration under diminished pressure, remove its organic impurity, in the Erlenmeyer flask connecting spherical condensating tube, add carbon black and hydrogen peroxide that 50g is washed, by magnetic stirring apparatus, mixture is stirred 3h at 70 DEG C of temperature, filter after being cooled to room temperature, repeatedly use deionized water wash filtrate to neutral, dry in the thermostatic drying chamber of 100 DEG C, and put into moisture eliminator constant weight,
In round-bottomed flask, add the oxidation-treated carbon black of 5g above-mentioned steps, 50ml phenol and 5ml concentration be the sodium hydroxide solution of 20%, is heated to 50 DEG C, stir speed (S.S.) 400r/min, under the environment of nitrogen, reacts 4h by magnetic stirrer.Reaction terminates rear filtration, by ethanol and distilled water repetitive scrubbing filtrate extremely neutrality, is dried to constant weight, obtains modified carbon black in the thermostatic drying chamber at 50 DEG C.
By the pitch F of 90 mass parts, (25 DEG C of penetration degrees are 80dmm, softening temperature is 49.6 DEG C) be heated to 130 DEG C, add the polyvinylpyrrolidone of 5 mass parts and the modified carbon black of 5 mass parts, 45min is stirred under the rotating speed of 3000rpm, maintain the temperature at 180 DEG C, reduce rotating speed and obtain modifying asphalt F to 600rpm stirring reaction 40min.
The above embodiment is only that its protection domain is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention, protection scope of the present invention is as the criterion with claims.
Claims (10)
1. can be used as a modified carbon black for asphalt additive, it is characterized in that, described modified carbon black by waste rubber through anaerobic high temperature pyrolysis, and successively through detergent washing, oxidizing and surfactant activation is obtained.
2. the modified carbon black that can be used as asphalt additive according to claim 1, is characterized in that, described modified carbon black is the globe of diameter 30nm ~ 100nm.
3. the preparation method that can be used as the modified carbon black of asphalt additive according to claim 1, is characterized in that, carries out as follows:
S1: take waste rubber as raw material, under anaerobic, through 500 DEG C ~ 600 DEG C high temperature pyrolysis, then granulates and forms the microspheroidal carbon black that diameter is 30nm ~ 100nm;
S2: employing washing composition repeatedly washs the carbon black obtained by S1, and by Büchner funnel filtration under diminished pressure, the organic impurity in removing carbon black;
S3: by the carbon black after S2 process and oxygenant with mass percent concentration be 0.5-2: 10 ratio mix, 2h ~ 3h is stirred at 70 DEG C ~ 90 DEG C temperature, filter after being cooled to room temperature, wash described carbon black to neutral, at 100 DEG C, carry out drying until constant weight;
S4: the carbon black after S3 process, phenol and strong base solution are mixed with the ratio that mass percent is 1: 10: 1, stir and be heated to 50 DEG C, stir speed (S.S.) is 300r/min ~ 400r/min, 2h ~ 4h is reacted under the environment of nitrogen, reaction terminates rear filtration, washing carbon black, to neutral, carry out drying until constant weight, obtains modified carbon black at 50 DEG C.
4. the preparation method that can be used as the modified carbon black of asphalt additive according to claim 3, is characterized in that, described washing composition is selected from least one in benzene,toluene,xylene, ethanol, acetone, chloroform, tetracol phenixin.
5. the preparation method that can be used as the modified carbon black of asphalt additive according to claim 3, is characterized in that, described oxygenant is selected from hydrogen peroxide, potassium bichromate solution, concentration are not less than at least one in the nitric acid of 60%.
6. the preparation method that can be used as the modified carbon black of asphalt additive according to claim 3, is characterized in that, the concentration of described strong base solution is 20% ~ 40%.
7. a modifying asphalt, it is characterized in that, be prepared from by melt blending by modified carbon black described in pitch, stablizer and claim 1, shared by each raw material, mass percent is: pitch 86% ~ 96%, modified carbon black 2% ~ 7%, stablizer 2% ~ 7%.
8. modifying asphalt according to claim 7, is characterized in that, described pitch is the one in road bitumen, and 25 DEG C of penetration degrees are 50dmm ~ 110dmm, and softening temperature is 42 DEG C ~ 60 DEG C.
9. modifying asphalt according to claim 7, is characterized in that, described stablizer is selected from that sodium metnylene bis-naphthalene sulfonate, SMA are copolymerized amine salt used, one in polyvinylpyrrolidone.
10. the preparation method of modifying asphalt according to claim 7, is characterized in that,
S11: take pitch, the modified carbon black of 2% ~ 7%, the stablizer of 2% ~ 7% that mass percent is 86% ~ 96% in proportion;
S12: by the asphalt heating to 120 in S11 DEG C ~ 140 DEG C, then add stablizer and modified carbon black, start shear mixer, at the rotating speed down cut 30min ~ 60min of 3000rpm ~ 6000rpm, make described modified carbon black be dispersed in pitch;
S13: S12 products therefrom is kept temperature 140 DEG C ~ 160 DEG C, reduces rotating speed to 500rpm ~ 1000rpm stirring reaction 30min ~ 45min, obtained modifying asphalt.
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| CN107286685A (en) * | 2017-07-04 | 2017-10-24 | 孙振轩 | Damaged tire thermal cracking carbon black asphalt modification additive |
| CN107298865A (en) * | 2016-04-15 | 2017-10-27 | 中路高科(北京)公路技术有限公司 | A kind of compound pyrolysis black pigment modifier and composite modified asphalt mixture |
| CN108410192A (en) * | 2018-03-29 | 2018-08-17 | 牛勇超 | A kind of modified pitch and its preparation process |
| CN109504134A (en) * | 2019-01-03 | 2019-03-22 | 蔡国政 | A kind of waste tire production carbon black treatment process |
| CN112011087A (en) * | 2020-07-21 | 2020-12-01 | 北京工业大学 | Asphalt thermal-oxidative aging resistant agent and preparation method thereof |
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| CN113201237A (en) * | 2021-04-30 | 2021-08-03 | 稷山县高盟色素炭黑有限公司 | Preparation method for improving blackness of gas-process carbon black and device for implementing method |
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Cited By (9)
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| CN107298865A (en) * | 2016-04-15 | 2017-10-27 | 中路高科(北京)公路技术有限公司 | A kind of compound pyrolysis black pigment modifier and composite modified asphalt mixture |
| CN106009121A (en) * | 2016-07-07 | 2016-10-12 | 芜湖风雪橡胶有限公司 | Abrasion-resistant rubber composition and preparation method of abrasion-resistant rubber |
| CN106829955A (en) * | 2017-01-23 | 2017-06-13 | 江苏理工学院 | A kind of method that utilization scrap tire rubber vacuum microwave prepares activated carbon |
| CN107286685A (en) * | 2017-07-04 | 2017-10-24 | 孙振轩 | Damaged tire thermal cracking carbon black asphalt modification additive |
| CN108410192A (en) * | 2018-03-29 | 2018-08-17 | 牛勇超 | A kind of modified pitch and its preparation process |
| CN109504134A (en) * | 2019-01-03 | 2019-03-22 | 蔡国政 | A kind of waste tire production carbon black treatment process |
| CN112011087A (en) * | 2020-07-21 | 2020-12-01 | 北京工业大学 | Asphalt thermal-oxidative aging resistant agent and preparation method thereof |
| CN112812580A (en) * | 2020-12-30 | 2021-05-18 | 中路交科科技股份有限公司 | High-viscosity high-elasticity modified asphalt for steel bridge deck and preparation method thereof |
| CN113201237A (en) * | 2021-04-30 | 2021-08-03 | 稷山县高盟色素炭黑有限公司 | Preparation method for improving blackness of gas-process carbon black and device for implementing method |
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