CN1073144C - Method for production of modified asphalt for construction - Google Patents
Method for production of modified asphalt for construction Download PDFInfo
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- CN1073144C CN1073144C CN97121664A CN97121664A CN1073144C CN 1073144 C CN1073144 C CN 1073144C CN 97121664 A CN97121664 A CN 97121664A CN 97121664 A CN97121664 A CN 97121664A CN 1073144 C CN1073144 C CN 1073144C
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Abstract
The present invention discloses a method for preparing modified building asphalt. Firstly, the asphalt raw material is processed, and modifiers are added in the basic asphalt after the asphalt achieves the certain index. The present invention not only has good performance of the prepared modified building asphalt, but also greatly saves the dosage of the modifiers and reduces the cost.
Description
Petroleum pitch has good thermoplastic, tackiness, and visco-elasticity is the base mateiral of construction waterproofing engineering.But because its susceptibility to temperature is stronger, i.e. hardening in winter embrittlement, deliquescing trickling in summer adopt pitch can't satisfy the needs of modern construction engineering as the buildings waterproof base material merely, so modified asphalt technology is developed rapidly.After in pitch, adding the high molecular polymer modification, make pitch have some characteristic of polymkeric substance, improved asphalt performance greatly, make its weathering resistance, temperature sensibility and all be significantly increased with the adaptability of substrate be full of cracks.
Over more than 100 year, people have carried out a large amount of exploration and practices in this field, use multiple high molecular polymer, and various technology has been carried out experimental study.But, up to the present, patent, the treatise of the domestic and international relevant this respect of being delivered and the study on the modification that majority were engaged in, all be residual oil with crude oil, or the pitch of the different trades mark directly carries out modification and research as basic asphalt, the improvement of asphalt performance all relies on expensive high molecular polymer properties-correcting agent to realize that its product cost is very high.The high molecular polymer add-on of the modifying asphalt that each producer of present China building materials system is produced is generally about 20 (w) %; United States Patent (USP) 4485201 has been announced a kind of modifying asphalt prescription, is example with example 1 only, in mass fraction, and pitch 3.00, cycloalkyl technical oil 0.42, shell DUTREX954 oil 0.105, oxidation inhibitor 0.0158, rubber powder 0.776, SBS 0.267, tackifier 0.01.Prescription can be calculated thus, and pitch only accounts for 65 (w) %, and various properties-correcting agent then account for 23.27 (w) %.
Therefore purpose of the present invention is exactly at above existing in prior technology shortcoming, proposes a kind of preparation method of modified asphalt for construction, reduces the add-on of high molecular polymer, thereby cost is reduced significantly.
Main points of the present invention organically combine the improvement of feedstock property and two kinds of technologies of high molecular polymer modification exactly, complement each other, and bring out the best in each other.
Pitch itself is a heterogeneous system, and wherein bituminous matter is the core of pitch colloidal structure, and it is dispersed in fragrance branch, the saturated branch by colloid, forms stable colloidal dispersion.In general, asphalt content is few, colloid, fragrance are divided, saturated minute many, the finely disseminated pitch of bituminous matter of content, its cohesiveness, plasticity, good fluidity, and temperature stability is relatively poor.The present invention just is being based on this thought, at first through handling, asphalt content in the pitch is increased relatively, saturated branch, fragrance divide content to reduce relatively, so that four components do match in the pitch are tending towards rationally, and keep its cohesiveness as far as possible, the characteristics of visco-elasticity, good fluidity, improve the deficiency of high and low temperature stability, thus the pitch that the visco-elasticity of making, ageing resistance etc. all have a more substantial increase, in order to basic asphalt as modifying asphalt.
In said process, when asphalt stock is handled, control 25 ℃ of penetration degrees of gained basic asphalt in the 40-1001/10mm scope, preferred 50-901/10mm; Ring and ball softening point in 20-90 ℃ of scope, preferred 40-80 ℃.
It is more to improve the basic asphalt method for quality, and with oxidation style, the blending method is more commonly used.For the single variety raw material, or form complementary distant plurality of raw materials, should be advisable with method for oxidation.
Building asphalt generally all requires its softening temperature higher (more than 90 ℃), and required oxidization time is also longer.Oxidation not only influences the processing power of device for a long time, and quality product is also had disadvantageous effect.Therefore people have just been developed the catalyzed oxidation technology of introducing catalyzer in the pitch oxidation process, to quicken its reaction.Compare with common oxidation, catalyzed oxidation both had can shorten the reaction times, reduce temperature of reaction, the character of catalytic oxidized asphalt obviously is better than advantages such as common oxidized bitumen.At present, the catalyzer that can be used for pitch oxidation has nearly hundred kinds, the used P that therefrom filters out for the inventor of the present invention
2O
5, H
2CO
3, Na
2CO
3, H
3PO
4, FeCl
3Deng.
According to the present invention, use these catalyzer, can carry out catalyzed oxidation to asphalt stock, to reach the purpose of improving its character.Usually the oxidizing process condition is: 150～290 ℃ of oxidizing temperatures, aspect ratio (charging or charging liquid level and tower, still diameter ratio) 2～10, air-blowing quantity 60～200m
3/ T.Hr, oxidization time 2～10Hr, catalyzer add-on [accounting for inlet amount (W)] 0.1～7%, mode of oxidizing can be continous way or intermittent type.Typical oxidizing process condition is: 200～260 ℃ of oxidizing temperatures, aspect ratio 3～6, air-blowing quantity 80～180M
3/ T.Hr, oxidization time 4～8Hr, 0.2～5% of catalyzer add-on.
According to the present invention, the high molecular polymer that modification is used can be natural rubber, synthetic rubber, synthetic plastics, waste old, synthetic rubber latex, synthetic resins etc.Wherein, SBS, APP effect are better.Modified technique can be with traditional chaotropic agent swelling, mechanical mixing method, also available other efficient ways etc.Yet with the miscible method modification of the Mechanical Crushing of first-selection of the present invention, technology is simpler, and effect is better.
Use the miscible method of Mechanical Crushing that adopts in the process of the present invention, be exactly in 160～200 ℃ heated bitumen, with the method for machinery particle diameter is broken for the homogeneous particulate that particle diameter is 4um continuously less than the high molecular polymer of 10mm, and under the high-speed stirring of crushing mechanism, make high molecular polymer and heated bitumen evenly miscible, form modified bitumen product.
Because the present invention organically combines catalytic oxidation modification and high molecular polymer modified technique, has received the effect of achieving many things at one stroke.The enforcement of this combination process, one: both raising by a relatively large margin the quality of modifying asphalt, again minimizing by a relatively large margin the add-on of polymkeric substance, generally more than 20% (w), thereby reduced product cost; Two: by the enforcement of this combination process, feedstock property is greatly improved, as the raw material of producing asphaltic products. in dual upgrading process to satisfy the quality product requirement for many being not suitable for.This just for enlarging raw material sources, increases output, and meeting the need of market provides condition; Three: because catalytic oxidation process has increased substantially the basic asphalt quality, just reduced the harsh requirement to polymer modifiers, providing for the use modified effect is poor slightly, still inexpensive, the wide properties-correcting agent in source achieves the goal may; Four; The enforcement of combination process has increased the handiness of modified technique.
Embodiment one
With a kind of paraffin-intermediate base vacuum residuum (25 ℃ of penetration degree 1741/10mm, 38 ℃ of ring and ball softening points, 25 ℃ of ductilities are 84cm) be raw material, the molecular weight of producing with yueyang, hunan general petrochemical works rubber plant is that 100000 the granular SBS of line style is a properties-correcting agent, preparation water-proof material modifying asphalt.Require the high-temperature heat-resistance degree of the glass fiber blank malthoid of the preparation of modifying asphalt thus to be higher than 90 ℃, low-temperature tenderness is lower than-25 ℃, and tensile strength is greater than 300N.
Earlier vacuum residuum is carried out the catalyzed oxidation upgrading on the medium-sized oxidation unit of 10 liters intermittent type.Specific implementation process is: the raw material residual oil 6.3Kg that will be heated to 150 ℃ adds in the stills for air blowing, and aspect ratio 4: 1 (ratio of work loading height and tower or still diameter) adds the H that accounts for raw material 2.3w% under stirring condition
3PO
4Catalyzer after stirring, was raised to 200 ℃ with temperature in the kettle in 30 minutes, the beginning air blowing oxidation, and air-blowing quantity is 170M
3/ THr, oxidation 4 hours, the softening temperature that records oxidized bitumen is 60 ℃, penetration degree 701/10mm, 25 ℃ of ductility 43cm, Flash brittle point-38 ℃.With this oxidized bitumen is that basic asphalt carries out the SBS modification.
This example is to adopt chaotropic agent swelling, paddling process modification, be chaotropic agent greater than 320 ℃ lubex promptly with initial boiling point, heating is dissolved the back and is mixed with 1: 1 (m) with SBS and be placed under the room temperature swelling 12 hours, be heated to 120 ℃ then, stir miscible joining after evenly in 160 ℃ the heated bitumen, and keep mixed solution under 160 ℃ of temperature, got final product in 1 hour with 1000～1200 rev/mins stirring velocitys stirrings.
With the catalytic oxidized asphalt is that basic asphalt carries out the SBS modification.Gross weight with SBS and basic asphalt is a benchmark, when the SBS add-on is 15w%, is-25 ℃ with the low-temperature tenderness of the glass fiber blank malthoid of this bitumen production, 95 ℃ of high-temperature heat-resistance degree, and tensile strength＞300N, every index all conforms with requirement.
Comparative example 1 with the same asphalt stock of embodiment 1 directly as basic asphalt, and do not carry out oxide treatment, carry out the SBS modification, when the add-on of SBS is 23w%, the low-temperature tenderness of the same tire base oil felt that makes with this modifying asphalt is qualified for-25 ℃, and high-temperature heat-resistance degree and tensile strength all can not meet the demands.
This shows that SBS 34.78% (m) is added at the basic asphalt end after oxide treatment is than oxide treatment.(amount 23% of (the not oxidised amount 15% of the amount 23%-of SBS that processing adds in this example)/not oxidised SBS that processing adds, method of calculation are herewith routine in following examples) through SBS that oxide treatment adds
Embodiment two
(25 ℃ of ductilities＞140cm) are raw material, when residual oil is preheated to 150 ℃, add in the stills for air blowing, add the H that accounts for raw material 1.5% (m) under stirring condition for 25 ℃ of penetration degree 1411/10mm, 41 ℃ of softening temperatures with a kind of vacuum residuum of cycloalkanes-intermediate base crude oil
3PO
4Catalyzer, and after stirring, in 30 minutes, temperature in the kettle is risen to 260 ℃ and begin air blowing oxidations.After 4 hours 20 minutes, the softening temperature of oxidized bitumen is 69 ℃, penetration degree 711/10mm, 25 ℃ of ductility 87cm, Flash brittle point-29 ℃.With this oxidized bitumen is that basic asphalt carries out the SBS modification.When basic asphalt is cooled to 180 ℃, begin to carry out modification with mechanical crushing method.Detailed process is when the crusher high speed rotating, and SBS is slowly added the crusher inlet that places heated bitumen equably, becomes the particulate that particle diameter is 4um after fragmentation, and forms evenly miscible modified bitumen product under high-speed stirring.
In the present embodiment, when the SBS add-on is 14w%, the modified asphalt felt low-temperature tenderness-25 that makes thus ℃, 95 ℃ of high-temperature heat-resistance degree, tensile strength＞300N, quality index meets the requirement among the embodiment one fully.
Comparative example 2 is raw materials used identical with embodiment 2, does not carry out oxide treatment, and the adding method of SBS is with embodiment 2, but will make the malthoid of equal performance the time, the add-on of SBS but will increase 39w%.
Embodiment three
With a kind of butane de-oiled asphalt of paraffinic crude and the residual oil of naphthenic base crude, after mixing with certain proportion is raw material (25 ℃ of penetration degree 1211/10mm, 41.7 ℃ of softening temperatures, 25 ℃ of ductility 107cm), the Atactic Polypropelene APP that produces with Liaoyang chemical industrial company is a properties-correcting agent, preparation waterproof roll modifying asphalt.Require the high-temperature heat-resistance degree of the glass fiber blank malthoid of the preparation of modifying asphalt thus to be higher than 100 ℃, low-temperature tenderness is lower than-10 ℃.
The raw material that is preheating to 150 ℃ is injected stills for air blowing, add the FeCl of 0.2w%
3After catalyzer stirred, within 30 minutes, with still temperature rise to 240 ℃, air-blowing quantity was 150M
3/ T.Hr, oxidation 5 hours, the softening temperature that records oxidized bitumen is 86 ℃, 25 ℃ of penetration degree 421/10mm, 25 ℃ of ductility 18cm, Flash brittle point-13 ℃.When oxidized bitumen is cooled to 170 ℃,,, make the APP modifying asphalt carrying out modification in the APP adding heated bitumen with Mechanical Crushing consolute method.
In the present embodiment, when the APP add-on is 9w%, the modified asphalt felt that makes, quality index satisfies the requirement in the present embodiment.
Comparative example 3 raw materials, properties-correcting agent do not carry out oxide treatment with embodiment 3, directly add properties-correcting agent and carry out modification, and when the add-on of APP was 12w%, quality product could satisfy index request, had increased 25w% than embodiment 3.
Annotate: the measurement of the high-temperature heat-resistance degree that the present invention relates to, low-temperature tenderness, tensile strength is undertaken by prescriptive procedure among the GB326-89.
Claims (5)
1, a kind of method for preparing modified asphalt for construction, comprise: in basic asphalt, add high molecular polymer, it is characterized in that at first adopting catalytic oxidation to handle asphalt stock, make gained basic asphalt ring and ball softening point in 20-90 ℃ of scope, 25 ℃ of penetration degrees and then add high molecular polymer in basic asphalt in the 40-1001/10mm scope; Described high molecular polymer is one or more in natural rubber, synthetic rubber, synthetic plastics, waste old, synthetic rubber latex, the synthetic resins; The processing condition that described catalytic oxidation is handled asphalt stock are: catalyzer is to be selected from H
3PO
4, P
2O
5, FeCl
3, Na
2CO
3And H
2CO
3In a kind of, oxidizing temperature is 150-290 ℃, aspect ratio is 2-10, air-blowing quantity is 60-200M
3/ T.Hr, oxidization time are 2-10 hour, and the catalyzer add-on accounts for the 0.1%-7% of raw material gross weight, and mode of oxidizing is continous way or intermittent type; The method of described adding high molecular polymer is the miscible method of chaotropic agent swelling, mechanical mixing method or Mechanical Crushing.
2, according to the described method for preparing modified asphalt for construction of claim 1, the softening temperature that it is characterized in that described basic asphalt is 40-80 ℃, and 25 ℃ of penetration degrees are in 50-90 1/10mm scope.
3,, it is characterized in that described catalyzed oxidation processing condition are according to the described method for preparing modified asphalt for construction of claim 1:
Catalyzer: H
3PO
4Or FeCl
3
Oxidizing temperature: 200-260 ℃;
Aspect ratio: 3-6;
Air-blowing quantity: 80-180M
3/ THr;
Oxidization time: 4-8 hour;
The catalyzer add-on accounts for the 0.2%-5% of raw material gross weight.
4,, it is characterized in that described high molecular polymer is one or both among SBS and the APP according to the described method for preparing modified asphalt for construction of claim 1.
5, according to the described method for preparing modified asphalt for construction of claim 1, it is characterized in that the miscible method of described Mechanical Crushing is meant that the method with machinery is broken for the homogeneous particulate that particle diameter is 4 μ m with particle diameter continuously less than the high molecular polymer of 10mm, under the high-speed stirring of crushing mechanism, high molecular polymer and heated bitumen is miscible equably, form modified bitumen product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121664A CN1073144C (en) | 1997-11-24 | 1997-11-24 | Method for production of modified asphalt for construction |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121664A CN1073144C (en) | 1997-11-24 | 1997-11-24 | Method for production of modified asphalt for construction |
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| Publication Number | Publication Date |
|---|---|
| CN1218085A CN1218085A (en) | 1999-06-02 |
| CN1073144C true CN1073144C (en) | 2001-10-17 |
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|---|---|---|---|
| CN97121664A Expired - Fee Related CN1073144C (en) | 1997-11-24 | 1997-11-24 | Method for production of modified asphalt for construction |
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| CN107988814A (en) * | 2017-11-21 | 2018-05-04 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of low temperature resistant modified asphalt waterproof coiled material |
| CN112878728A (en) * | 2021-02-23 | 2021-06-01 | 安徽墨砂工程修缮技术有限公司 | Repairing method for basement leakage |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US448520A (en) * | 1891-03-17 | hig-g-inbottom | ||
| CN1139727A (en) * | 1995-07-05 | 1997-01-08 | 哈尔滨市顺达建筑材料厂 | Production method for rubber plastics modified bitumen water proof coiled material |
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1997
- 1997-11-24 CN CN97121664A patent/CN1073144C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US448520A (en) * | 1891-03-17 | hig-g-inbottom | ||
| CN1139727A (en) * | 1995-07-05 | 1997-01-08 | 哈尔滨市顺达建筑材料厂 | Production method for rubber plastics modified bitumen water proof coiled material |
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| CN1218085A (en) | 1999-06-02 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMIC Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL RESEARCH INSTITUTE |
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Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Petro-Chemical Inst., SINOPEC |
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