CN106867557A - A kind of preparation method of high softening point bitumen - Google Patents
A kind of preparation method of high softening point bitumen Download PDFInfo
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- CN106867557A CN106867557A CN201710135469.XA CN201710135469A CN106867557A CN 106867557 A CN106867557 A CN 106867557A CN 201710135469 A CN201710135469 A CN 201710135469A CN 106867557 A CN106867557 A CN 106867557A
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- softening point
- preparation
- high softening
- point bitumen
- bitumen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
A kind of preparation method of high softening point bitumen is that softening point is less than into 100oThe asphalt stock powder of C is placed in autoclave, and catalyst and crosslinking agent are added at room temperature, under the conditions of rotating speed is 50 500 r/min, is uniformly mixed, then with 2 10oThe programming rate of C/min is warming up to 200 350oC, by, from pressure is risen, 1 8h is reacted in pressurize, and exhaust bleeds off pressure rear cooling discharge, obtains final product high softening point bitumen in kettle.The present invention has the advantages that high softening-point, in high yield.
Description
Technical field
The invention belongs to a kind of method that high softening point bitumen is prepared by way of catalytic crosslinking.
Background technology
High softening point bitumen has coking value and excellent resistance to elevated temperatures higher, and it is in carbon refractory, pitch
The aspect such as based carbon fiber and spheric active carbon is widely used.Especially in the preparation process of asphalt-base globular active carbon
In, can effectively prevent spherula from melting deformation in process and bonding from high softening point bitumen raw material.
Traditionally, the production of high softening point bitumen typically uses solvent deasphalting or air blowing oxidation technique.The former generally adopts
With low-carbon alkanes cycling extraction asphalt stock, light component content is reduced.As described in patent of invention CN202766477U, using butane
As extractant, coal tar pitch is extracted at supercritical conditions.The softening point of this technique products obtained therefrom is relatively low, and solvent recovery is tired
Difficulty, complex process.And air blowing oxidation technique blasts large quantity of air promotion pitch polycondensation under relying primarily on high temperature.According to patent
CN102391885A and patent CN1183222C reports that oxidation reaction system needs to be in 200 for a long timeoMore than C, exist coking and
The risk caught fire, and due to gas skewness, oxidation efficiency is relatively low, asphalt softening point lifting effect is undesirable.
Therefore, other patents of invention are improved, the method that such as patent CN102363731A is provided is first to drip raw material
Green grass or young crops melting simultaneously carries out high temperature, high-speed oxidation, then is passed to vaporific tempering tower and carries out rapid flash；Patent CN105567275A is
First by dipping agent bitumen through air oxidation, add in scraper film evaporator, carry out vacuum distillation, high-purity is obtained high soft
Change point pitch；Patent CN103184062A be by refined bitumen constant temperature thermal polycondensation after, then pull out light group through vacuum wiped film vaporization
Point；Method disclosed in patent CN104946289A is first to carry out airoxidation to mid temperature pitch, then uses what is vacuumized
Method pulls out part light component.There is general character in above method, be first to be processed through thermal polycondensation, then walked through flash distillation, vacuum distillation etc.
Rapid removing light component.Complex process, it is higher to the requirement of equipment vacuum degree, and produce substantial amounts of light group of the pitch that cannot effectively utilize
Point, product yield is relatively low, influences integrated cost.
At present, to improve asphalt softening point, the processing mode of catalytic asphalt component cross-link is taken seriously, and which is by adding
Enter catalyst or property-modifying additive to improve pitch thermal condensation reaction efficiency.Patent CN102464989A discloses a kind of high soft
Change the preparation method of point pitch, mix with reaction additives after pitch is heated into molten condition first, then in 200-340oC
Lower air blowing oxidation 3-10 hours, wherein additive is：One kind or several in copper sulfide, zinc chloride, iron chloride and phosphorus pentoxide
Kind, and polyphosphoric acids, product softening point is up to 150oC；Patent CN1760331A is related to a kind of the modified of adjustable softening point
After the production method of pitch, i.e. asphalt stock are with acid adjustment pH value, mix with formaldehyde, metaformaldehyde or paraformaldehyde, in 100-
150oProduct softening point is up to 134 after C polymerase 10 .1-24 hoC.It can be seen that, the method for catalytic crosslinking can lower temperature and compared with
Promote asphalt softening point lifting in short time, be conducive to energy-saving, but the softening point of gained pitch is relatively low, is typically extremely difficult to
More than 180 DEG C.
The content of the invention
For preparing at present, the easy coking of product present in high softening point bitumen technique, yield are low and softening point is low asks
Topic, the present invention proposes a kind of by catalytic asphalt component to carry out cross-linking reaction to prepare high softening-point, in high yield asphaltic products
Method.
The preparation method of high softening point bitumen of the present invention, comprises the following steps：
Softening point is less than 100oThe asphalt stock powder of C is placed in autoclave, and catalyst and crosslinking agent are added at room temperature,
Under the conditions of rotating speed is 50-500 r/min, it is uniformly mixed, then with 2-10oThe programming rate of C/min is warming up to 200-350oC,
By, from pressure is risen, pressurize reaction 1-8h, exhaust bleeds off pressure rear cooling discharge, obtains final product high softening point bitumen in kettle.
As described above, softening point is less than 100oThe asphalt stock of C is included in coal tar asphalt, asphalt and bitumen
One or more mixtures, the particle diameter of asphalt stock powder is less than 50 mesh.
As described above, during catalyst is lewis acid catalyst, i.e. anhydrous Aluminum chloride, iron chloride, zinc chloride and stannic chloride
One or more, and described lewis acid catalyst addition accounts for the 1% -10% of asphalt stock silty amount, preferably 2%-
5%, the particle diameter of catalyst is less than 50 mesh.
As described above, crosslinking agent includes：One or more in carbon tetrachloride, chloroform, dichloromethane and bromofom, and it is described
Crosslinking agent addition accounts for the 5% -30% of asphalt stock silty amount, preferably 10%-20%.
Inventive process have the advantage that： 1）Using Louis acid catalysis asphaltene molecule itself and asphaltene molecule and friendship
Join the polymerisation of agent, asphalt softening point, prepared high softening-point drip can be effectively improved in lower temperature and in the short period
Blue or green softening point is 180oMore than C；2）In process of production, premixed at room temperature with catalyst, crosslinking agent using powder raw material,
Substantially increase the contact effect of catalyst and crosslinking agent with pitch, it is to avoid the sticky caused material of system is mixed when high temperature feeds intake
Close uneven；3）Reaction is completed in closed autoclave, is produced from boosting, and being conducive to thermal condensation to react is carried out；4）It is soft
The lifting for changing point depends on the crosslinking polycondensation of pitch light component rather than merely pulls out light component, improves product yield；5）It is whole
One pot of completion of individual reaction, saves the steps such as material transfer, distillation, simple to operate.
Specific embodiment
The inventive method will be described further by some embodiments below, but therefore not limit this hair
Bright method.Wherein, the percentage composition is weight/mass percentage composition.
Embodiment 1
By 100 g softening points 75oThe coal tar asphalt powder of C（80 mesh）It is placed in autoclave, the anhydrous chlorine of 1 g is added at room temperature
Change aluminium powder (80 mesh) and 10 g chloroformic solutions, in the case where rotating speed is 50 r/min, be uniformly mixed, then with 5oThe liter of C/min
Warm speed is warming up to 250oC, by, from pressure is risen, 1 h is reacted in pressurize in kettle；Exhaust bleeds off pressure rear cooling discharge, gained Asphalt Production
Product softening point 228oC, yield 80%.
Embodiment 2
By 200 g softening points 45oThe asphalt powder of C（60 mesh）It is placed in autoclave, the anhydrous chlorine of 10 g is added at room temperature
Change iron powder（80 mesh）With 10 g carbon tetrachloride solutions, in the case where rotating speed is 500 r/min, it is uniformly mixed, then with 10oC/
The programming rate of min is warming up to 350oC, by, from pressure is risen, 4 h are reacted in pressurize in kettle；Exhaust bleeds off pressure rear cooling discharge, gained
Asphaltic products softening point 264oC, yield 73%.
Embodiment 3
By 200 g softening points 80oThe coal tar asphalt milling of C（60 mesh）It is placed in autoclave, adds 1 g anhydrous at room temperature
Aluminum chloride powder（80 mesh）, 5 g anhydrous ferric chloride powder（80 mesh）, 10 g carbon tetrachloride solutions and 10 g chloroformic solutions, stirring
Well mixed, rotating speed is 200 r/min；With 2oThe programming rate of C/min is to 300oC, by, from pressure is risen, pressurize reacts 3 in kettle
h；Exhaust bleeds off pressure rear cooling discharge, gained asphaltic products softening point 271oC, yield 78%.
Embodiment 4
By the coal tar asphalt powder of 150 g（Softening point 75oC, 60 mesh）With asphalt powder（Softening point 45oThe mesh of C 60）Mixture
（Both compare 1 at weight:1）It is placed in autoclave；3 g anhydrous zinc chloride powder are added at room temperature（80 mesh）It is molten with 45 g bromofoms
Liquid, is uniformly mixed, and rotating speed is 200 r/min；With 2oThe programming rate of C/min is to 200oC, by pressure is risen in kettle certainly, protects
8 h of pressure reaction；Exhaust bleeds off pressure rear cooling discharge, gained asphaltic products softening point 193oC, yield 84%.
Embodiment 5
By 100 g softening points 70oThe bitumen milling of C（60 mesh）It is placed in autoclave, adds 10 g anhydrous at room temperature
Chlorination tin powder（80 mesh）With 30g dichloromethane solutions, it is uniformly mixed, rotating speed is 400 r/min；With 5oThe liter of C/min
Warm speed is to 220oC, by, from pressure is risen, 4 h are reacted in pressurize in kettle；Exhaust bleeds off pressure rear cooling discharge, and gained asphaltic products is soft
Change point 185oC, yield 81%.
Embodiment 6
By the asphalt powder of 100 g（Softening point 45oC, 60 mesh）With bitumen powder（Softening point 70oC, 60 mesh）Mixture
（Both compare 4 at weight:1）Mixture is placed in autoclave；1 g anhydrous Aluminum chloride powder is added at room temperature（80 mesh）, 2 g without
Water zinc chloride powder（80 mesh）, 10 g carbon tetrachloride solutions and 10 g chloroformic solutions, be uniformly mixed, rotating speed is 250 r/
min；With 5oThe programming rate of C/min is to 250oC, by, from pressure is risen, 6 h are reacted in pressurize in kettle；Exhaust lowers the temperature after bleeding off pressure
Material, gained asphaltic products softening point 205oC, yield 79%.
Embodiment 7
By the coal tar asphalt powder of 200 g（Softening point 75oC, 80 mesh）, asphalt powder（Softening point 45oC, 60 mesh）With it is natural
Asphalt powder（Softening point 70oC, 60 mesh）Mixture（Three's weight compares 3:1:1）It is placed in autoclave；2 g are added at room temperature
Anhydrous Aluminum chloride powder（80 mesh）, 1 g anhydrous ferric chloride powder（80 mesh）, 3 g anhydrous zinc chloride powder（80 mesh）, 10 g tetrachloros
Change carbon solution, 10 g chloroformic solutions and 10 g dichloromethane solutions, be uniformly mixed, rotating speed is 300 r/min；With 6oC/
The programming rate of min is to 240oC, by, from pressure is risen, 4 h are reacted in pressurize in kettle；Exhaust bleeds off pressure rear cooling discharge, gained pitch
Product softening point 235oC, yield 81%.
Embodiment 8
By the coal tar asphalt powder of 300 g（Softening point 75oC, 80 mesh）With bitumen powder（Softening point 70oC, 80 mesh）Mixture
（Both compare 2 at weight:1）It is placed in autoclave；3 g anhydrous Aluminum chloride powder are added at room temperature（80 mesh）, the anhydrous chlorinations of 2 g
Iron powder（80 mesh）, 20 g chloroformic solutions and 10 g bromofom solution, be uniformly mixed, rotating speed is 300 r/min；With 2oC/
The programming rate of min is to 280oC, by, from pressure is risen, 4 h are reacted in pressurize in kettle；Exhaust bleeds off pressure rear cooling discharge, gained pitch
Product softening point 252oC, yield 72%.
Claims (11)
1. a kind of preparation method of high softening point bitumen, it is characterised in that comprise the following steps：
Softening point is less than 100oThe asphalt stock powder of C is placed in autoclave, and catalyst and crosslinking agent are added at room temperature,
Under the conditions of rotating speed is 50-500 r/min, it is uniformly mixed, then with 2-10oThe programming rate of C/min is warming up to 200-350oC,
By, from pressure is risen, pressurize reaction 1-8h, exhaust bleeds off pressure rear cooling discharge, obtains final product high softening point bitumen in kettle.
2. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the softening point is less than
100oThe asphalt stock of C includes one or more mixtures in coal tar asphalt, asphalt and bitumen.
3. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the particle diameter of asphalt stock powder
Less than 50 mesh.
4. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the catalyst is Louis
This acid catalyst.
5. a kind of preparation method of high softening point bitumen as claimed in claim 4, it is characterised in that the Louis acid catalysis
Agent is one or more in anhydrous Aluminum chloride, iron chloride, zinc chloride, stannic chloride.
6. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the catalyst loading
Account for the 1% -10% of asphalt stock silty amount.
7. a kind of preparation method of high softening point bitumen as claimed in claim 6, catalyst loading described in its feature accounts for drip
The 2%-5% of blue or green raw material silty amount.
8. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the particle diameter of catalyst is less than
50 mesh.
9. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the crosslinking agent includes four
One or more in chlorination carbon, chloroform, dichloromethane, bromofom.
10. a kind of preparation method of high softening point bitumen as claimed in claim 1, it is characterised in that the crosslinking agent addition
Account for the 5% -30% of asphalt stock silty amount.
A kind of 11. preparation methods of high softening point bitumen as claimed in claim 1, it is characterised in that the crosslinking agent addition
Account for the 10%-20% of asphalt stock silty amount.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720747A (en) * | 2017-10-31 | 2018-02-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method rich in mesopore asphalt-base globular active carbon |
| CN111423592A (en) * | 2020-04-10 | 2020-07-17 | 中国科学院山西煤炭化学研究所 | Preparation method of low-viscosity high-carbon-residue-rate binder asphalt for carbon materials |
| CN112079958A (en) * | 2019-06-12 | 2020-12-15 | 中国石化扬子石油化工有限公司 | Preparation method of carbon-five copolymerized petroleum resin |
| WO2022077090A1 (en) * | 2020-10-16 | 2022-04-21 | Adven Industries Inc. | Process for the control of softening points of petroleum hydrocarbon materials |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213677A (en) * | 1990-10-22 | 1993-05-25 | Mitsubishi Kasei Corporation | Spinning pitch for carbon fibers and process for its production |
| CN1185491A (en) * | 1996-12-20 | 1998-06-24 | 中国科学院山西煤炭化学研究所 | Process for preparing middle phase asphalt |
| EP1717275A1 (en) * | 2005-04-25 | 2006-11-02 | Repsol Ypf S.A. | Bituminous binder, process for applying the same and its use for road paving |
| CN102169988A (en) * | 2011-03-30 | 2011-08-31 | 深圳市翔丰华科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103421467A (en) * | 2013-08-16 | 2013-12-04 | 山西喜跃发路桥建筑材料有限公司 | High-performance rubber asphalt pouring sealant and preparation method thereof |
| CN105720258A (en) * | 2014-12-03 | 2016-06-29 | 上海杉杉科技有限公司 | Lithium ion battery negative electrode material and preparation method and application thereof, and lithium ion battery |
-
2017
- 2017-03-09 CN CN201710135469.XA patent/CN106867557B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213677A (en) * | 1990-10-22 | 1993-05-25 | Mitsubishi Kasei Corporation | Spinning pitch for carbon fibers and process for its production |
| CN1185491A (en) * | 1996-12-20 | 1998-06-24 | 中国科学院山西煤炭化学研究所 | Process for preparing middle phase asphalt |
| EP1717275A1 (en) * | 2005-04-25 | 2006-11-02 | Repsol Ypf S.A. | Bituminous binder, process for applying the same and its use for road paving |
| CN102169988A (en) * | 2011-03-30 | 2011-08-31 | 深圳市翔丰华科技有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103421467A (en) * | 2013-08-16 | 2013-12-04 | 山西喜跃发路桥建筑材料有限公司 | High-performance rubber asphalt pouring sealant and preparation method thereof |
| CN105720258A (en) * | 2014-12-03 | 2016-06-29 | 上海杉杉科技有限公司 | Lithium ion battery negative electrode material and preparation method and application thereof, and lithium ion battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720747A (en) * | 2017-10-31 | 2018-02-23 | 中国科学院山西煤炭化学研究所 | A kind of preparation method rich in mesopore asphalt-base globular active carbon |
| CN107720747B (en) * | 2017-10-31 | 2020-02-14 | 中国科学院山西煤炭化学研究所 | Preparation method of mesoporous-asphalt-based spherical activated carbon |
| CN112079958A (en) * | 2019-06-12 | 2020-12-15 | 中国石化扬子石油化工有限公司 | Preparation method of carbon-five copolymerized petroleum resin |
| CN111423592A (en) * | 2020-04-10 | 2020-07-17 | 中国科学院山西煤炭化学研究所 | Preparation method of low-viscosity high-carbon-residue-rate binder asphalt for carbon materials |
| WO2022077090A1 (en) * | 2020-10-16 | 2022-04-21 | Adven Industries Inc. | Process for the control of softening points of petroleum hydrocarbon materials |
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