CN106867557B - A kind of preparation method of high softening point bitumen - Google Patents
A kind of preparation method of high softening point bitumen Download PDFInfo
- Publication number
- CN106867557B CN106867557B CN201710135469.XA CN201710135469A CN106867557B CN 106867557 B CN106867557 B CN 106867557B CN 201710135469 A CN201710135469 A CN 201710135469A CN 106867557 B CN106867557 B CN 106867557B
- Authority
- CN
- China
- Prior art keywords
- softening point
- high softening
- asphalt
- preparation
- bitumen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- 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 by softening point lower 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 revolving speed is 50-500 r/min, is uniformly mixed, then with 2-10oThe heating rate of C/min is warming up to 200-350oC, by, from boosting power, 1-8h is reacted in pressure maintaining in kettle, exhaust bleeds off pressure rear cooling discharge to get high softening point bitumen.The present invention has the advantages that high softening-point, high yield.
Description
Technical field
The method that the invention belongs to a kind of to prepare high softening point bitumen by way of catalytic crosslinking.
Background technique
High softening point bitumen coking value with higher and excellent high temperature resistance, in carbon refractory, pitch
Based carbon fiber and spheric active carbon etc. are widely used.Especially in the preparation process of asphalt-base globular active carbon
In, it selects high softening point bitumen raw material to can effectively prevent spherula and melts deformation and bonding in process.
Traditionally, the production of high softening point bitumen generally uses solvent deasphalting or air blowing oxidation technique.The former usually 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 lower, and solvent recovery is tired
Difficulty, complex process.And air blowing oxidation technique relies primarily on and blasts large quantity of air promotion pitch polycondensation under high temperature.According to patent
CN102391885A and patent CN1183222C report, oxidation reaction system need to be in 200 for a long timeoC or more, there are coking and
The risk of kindling, and since gas is unevenly distributed, oxidation efficiency is lower, and it is undesirable that asphalt softening point promotes effect.
For this purpose, other patents of invention are improved, if the patent CN102363731A method provided is first to drip raw material
Blueness melts and carries out high temperature, high-speed oxidation, then is passed to misty tempering tower and carries out rapid flash；Patent CN105567275A is
Dipping agent bitumen is added in scraper film evaporator through air oxidation first, is evaporated under reduced pressure, it is soft that high-purity height is made
Change point pitch；Patent CN103184062A is then to pull out light group through vacuum wiped film vaporization for after refined bitumen constant temperature thermal polycondensation
Point；Method disclosed in patent CN104946289A is first then to use to vacuumize to mid temperature pitch progress airoxidation
Method pulls out part light component.There are general character for above method, are the step such as first to handle, then flashed, be evaporated under reduced pressure through thermal polycondensation
Rapid removing light component.Complex process, it is more demanding to equipment vacuum degree, and generate light group of pitch for can not largely efficiently using
Point, product yield is lower, influences overall cost.
Currently, the processing mode of catalytic asphalt component cross-link is taken seriously to improve asphalt softening point, which is by adding
Enter catalyst or modified additive, Lai Tigao pitch thermal condensation reaction efficiency.Patent CN102464989A discloses a kind of high soft
The preparation method for changing point pitch, pitch is heated to after molten condition mixing with reaction additives, then in 200-340 firstoC
Lower air blowing oxidation 3-10 hours, wherein additive are as follows: one of copper sulfide, zinc chloride, iron chloride and phosphorus pentoxide are several
Kind and polyphosphoric acids, product softening point is up to 150oC；Patent CN1760331A is related to a kind of modification of adjustable softening point
The production method of pitch, i.e. asphalt stock are mixed, in 100- with after acid adjustment pH value with formaldehyde, metaformaldehyde or paraformaldehyde
150oProduct softening point is up to 134 after C polymerase 10 .1-24 hoC.As it can be seen that the method for catalytic crosslinking can lower temperature and compared with
Promote asphalt softening point to be promoted in short time, is beneficial to energy conservation consumption reduction, but the softening point of gained pitch is lower, is generally extremely difficult to
180 DEG C or more.
Summary of the invention
For preparing at present, the easy coking of product present in high softening point bitumen technique, yield are low low with softening point etc. to be asked
Topic, the present invention propose a kind of to carry out cross-linking reaction by catalytic asphalt component to prepare high softening-point, high yield asphaltic products
Method.
The preparation method of high softening point bitumen of the present invention, includes the following steps:
Softening point is lower than 100oThe asphalt stock powder of C is placed in autoclave, and catalyst and crosslinking are added at room temperature
Agent is uniformly mixed, then under the conditions of revolving speed is 50-500 r/min with 2-10oThe heating rate of C/min is warming up to 200-
350oC, by, from boosting power, 1-8h is reacted in pressure maintaining in kettle, exhaust bleeds off pressure rear cooling discharge to get high softening point bitumen.
As described above, softening point is lower than 100oThe asphalt stock of C includes in coal tar asphalt, asphalt and bitumen
One or more of mixtures, the partial size of asphalt stock powder is less than 50 mesh.
As described above, catalyst is lewis acid catalyst, i.e., in anhydrous aluminum chloride, iron chloride, zinc chloride and stannic chloride
One or more, and the lewis acid catalyst additive amount accounts for the 1% -10% of asphalt stock silty amount, preferably 2%-
5%, the partial size of catalyst is less than 50 mesh.
As described above, crosslinking agent includes: one or more of carbon tetrachloride, chloroform, methylene chloride and bromofom, and described
Crosslinking agent additive amount 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
The polymerization reaction for joining agent, in lower temperature and can effectively improve asphalt softening point in the short period, prepared high softening-point drip
Green softening point is 180oC or more；2) it in process of production, is premixed at room temperature using powder raw material and catalyst, crosslinking agent,
The contact effect of catalyst and crosslinking agent with pitch is substantially increased, the sticky caused material of system is mixed when high temperature being avoided to feed intake
It closes uneven；3) reaction is completed in closed autoclave, is produced from boosting, is conducive to thermal condensation reaction and is carried out；4) soft
The promotion for changing point depends on the crosslinking polycondensation of pitch light component rather than merely pulls out light component, improves product yield；5) whole
It is a reaction one pot completion, save material transfer, distillation and etc., it is easy to operate.
Specific embodiment
The method of the present invention will be described further by several embodiments below, but therefore not limit this hair
Bright method.Wherein, the percentage composition is mass percentage.
Embodiment 1
By 100 g softening points 75oThe coal tar asphalt powder (80 mesh) of C is placed in autoclave, be added at room temperature 1 g without
Water aluminum chloride powder (80 mesh) and 10 g chloroformic solutions are uniformly mixed, then in the case where revolving speed is 50 r/min with 5oC/min
Heating rate be warming up to 250oC, by, from boosting power, 1 h is reacted in pressure maintaining in kettle；Exhaust bleeds off pressure rear cooling discharge, gained drip
Green product softening point 228oC, yield 80%.
Embodiment 2
By 200 g softening points 45oThe asphalt powder (60 mesh) of C is placed in autoclave, be added at room temperature 10 g without
Water chlorination iron powder (80 mesh) and 10 g carbon tetrachloride solutions are uniformly mixed in the case where revolving speed is 500 r/min, then with
10oThe heating rate of C/min is warming up to 350oC, by, from boosting power, 4 h are reacted in pressure maintaining 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 (60 mesh) of C is placed in autoclave, and 1 g is added at room temperature
Anhydrous aluminum chloride powder (80 mesh), 5 g anhydrous ferric chloride powder (80 mesh), 10 g carbon tetrachloride solutions and 10 g chloroformic solutions,
It is uniformly mixed, revolving speed is 200 r/min；With 2oThe heating rate of C/min is to 300oC, by power of boosting certainly in kettle, pressure maintaining
React 3 h；Exhaust bleeds off pressure rear cooling discharge, gained asphaltic products softening point 271oC, yield 78%.
Embodiment 4
By the coal tar asphalt powder (softening point 75 of 150 goC, 60 mesh) and asphalt powder (softening point 45o60 mesh of C) it is mixed
Object (the two weight ratio 1:1) is closed to be placed in autoclave；3 g anhydrous zinc chloride powder (80 mesh) and 45 g bromines are added at room temperature
Imitative solution, is uniformly mixed, and revolving speed is 200 r/min；With 2oThe heating rate of C/min is to 200oC, by boosting certainly in kettle
8 h are reacted in power, pressure maintaining；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 (60 mesh) of C is placed in autoclave, and 10 g are added at room temperature
Anhydrous stannic chloride powder (80 mesh) and 30g dichloromethane solution, are uniformly mixed, and revolving speed is 400 r/min；With 5oC/min
Heating rate to 220oC, by, from boosting power, 4 h are reacted in pressure maintaining in kettle；Exhaust bleeds off pressure rear cooling discharge, gained Asphalt Production
Product softening point 185oC, yield 81%.
Embodiment 6
By the asphalt powder (softening point 45 of 100 goC, 60 mesh) and bitumen powder (softening point 70oC, 60 mesh) mixing
Object (the two weight ratio 4:1) mixture is placed in autoclave；1 g anhydrous aluminum chloride powder (80 mesh), 2 g are added at room temperature
Anhydrous zinc chloride powder (80 mesh), 10 g carbon tetrachloride solutions and 10 g chloroformic solutions, are uniformly mixed, and revolving speed is 250 r/
min；With 5oThe heating rate of C/min is to 250oC, by, from boosting power, 6 h are reacted in pressure maintaining in kettle；Exhaust cools down out after bleeding off pressure
Material, gained asphaltic products softening point 205oC, yield 79%.
Embodiment 7
By the coal tar asphalt powder (softening point 75 of 200 goC, 80 mesh), asphalt powder (softening point 45oC, 60 mesh) and day
Right asphalt powder (softening point 70oC, 60 mesh) mixture (three weight ratio 3:1:1) is placed in autoclave；2 are added at room temperature
G anhydrous aluminum chloride powder (80 mesh), 1 g anhydrous ferric chloride powder (80 mesh), 3 g anhydrous zinc chloride powder (80 mesh), 10 g tetra-
Carbon chloride solution, 10 g chloroformic solutions and 10 g dichloromethane solutions, are uniformly mixed, and revolving speed is 300 r/min；With 6oC/
The heating rate of min is to 240oC, by, from boosting power, 4 h are reacted in pressure maintaining 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 (softening point 75 of 300 goC, 80 mesh) and bitumen powder (softening point 70oC, 80 mesh) it is mixed
Object (the two weight ratio 2:1) is closed to be placed in autoclave；It is anhydrous that 3 g anhydrous aluminum chloride powder (80 mesh), 2 g are added at room temperature
Chlorination iron powder (80 mesh), 20 g chloroformic solutions and 10 g bromofom solution, are uniformly mixed, and revolving speed is 300 r/min；With
2oThe heating rate of C/min is to 280oC, by, from boosting power, 4 h are reacted in pressure maintaining in kettle；Exhaust bleeds off pressure rear cooling discharge, gained
Asphaltic products softening point 252oC, yield 72%.
Claims (6)
1. a kind of preparation method of high softening point bitumen, it is characterised in that the following steps are included:
Softening point is placed in autoclave lower than 100 DEG C of asphalt stock powder, be added at room temperature lewis acid catalyst and
Crosslinking agent is uniformly mixed under conditions of revolving speed is 50-500 r/min, then is heated up with the heating rate of 2-10 DEG C/min
To 200-350 DEG C, by, from boosting power, 1-8h is reacted in pressure maintaining in kettle, exhaust bleeds off pressure rear cooling discharge to get high softening-point drip
It is green；
The lewis acid catalyst is one or more of anhydrous aluminum chloride, iron chloride, zinc chloride, stannic chloride；
The additive amount of the catalyst accounts for the 1% -10% of asphalt stock silty amount；
The crosslinking agent includes one or more of carbon tetrachloride, chloroform, methylene chloride, bromofom；
The crosslinking agent additive amount accounts for the 5% ~ 30% of asphalt stock silty amount.
2. a kind of preparation method of high softening point bitumen as described in claim 1, it is characterised in that the softening point is lower than 100
DEG C asphalt stock powder include one or more of coal tar asphalt, asphalt and bitumen mixture.
3. a kind of preparation method of high softening point bitumen as described in claim 1, it is characterised in that the asphalt stock powder
Partial size is less than 50 mesh.
4. a kind of preparation method of high softening point bitumen as described in claim 1, it is characterised in that the addition of the catalyst
Amount accounts for the 2% ~ 5% of asphalt stock silty amount.
5. a kind of preparation method of high softening point bitumen as described in claim 1, it is characterised in that the partial size of the catalyst
Less than 50 mesh.
6. a kind of preparation method of high softening point bitumen as described in claim 1, it is characterised in that the crosslinking agent additive amount
Account for the 10% ~ 20% of asphalt stock silty amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710135469.XA CN106867557B (en) | 2017-03-09 | 2017-03-09 | A kind of preparation method of high softening point bitumen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710135469.XA CN106867557B (en) | 2017-03-09 | 2017-03-09 | A kind of preparation method of high softening point bitumen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106867557A CN106867557A (en) | 2017-06-20 |
| CN106867557B true CN106867557B (en) | 2019-09-10 |
Family
ID=59170627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710135469.XA Active CN106867557B (en) | 2017-03-09 | 2017-03-09 | A kind of preparation method of high softening point bitumen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106867557B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP4229117A1 (en) * | 2020-10-16 | 2023-08-23 | Tangold Inc. | Process for the control of softening points of petroleum hydrocarbon materials |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0482560B1 (en) * | 1990-10-22 | 1998-01-21 | Mitsubishi Chemical Corporation | Spinning pitch for carbon fibers and process for its production |
| CN1053001C (en) * | 1996-12-20 | 2000-05-31 | 中国科学院山西煤炭化学研究所 | Process for preparing middle phase asphalt |
| ES2261077B1 (en) * | 2005-04-25 | 2007-12-16 | Repsol Ypf, S.A. | BITUNIMOUS BINDING, PROCEDURE FOR THE APPLICATION OF THE SAME AND ITS USE FOR ROAD PAVING. |
| CN102169988B (en) * | 2011-03-30 | 2012-12-26 | 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 |
| CN105720258B (en) * | 2014-12-03 | 2019-05-31 | 上海杉杉科技有限公司 | Lithium ion battery negative material and its preparation method and application, lithium ion battery |
-
2017
- 2017-03-09 CN CN201710135469.XA patent/CN106867557B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106867557A (en) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106867557B (en) | A kind of preparation method of high softening point bitumen | |
| CN105567275B (en) | A kind of production method for preparing high-purity high softening point bitumen | |
| CN110003932B (en) | Method for preparing high-quality mesophase pitch by ternary co-carbonization | |
| CN103045044A (en) | Energy-saving and environment-friendly powder coating and preparation method thereof | |
| CN103013298A (en) | Powder coating containing modified nanocarbon and preparation method of powder coating | |
| CN111424328B (en) | Nylon melt direct spinning method comprising vapor extraction and liquid phase extraction | |
| CN102838718B (en) | Hyperbranched polyurethane containing isocyanate groups, as well as preparation method and application of hyperbranched polyurethane | |
| CN105038603B (en) | The preparation method of high-softening-point rosin glyceride | |
| CN109399632A (en) | A method of preparing asphalt-base globular active carbon | |
| CN104177766B (en) | A kind of Graphene furane resins composite and preparation method thereof | |
| CN108485694A (en) | A method of carbonizatin method prepares high-quality mesophase pitch altogether | |
| CN102127369A (en) | Method for preparing disproportionated rosin | |
| CN101367506A (en) | Method for preparing insoluble sulfur | |
| CN110498690A (en) | A kind of preparation method of hard heat-insulated carbon felt | |
| CN1053894C (en) | Preparation of 4,4-dipyridine | |
| CN103923262A (en) | Method for grafting and modifying chlorinated polypropylene through maleic anhydride | |
| CN104497305B (en) | A kind of high fluidity high-temperature nylon and preparation method thereof | |
| CN112538362B (en) | Method for improving rheological property of coal tar pitch | |
| JPS5925828B2 (en) | Process for producing powder coatings for coating metals at high temperatures based on polylaurinlactam powder | |
| CN109183187A (en) | A method of the high ortho phenolic fiber of boron modification is prepared using wet spinning | |
| CN110317621A (en) | A kind of collaboration of multikey is controllable promote in the stabilized method of soft pitch | |
| CN103059893A (en) | Method for preparing mesophase pitch by utilizing electrochemical catalysis | |
| CN102627554A (en) | Preparation method of methylene disalicylic acid | |
| CN103073717B (en) | A kind of preparation method of PATMDT/11 | |
| CN105175665B (en) | The preparation method of ink resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |