CN106244183A - A kind of environment-friendly coal Colophonium and preparation method thereof - Google Patents
A kind of environment-friendly coal Colophonium and preparation method thereof Download PDFInfo
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- CN106244183A CN106244183A CN201610679952.XA CN201610679952A CN106244183A CN 106244183 A CN106244183 A CN 106244183A CN 201610679952 A CN201610679952 A CN 201610679952A CN 106244183 A CN106244183 A CN 106244183A
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- coal tar
- tar pitch
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- colophonium
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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
- C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of environment-friendly coal Colophonium for road pavement and preparation method thereof.This environment-friendly coal Colophonium, with the coal tar pitch of coal tar industry by-product as primary raw material, dissolves through high boiling point diluent, with fatty aldehyde, unsaturated aliphatic carboxylate as modifying agent, effectively reduces condensed-nuclei aromatics content.The present invention substantially reduces the content of coal tar pitch benzo [α] pyrene by chemical method, and technique is simple, equipment requirements is low, it is simple to large-scale production, application.
Description
Technical field
The invention belongs to the chemical modification technique field of heavy coal tar, a kind of environment-friendly type for road pavement
Coal tar pitch and preparation method thereof.
Background technology
Coal tar pitch is also referred to as heavy coal tar, coal tar asphalt, it be coal tar extract light oil, carbolic oil, naphtalene oil, washing oil and
Residue after the fractions such as carbolineum, accounts for more than the 50% of coal tar gross mass.Compared with asphalt, the aromaticity of coal tar pitch
Height, polarity are big, have good compatibility and affinity with sand material, the resistance to deformation on coal tar pitch road surface, wear-resistant, the safety of driving
Property prominent.Meanwhile, the condensed-nuclei aromatics content of coal tar pitch is higher than carcinogens such as asphalt, particularly benzo [α] pyrene (BaP)
Content is up to 1.0%, seriously constrains coal tar pitch application in terms of road pavement.CN104593032A selects methyl phenyl ethers anisole, right
Benzene dimethanol, benzophenone, formaldehyde, metaformaldehyde, paraformaldehyde, benzaldehyde are modifying agent, pyrovinic acid, ethylsulfonic acid, benzene sulphur
Acid, sulfamic acid, p-methyl benzenesulfonic acid are accelerator, through 120～350 DEG C of reactions, decompression distillation, the BaP content fall of coal tar pitch
To below 500ppm.CN103450693A is with paraformaldehyde, metaformaldehyde, coumarone indene resin, epoxy resin, Polyethylene Glycol for changing
Property agent, composite modified with residual oil, macromolecular material, polyphosphoric acids, elemental sulfur, BaP removal efficiency is up to 74.8%.
CN103834423A with dehydrated alcohol and toluene as solvent, under toluenesulfonic acid or anhydrous Aluminum chloride catalytic action by anhydride or
Fragrant and mellow modified medium temperature coal pitch or low temperature coal tar pitch, BaP reduction rate reaches more than 90%.CN105238429A with toluenesulfonic acid is
Catalyst, vacuum distillation recovered solvent hexamethylene modified through terephthalaldehyde, i.e. prepare and build the road with modified coal pitch, BaP reduction
Rate reaches 84.51%, and softening point is more than 100 DEG C.CN104194357A reaches with potassium permanganate modified coal pitch, BaP content reduction rate
To more than 65%.Obviously, using the method for modifying of high volatile organic solvent, production security is relatively low and to equipment requirements relatively
Height, is not easy to scalable technology application.
A kind of environment-friendly coal Colophonium for road pavement of invention and preparation method thereof.This environment-friendly coal Colophonium
With coal tar pitch as primary raw material, dissolve through high boiling point diluent, changed by catalysis fatty aldehyde, unsaturated aliphatic carboxylate
Property coal tar pitch, effectively reduces condensed-nuclei aromatics content.
Summary of the invention:
The concrete technical problems that the invention solves the problems that is to provide a kind of environment-friendly coal Colophonium being suitable to road pavement and system thereof
Preparation Method.This environment-friendly coal Colophonium is with the coal tar pitch of coal tar industry by-product as primary raw material, molten through high boiling point diluent
Solve, with fatty aldehyde, unsaturated aliphatic carboxylate as modifying agent, effectively reduce condensed-nuclei aromatics content.The present invention is by chemistry
Method substantially reduces the content of coal tar pitch benzo [α] pyrene, and technique is simple, equipment requirements is low, it is simple to large-scale production, application.
The technical scheme is that
A kind of environment-friendly coal Colophonium, is formed by fatty aldehyde, unsaturated aliphatic carboxylate chemical modification, and its material forms
And proportioning includes:
Described coal tar pitch is coal tar pitch, and softening point is 95-110 DEG C, and toluene insolubles content is 20%-23%,
Quinoline insolubles content 7%-9%.
Described diluent is one or both in aromatic naphtha, residual oil；The initial boiling point of described aromatic naphtha is more than 230 DEG C,
Described residual oil divides containing saturated point of 70%-80%, 2%-10% fragrance, 10%-20% colloid and the asphalitine of less than 0.5%.
Described fatty aldehyde is one or both in formaldehyde, metaformaldehyde, glutaraldehyde.
Described catalyst is one or both in triethanolamine, sodium hydroxide.
Described unsaturated aliphatic carboxylate be butyl methacrylate, Isooctyl acrylate monomer, dibutyl maleate and
One or both in di-2-ethylhexyl maleate.
The preparation method of described environment-friendly coal Colophonium, comprises the steps:
(1) coal tar pitch is added in reactor, be warming up to 90-130 DEG C and make coal tar pitch melt, add diluent,
Stir 1-2 hour under 500-700rpm rotating speed；
(2) in above-mentioned system, add fatty aldehyde and catalyst, react 1-2 hour；
(3) adding unsaturated aliphatic carboxylate at 90-130 DEG C, react 1-2 hour, cooling, discharging i.e. obtain environment protection coal
Asphaltic products.
In described step (1), the temperature making coal tar pitch melted is preferably 110-120 DEG C.
In described step (3), reaction temperature is preferably 120-130 DEG C.
The invention has the beneficial effects as follows:
(1) present invention is using coal tar pitch as raw material, with the use of aromatic naphtha or residual oil, does not uses carbolineum, preferably ensures
The safety in utilization of production security and product.
(2) present invention does not uses the macromolecular compounds such as epoxy resin, waste rubber powder, SBS, PVC, PET, equipment requirements
The highest, energy consumption is low, with short production cycle.
(3) present invention does not uses the volatile organic matters such as hexamethylene, and production security is high, technique is simple.
(4) present invention does not uses asphalt, has given full play to the price advantage of coal tar pitch.
(5) present invention is with coal tar pitch as key component, and its relative mass number is higher than 70%, maximally utilises
Coal tar pitch resource and performance advantage thereof.
(6) fatty aldehyde of the present invention is with the use of base catalyst, and the corrosivity of equipment is significantly lower than acidic catalyst.
(7) present invention uses unsaturated aliphatic carboxylate-modified on the basis of fatty aldehyde modification, not only improves reduction
The residual volume of free formaldehyde, is beneficial to again reduce condensed-nuclei aromatics content further, and the security performance of coal tar pitch is higher.
(8) present invention can make the condensed-nuclei aromatics Bap content reduction rate of coal tar pitch reach more than 80%, the safety of coal tar pitch
Property significantly improves.
Detailed description of the invention
The present invention is further described below in conjunction with detailed description of the invention:
Embodiment one
Take 100g coal tar pitch to add in reactor, be warming up to 110 DEG C and make coal tar pitch soften, add 30g diluent,
Stir 1 hour under the rotating speed of 500rpm, make coal tar pitch be completely dissolved；System temperature is down to 95 DEG C, adds 3g fatty aldehyde and 3g urges
Agent is reacted 1 hour；System is warming up to 120 DEG C, is slowly added to 5g unsaturated aliphatic carboxylate, cooling, discharging after 1 hour
Obtain environment protection coal asphaltic products.
In the present embodiment: diluent is aromatic naphtha, fatty aldehyde is paraformaldehyde, and catalyst is triethanolamine, unsaturated lipid
Aliphatic carboxylic acid's ester is butyl methacrylate.
Softening point, needle penetration and ductility are according to the method test of " GBT 15180-2010 heavy traffic paving asphalt ".
BaP reduction rate method of testing: accurately weigh a certain amount of coal tar pitch, dissolves with thiacyclohexane, after ultrasonic wave concussion,
Stand 24 hours, take part solution dehydrated alcohol and be diluted to detectable concentration, add cuvette, with Varian company of the U.S.
Cary300 type ultraviolet-visible spectrophotometer measures its BaP content.BaP reduction rate refers in raw coal Colophonium BaP content and changes
The difference of BaP content and the ratio of BaP content in raw coal Colophonium in property coal tar pitch, it may be assumed that
In formula, P BaP reduction rate, %；BaP content in C raw coal Colophonium, wt%；In C ' modified coal pitch
BaP content, wt%.
Embodiment two
Implement step with embodiment one.Difference is: as unsaturated aliphatic carboxylate, wait the propylene of mass fraction
Butyl methacrylate in the different monooctyl ester alternative embodiment one of acid.
Method of evaluating performance is with embodiment one.
Embodiment three
Take 100g coal tar pitch to add in reactor, be warming up to 110 DEG C and make coal tar pitch soften, add 25g diluent,
Stir 1 hour under the rotating speed of 500rpm, make coal tar pitch be completely dissolved；System temperature is down to 95 DEG C, adds 3g fatty aldehyde and 3g urges
Agent is reacted 1.5 hours；System is warming up to 125 DEG C, is slowly added to the reaction of 10g unsaturated aliphatic carboxylate, after 1.5 hours
Cooling, discharging i.e. obtain environment protection coal asphaltic products.
In the present embodiment: diluent is residual oil, fatty aldehyde is paraformaldehyde, and catalyst is triethanolamine, unsaturated fatty acids
Race's carboxylate is dibutyl maleate.
Method of evaluating performance is with embodiment one.
Embodiment four
Implement step with embodiment three.Difference is: diluent is aromatic naphtha.
Method of evaluating performance is with embodiment one.
Embodiment five
Implement step with embodiment three.Difference is: diluent is aromatic naphtha, and unsaturated aliphatic carboxylate is Malaysia
Dioctyl phthalate.Method of evaluating performance is with embodiment one.
The performance of subordinate list embodiment of the present invention modified coal pitch and BaP reduction rate
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
The detailed description of the invention of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention by institute
The claims submitted to determine scope of patent protection.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. an environment-friendly coal Colophonium, is formed by fatty aldehyde, unsaturated aliphatic carboxylate chemical modification, its material composition and
Proportioning includes:
Described coal tar pitch is coal tar pitch, and softening point is 95-110 DEG C, and toluene insolubles content is 20%-23%, quinoline
Insolubles content 7%-9%；
Described diluent is one or both in aromatic naphtha, residual oil；The initial boiling point of described aromatic naphtha is more than 230 DEG C, described
Residual oil divides containing saturated point of 70%-80%, 2%-10% fragrance, 10%-20% colloid and the asphalitine of less than 0.5%；
Described fatty aldehyde is one or both in formaldehyde, metaformaldehyde, glutaraldehyde.
2. catalyst as claimed in claim 1 is one or both in triethanolamine, sodium hydroxide.
3. unsaturated aliphatic carboxylate as claimed in claim 1 is butyl methacrylate, Isooctyl acrylate monomer, maleic acid
One or both in dibutyl ester and di-2-ethylhexyl maleate.
4. the preparation method of environment-friendly coal Colophonium as claimed in claim 1, comprises the steps:
(1) coal tar pitch is added in reactor, be warming up to 90-130 DEG C and make coal tar pitch melt, add diluent, at 500-
Stir 1-2 hour under 700rpm rotating speed；
(2) in above-mentioned system, add fatty aldehyde and catalyst, react 1-2 hour；
(3) adding unsaturated aliphatic carboxylate at 90-130 DEG C, react 1-2 hour, cooling, discharging i.e. obtain environment protection coal Colophonium
Product.
5., in step (1) as claimed in claim 4, the temperature making coal tar pitch melted is preferably 110-120 DEG C.
6., in step (3) as claimed in claim 4, reaction temperature is preferably 120-130 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610679952.XA CN106244183B (en) | 2016-08-16 | 2016-08-16 | A kind of environment-friendly coal pitch and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610679952.XA CN106244183B (en) | 2016-08-16 | 2016-08-16 | A kind of environment-friendly coal pitch and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106244183A true CN106244183A (en) | 2016-12-21 |
| CN106244183B CN106244183B (en) | 2019-07-19 |
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| CN201610679952.XA Expired - Fee Related CN106244183B (en) | 2016-08-16 | 2016-08-16 | A kind of environment-friendly coal pitch and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108382039A (en) * | 2017-10-13 | 2018-08-10 | 深圳海川新材料科技股份有限公司 | A kind of ordor removing modified asphalt waterproof coiled material and preparation method thereof |
| CN114702833A (en) * | 2022-04-02 | 2022-07-05 | 江西新越沥青有限公司 | Preparation method of environment-friendly modified waterproof asphalt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976773A (en) * | 2012-11-23 | 2013-03-20 | 上海柯瑞冶金炉料有限公司 | Coal tar pitch binding agent and preparation method thereof |
| CN103450693A (en) * | 2013-09-18 | 2013-12-18 | 交通运输部公路科学研究所 | Compound modified coal pitch and preparation method thereof |
| CN104119941A (en) * | 2014-07-14 | 2014-10-29 | 天津森聚柯密封涂层材料有限公司 | Preparation method of modified asphalt |
-
2016
- 2016-08-16 CN CN201610679952.XA patent/CN106244183B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976773A (en) * | 2012-11-23 | 2013-03-20 | 上海柯瑞冶金炉料有限公司 | Coal tar pitch binding agent and preparation method thereof |
| CN103450693A (en) * | 2013-09-18 | 2013-12-18 | 交通运输部公路科学研究所 | Compound modified coal pitch and preparation method thereof |
| CN104119941A (en) * | 2014-07-14 | 2014-10-29 | 天津森聚柯密封涂层材料有限公司 | Preparation method of modified asphalt |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108382039A (en) * | 2017-10-13 | 2018-08-10 | 深圳海川新材料科技股份有限公司 | A kind of ordor removing modified asphalt waterproof coiled material and preparation method thereof |
| CN114702833A (en) * | 2022-04-02 | 2022-07-05 | 江西新越沥青有限公司 | Preparation method of environment-friendly modified waterproof asphalt |
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| CN106244183B (en) | 2019-07-19 |
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Granted publication date: 20190719 Termination date: 20200816 |