CN106336884B - A kind of preparation method of environment-friendly modified coal tar asphalt - Google Patents
A kind of preparation method of environment-friendly modified coal tar asphalt Download PDFInfo
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- CN106336884B CN106336884B CN201610895574.9A CN201610895574A CN106336884B CN 106336884 B CN106336884 B CN 106336884B CN 201610895574 A CN201610895574 A CN 201610895574A CN 106336884 B CN106336884 B CN 106336884B
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- coal tar
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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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- Working-Up Tar And Pitch (AREA)
Abstract
A kind of preparation method of environment-friendly modified coal tar asphalt, the method is uniformly to mix medium temperature coal tar pitch and Catalyzed by Potassium Bisulfate agent, add the aprotic organic solvent and 10- undecylene aldehyde modifying agent that low boiling point easily recycles simultaneously, so that it is fully dissolved and is persistently stirred with certain rotating speed, at 30-70 DEG C of temperature, reflux condensation mode reacts 1-8 hours；Reaction terminates, the aprotic organic solvent that easily recycles of recycling low boiling point, by the solid matter aeration-drying 24 hours of acquisition, obtains environment-friendly modified coal tar asphalt.Operating procedure of the present invention is simple, and amount of modifier is few, and catalyst amount is also few, and reaction temperature is low, and solvent is Ke Xunhuanliyong, and industrial production is at low cost.The total content for 16 kinds of toxicity polycyclic aromatic hydrocarbons that U.S. EPA emphasis detects in modified coal tar pitch substantially reduces, and is modified as low temperature coal tar pitch by medium temperature coal pitch.
Description
Technical field
The present invention relates to a kind of preparation method of environment-friendly modified coal tar asphalt, specific method is a kind of application 10- ten
Preparation method of one olefine aldehydr as the environment-friendly coal pitch of modifying agent.
Technical background
China is the maximum country of smelter coke production and consumption amount in the world, in State Statistics Bureau's bulletin display 2014
State's coke output is 4.76 hundred million tons.It is calculated according to 5% or so coal tar of coke by-product per ton, the annual high temperature coal-tar yield of China
Up to 20,000,000 tons or more, according to 50-60% calculation of yield, coal tar processing enterprise can output high temperature coal-tar pitch (with
Lower abbreviation coal tar pitch) up to 10,000,000 tons or more, cheap, the coal tar pitch of these by-products is except only a few is for doing electrode pitch
Outside binder and carbon material, most of to be used as fuel combustion or directly exported external, this makes the processing and utilization of domestic coal tar pitch
Rate is extremely low.Relative to asphalt, coal tar pitch has many advantages, such as wetting and adhesion property is good and erosion-resisting characteristics is strong, lacks
Point is contained in a large amount of toxic polycyclic aromatic hydrocarbon substance, especially coal tar pitch containing Environmental Protection Agencies such as benzo (a) pyrenes (BaP)
(EPA) the 16 kinds of polycyclic aromatic hydrocarbons (PAHs) confirmed have carcinogenic, teratogenesis, cause gene mutation effect, are environment and the ecosystem
Poisonous substance significantly limits the extensive use of coal tar pitch.Therefore, being modified processing to coal tar pitch reduces its Poisoning PAHs's
It is a difficult point studied both at home and abroad that content, which is prepared into high-performance environment protection type coal tar pitch,.
103834421 A of Chinese patent CN are disclosed " a kind of preparation method of environment-friendly modified coal tar pitch ".The preparation
Method then at 70~90 DEG C and is stirred in the medium temperature coal pitch of 20~30 parts of quality or low temperature coal tar pitch merging reaction kettle
Under the conditions of speed is 80~100r/min, the mixed solvent of 67~77 parts of quality is added into the reaction kettle, stirs 10min,
Under the conditions of mutually synthermal and mixing speed, the modifying agent and 0.20~0.32 part of quality of 2.6~3.2 parts of quality are sequentially added
Sulfuric acid, stir 1~5h, obtain coal tar pitch mixture.Finally by gained coal tar pitch mixture 100~110 DEG C of conditions next time
Receive solvent, you can environment-friendly modified coal tar pitch is made.But for the effect of coal tar pitch modification and modification in the preparation method
Coal tar pitch performance indicator afterwards has no detailed description.According to the common knowledge of this field, due to the group of coalite tar pitch itself
At feature and corresponding physico-chemical property, the problem for causing its modified naphthalene content high is difficult to solve, therefore in the condition of middle low temperature
Under, the stability and ageing resistance of modified low temperature coal tar pitch are poor.
105419361 A of Chinese patent CN are disclosed " a kind of composite modified coal tar pitch and preparation method thereof ".The modification
Each raw material composition includes 30-90 parts of medium temperature coal pitch, 10-70 parts of asphalt, phthalic acid ester in mass ratio in method
0.1-5 parts, 0-10 parts of polyethylene glycol, 0.1-10 parts of SBS modifier, 0-5 parts of nano-calcium carbonate, SBS obtained is compound after processing
Modified coal pitch can significantly reduce containing for polycyclic aromatic hydrocarbon in modified pitch although improving the high temperature performance of coal tar pitch
Amount, but the disadvantage is that modifying agent type is more and dosage is big, limit its industrial applications.Chinese patent CN104194357A,
Disclose " a method of reducing polycyclic aromatic hydrocarbon content in coal tar asphalt ".This method is to fill coal tar pitch under brittleness temperature
Divide freezing, then obtain being less than 80 mesh asphalt powders after crushed, asphalt powder is added in liquor potassic permanganate under room temperature, is kept stirring
Speed reacts 180min, and obtained modified coal pitch benzo [a] pyrene content reduced rate is up to 65% or more, but due to changing
Property agent using the extremely strong potassium permanganate of oxidisability, coal tar pitch premature oxidation aging is easily caused in modifying process, to reduce
The performance of coal tar pitch.
Invention content
In order to solve the above technical problem, the present invention provides a kind of environment-friendly modified coal tar asphaltes, it is therefore intended that adopts
With simple and feasible technology, suitable modifying agent is selected to be modified medium temperature coal pitch, farthest reduced in coal tar pitch
16 kinds of toxicity polycyclic aromatic hydrocarbon contents of U.S. EPA emphasis detection, the especially content of the carcinogenic polycyclic aromatic hydrocarbon such as benzo [a] pyrene, make
Modified coal tar pitch is further improved in performance.
To solve the above-mentioned problems, the technical solution used in the present invention is specific as follows.
A kind of preparation method of environment-friendly modified coal tar asphalt, including two specific steps：(1) medium temperature coal tar is dripped
Green and Catalyzed by Potassium Bisulfate agent is fitted into reactor after mixing, and the aprotic that low boiling point easily recycles then, which is added, simultaneously has
Solvent and 10- undecylene aldehyde modifying agent, and persistently stirred with certain rotating speed, at 30~70 DEG C of temperature, reaction 1~8 is small
When；(2) after reaction, the aprotic organic solvent that the low boiling point easily recycles, the solid matter drying 24 of acquisition are recycled
Hour, obtain environment-friendly modified coal tar asphalt.
Further, the dosage of Catalyzed by Potassium Bisulfate agent is the medium temperature coal tar asphalt quality in the preparation method
1%~9%；The dosage of 10- undecylene aldehyde modifying agent is the 2%~10% of the medium temperature coal tar asphalt quality.
In the method for the present invention, using medium temperature coal pitch raw material or hard pitch raw material, using potassium acid sulfate as catalyst,
10- undecylene aldehydes are that modifying agent passes through tune in the aprotic organic solvent that the low boiling points such as benzene, toluene, tetrahydrofuran easily recycle
Section response parameter can also equally achieve the object of the present invention.A kind of preferred technical solution is, reaction raw materials select the granularity to be
80 mesh, the medium temperature coal tar pitch that softening point is 70~90 DEG C；The aprotic organic solvent that low boiling point easily recycles selects hexamethylene
Alkane, dosage are 6~10 times of medium temperature coal tar asphalt quality.
Further, reaction temperature is 45~55 DEG C in above-mentioned preparation method, and the reaction time is 3~5 hours.
Further, after reaction, using vacuum distillation recovered solvent hexamethylene.
The best technical solution of the present invention be used in the preparation method raw material composition and its content for：Medium temperature coal
Tar asphalt；8% (relative to coal tar pitch quality, the same below) 10- undecylene aldehyde modifying agent；5% Catalyzed by Potassium Bisulfate agent；8 times
Cyclohexane solvent；Temperature is 45-55 DEG C, and the time is 3-5 hours.In the technical solution, the coal tar asphalt is medium temperature coal tar
Oil asphalt, granularity are 80 mesh, and softening point is 70-90 DEG C.
Using a kind of preparation method of environment-friendly modified coal tar asphalt of the present invention, compared with prior art, advantage with
Good effect is as follows：
The environment-friendly modified coal tar asphalt of the present invention, be using 10- undecylene aldehydes under hexamethylene effect in coal tar pitch
Polycyclic aromatic hydrocarbon carry out electrophilic substitution reaction, while polycyclic aromatic hydrocarbon content in reducing coal tar pitch, also improve medium temperature coal drip
Green performance.Especially in highly preferred embodiment of the present invention, 16 kinds of total reduced rates of polycyclic aromatic hydrocarbon reach 91.10% in coal tar pitch,
The reduced rate of wherein benzo [a] pyrene is up to 93.14%；Coal tar pitch softening point is reduced to 38.20 DEG C by 87.00 DEG C, toluene insoluble
Object is increased by 21.16% to 26.43%, and quinoline insolubles are increased by 5.25% to 8.32%, and coking value is dropped to by 50.91%
48.91%.
Device is simple to operation used by the preparation method of the environment-friendly modified coal tar asphalt of the present invention, under normal pressure,
It is reacted under the conditions of 30-70 DEG C, the dosage of modifying agent 10- undecylene aldehydes is only coal tar pitch dosage 2-10%, catalyst sulfuric acid hydrogen potassium
Dosage be coal tar pitch dosage 1-9%, and catalyst sulfuric acid hydrogen potassium, price is low, derives from a wealth of sources；Solvent is recycled by vacuum distillation
It can utilize again.Therefore, the method for the present invention is with operating procedure is simple, reaction temperature is low, modifying agent and catalyst amount are few, molten
The advantages that agent is Ke Xunhuanliyong, industrial production is at low cost.
The environment-friendly modified coal tar asphalt of the present invention, 16 kinds of total reduced rates of polycyclic aromatic hydrocarbon reach in modified raw material coal tar pitch
91.10%, while polycyclic aromatic hydrocarbon content in capable of reducing coal tar pitch, coal tar pitch performance also significantly improves, and can be used for building the road
The deep processing of asphalt stock or other high added value coal asphalt products.
Specific implementation mode
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.
In following embodiment using used raw material as medium temperature coal pitch (softening point between 70-90 DEG C, granularity 80
Mesh), modifying agent and catalyst are respectively 10- undecylene aldehydes modifying agent, potassium acid sulfate, and solvent uses aprotic organic solvent ring
Hexane.
The detection of polycyclic aromatic hydrocarbon content uses gas chromatography in coal tar pitch, and wherein naphthalene content is too low is not achieved gas-chromatography
Detection limits and ignores and do not remember, isomer can not be efficiently separated and is combined benzo [b] fluoranthene each other with benzo [k] fluoranthene
It calculates, the content of modified also some polycyclic aromatic hydrocarbons is too low to be not achieved gas chromatographic detection limit and ignore and do not remember.
Embodiment 1
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 6%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 1
Embodiment 2
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 2
With reference to standard GB/T/T 4507-1999, GB/T 2292-1997, GB/T 2293-1997, GB/T 8727-
2008, rear coal tar pitch softening point, toluene insolubles, quinoline insolubles, coking value before modified are determined and are compared, specifically
Coal tar pitch softening point, toluene insolubles, quinoline insolubles, coking value are measured to compare and refer to table 3 after before modified.
Table 3
Embodiment 3
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, at the same add 50mL solvents hexamethylene and
10% modifying agent 10- undecylene aldehydes, are stirred to react 4 hours at 50 DEG C.The content of polycyclic aromatic hydrocarbon refers in modified coal tar pitch
Mark is as follows：
Table 4
Embodiment 4
By 5.00g coal tar pitch, 3% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvents hexamethylene and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 5
Embodiment 5
By 5.00g coal tar pitch, 7% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 6
Embodiment 6
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 40 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 7
Embodiment 7
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 4 hours at 60 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 8
Embodiment 8
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 2 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 9
Embodiment 9
By 5.00g coal tar pitch, 5% catalyst sulfuric acid hydrogen potassium uniformly mixes, while adding 50mL solvent hexamethylenes, and 8%
Modifying agent 10- undecylene aldehydes are stirred to react 6 hours at 50 DEG C.The content's index of polycyclic aromatic hydrocarbon is such as in modified coal tar pitch
Under：
Table 10
Above said content is only the basic explanation under present inventive concept, it should be noted that using other softening points and
The non-matter that the medium temperature coal pitch raw material or the low boiling points such as hard pitch raw material and benzene, toluene, tetrahydrofuran of granularity easily recycle
Subtype organic solvent can also realize that the present invention " farthest reduces polycyclic virtue in coal tar pitch by adjusting response parameter
Hydrocarbon content, the especially content of carcinogenic substance polycyclic aromatic hydrocarbon, solve the toxicity problem of coal tar pitch " purpose.Therefore, side of the present invention
In method, raw material is not limited to softening point between 70-90 DEG C, the medium temperature coal pitch that granularity is 80 mesh, and reaction is used
Solvent be equally also not limited to hexamethylene.In addition, the present invention also can be used others without prejudice to spirit of that invention or main spy
The concrete form of sign is summarized, any equivalent exchange that all technical solutions according to the present invention are done, belongs to the guarantor of the present invention
Protect range.
Claims (5)
1. a kind of preparation method of environment-friendly modified coal tar asphalt, it is characterised in that：By medium temperature coal tar pitch and hydrogen sulfate
Potassium catalyst is fitted into reactor after mixing, be then added simultaneously aprotic organic solvent that low boiling point easily recycles and
10- undecylene aldehyde modifying agent, and persistently stirred with certain rotating speed, at 30~70 DEG C of temperature, react 1~8 hour；Reaction knot
Shu Hou recycles the aprotic organic solvent that the low boiling point easily recycles, and the solid matter of acquisition is dried 24 hours, and ring is obtained
Guarantor's type modified coal tar pitch；The dosage of Catalyzed by Potassium Bisulfate agent is the medium temperature coal tar asphalt quality in the preparation method
1%~9%；The dosage of 10- undecylene aldehyde modifying agent is the 2%~10% of the medium temperature coal tar asphalt quality.
2. the preparation method of environment-friendly modified coal tar asphalt as described in claim 1, it is characterised in that：The medium temperature coal tar
The granularity of oil asphalt is 80 mesh, and softening point is 70~90 DEG C.
3. the preparation method of environment-friendly modified coal tar asphalt as described in claim 1, it is characterised in that：The low boiling point is easy
The aprotic organic solvent of recycling is hexamethylene, and dosage is 6~10 times of the medium temperature coal tar asphalt quality.
4. the preparation method of environment-friendly modified coal tar asphalt as described in claim 1, it is characterised in that：The reaction temperature
It it is 45~55 DEG C, the reaction time is 3~5 hours.
5. the preparation method of environment-friendly modified coal tar asphalt as claimed in claim 3, it is characterised in that：After reaction,
Using vacuum distillation recovered solvent hexamethylene.
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| CN103468009B (en) * | 2013-09-26 | 2016-05-25 | 山西盛驰科技有限公司 | A kind of modified pavement asphalt and production technology |
| CN105238429B (en) * | 2015-10-19 | 2017-10-24 | 太原理工大学 | A kind of preparation method built the road with low toxicity modified coal pitch |
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