CN110437628B

CN110437628B - Modifier mother liquor, road asphalt and synthesis method thereof

Info

Publication number: CN110437628B
Application number: CN201810420142.1A
Authority: CN
Inventors: 徐青柏; 陈杰; 宣根海; 宁爱民; 李志军; 程国香; 申峻; 侯荣国
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-05-04
Filing date: 2018-05-04
Publication date: 2021-05-04
Anticipated expiration: 2038-05-04
Also published as: CN110437628A

Abstract

The invention discloses a modifier mother liquor, road asphalt and a synthetic method thereof. The modifier mother liquor comprises the following raw materials in parts by weight: 78-94 parts of modified anthracene oil, 0.4-3.5 parts of polyphosphoric acid and 4-20 parts of SBS. The modified anthracene oil is prepared by performing nucleophilic addition, graft polymerization and the like on a phthalaldehyde compound and anthracene oil fraction, and performing condensation modification on the modified anthracene oil by polyphosphoric acid, so that the modified anthracene oil reaches a proper condensation degree, and the aromaticity and the content of proper colloid of the modified anthracene oil are improved. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt can be reduced.

Description

Modifier mother liquor, road asphalt and synthesis method thereof

Technical Field

The invention belongs to the technical field of chemical industry, mainly relates to a modifier mother liquor, road asphalt and a synthetic method thereof, and particularly relates to a preparation method of road asphalt produced by taking coal asphalt and petroleum asphalt as raw materials.

Background

With the continuous expansion of highway construction scale, the demand of road asphalt market is also increased at a high speed. Currently, petroleum resources are increasingly deficient, while coal tar pitch (coal pitch) has a low added value in processing and a market price of about half of that of petroleum pitch, and therefore researchers are constantly researching whether coal pitch can be used as a raw material for producing road pitch. The coal tar pitch produced by the traditional method has the defects of poor heat sensitivity, easy aging, poor ductility and the like, and can not meet the requirements of road engineering construction. Aiming at the defects of the coal tar pitch in the service performance, the coal tar pitch and the petroleum pitch are mixed, so that the performance of the road asphalt material can be improved, and the method is one of feasible practical technologies.

The modified petroleum asphalt prepared by taking SBS as a polymer modifier improves the high-low temperature performance and the temperature sensitivity of the petroleum road asphalt due to the modification effect of SBS, so that the bearing capacity and the fatigue resistance of the modified asphalt pavement are improved.

CN101985526A discloses a composite modified asphalt for high-grade roads and a preparation method thereof, which is a method for preparing the composite modified asphalt by adopting 69-90% of petroleum asphalt, 5-30% of coal asphalt, 1-10% of styrene-butadiene-styrene block copolymer and the like, and the preparation process comprises the steps of heating the petroleum asphalt, the coal asphalt, the styrene-butadiene-styrene block copolymer and the like together, grinding by a colloid mill, stirring and developing to prepare a target product. The conventional production process of the modified asphalt is adopted to grind and shear all materials, the grinding time is long, the power consumption is high, and the asphalt flexibility is poor, the elasticity and the low-temperature performance are poor and the thermal storage stability is poor due to the fact that the asphalt content of the coal asphalt is too high, the number of rubber cores in an asphalt colloid structure is too much, and the colloid structure composition of the asphalt is influenced.

CN103694716A discloses a modified coal pitch and a preparation method thereof, which is a method for preparing modified pitch by adopting 10-20 parts of petroleum pitch, 50-30 parts of coal pitch, 1-4 parts of SBS, 5-35 parts of waste rubber powder, 0.5-1 part of flame retardant and the like. In the method, the coal tar pitch accounts for a relatively high proportion (50-30 parts of coal tar pitch), the petroleum pitch accounts for a relatively small proportion (10-20 parts of petroleum pitch), and meanwhile, due to the fact that the asphaltene content of the coal tar pitch is too high (generally more than 20%), the asphaltene content in an asphalt colloid structure is too high, the asphalt colloid composition is unreasonably matched, the asphalt flexibility is poor, and the low-temperature performance and the heat storage stability are poor. In addition, the addition of 5 to 35 parts of waste rubber powder to asphalt results in excessively high blending temperature and poor thermal storage stability of asphalt. The preparation process comprises the steps of premixing the petroleum asphalt, the coal asphalt and the cosolvent with SBS, grinding by a colloid mill, and grinding the components with larger proportion such as the petroleum asphalt, the coal asphalt, the cosolvent and SBS by the colloid mill in the grinding process, wherein the grinding amount is large and the power consumption is large.

Neither of the above techniques addresses the detoxification properties of bitumen.

CN102585527A discloses a modified coal pitch and a preparation method thereof, wherein 70-80% of petroleum pitch, 10-20% of coal pitch and 10-20% of diatomite are subjected to hot-melt mixing, the prepared mixed pitch has good adhesiveness, the dynamic stability of the prepared asphalt mixture is improved by 3-4 times, and the anti-rutting capability is improved. Meanwhile, the diatomite is adopted to adsorb unsaturated aromatic hydrocarbons such as naphthalene and phenol contained in the coal tar pitch, so that the toxicity of the coal tar pitch is reduced.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a modifier mother liquor, road asphalt and a preparation method thereof, in particular to road asphalt produced by coal asphalt and petroleum asphalt raw materials and a preparation method thereof. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt can be reduced.

The invention provides a modifier mother solution, which comprises the following raw materials in parts by weight:

78-94 parts of modified anthracene oil, preferably 80-92 parts;

0.4-3.5 parts of polyphosphoric acid, preferably 0.8-3.2 parts;

4-20 parts of SBS, preferably 6-18 parts;

wherein the modified anthracene oil is obtained by modifying anthracene oil with phthalaldehyde compounds.

The modified anthracene oil provided by the invention comprises the following raw materials in parts by weight:

75-98 parts of anthracene oil, preferably 85-95 parts;

2-25 parts of phthalaldehyde compound, preferably 5-15 parts;

0.5-5 parts of catalyst, preferably 1-4 parts.

The distillation range of the anthracene oil is 300-385 ℃, and the preferred distillation range is 320-360 ℃.

The phthalaldehyde compound is one or a mixture of terephthalaldehyde, m-phthalaldehyde and o-phthalaldehyde.

The catalyst is one or a mixture of more of trifluoromethanesulfonic acid, potassium bisulfate and concentrated sulfuric acid.

The method for preparing the modified anthracene oil comprises the following steps: adding anthracene oil into a reaction kettle, adding a phthalaldehyde compound and a catalyst, heating, raising the temperature, controlling the reaction temperature to be 150-270 ℃, preferably 160-260 ℃, stirring for 0.5-5.0 hours at the stirring speed of 200-1000 rpm, and thus obtaining the modified anthracene oil.

The polyphosphoric acid concentration of the polyphosphoric acid is 105-116 wt%.

The molecular weight of SBS is 10-20 ten thousand, and it is linear structure or star structure.

In a second aspect, the present invention provides a process for preparing a modifier mother liquor, comprising:

(1) adding the modified anthracene oil into a reaction kettle, adding part of polyphosphoric acid, heating to raise the temperature, controlling the reaction temperature to be 80-140 ℃, preferably 90-130 ℃, and stirring;

(2) heating continuously, adding the rest polyphosphoric acid, controlling the reaction temperature to be 120-220 ℃, preferably 140-180 ℃, and stirring to obtain a modified mother liquor intermediate;

(3) and adding SBS into the reaction kettle, controlling the temperature of the reaction kettle to be 120-180 ℃, preferably 140-160 ℃, and stirring to obtain the modifier mother liquor.

In the method for preparing the modifier mother liquor, part of polyphosphoric acid is added in the step (1), and the rest polyphosphoric acid is added in the step (2), wherein the mass ratio of the polyphosphoric acid added in the step (1) to the polyphosphoric acid added in the step (2) is 1: 3-2: 3.

in the method for preparing the modifier mother liquor, the stirring time in the step (1) is 0.5-5.0 hours, and the stirring speed is 200-1000 rpm.

In the method for preparing the modifier mother liquor, the stirring time in the step (2) is 0.5-5.0 hours, and the stirring speed is 200-2000 rpm.

In the method for preparing the modifier mother liquor, the stirring time in the step (3) is 1-10 hours, and the stirring speed is 2000-6000 rpm.

The third aspect of the invention also provides road asphalt, which comprises the following raw materials in parts by weight:

5-40 parts of coal tar pitch,

50-70 parts of petroleum asphalt,

8-20 parts of modifier mother liquor.

The coal pitch is medium-temperature coal pitch with the asphaltene content of less than 30wt%, and the softening point is 72-95 ℃.

The content of asphaltene in the petroleum asphalt is less than 10wt%, and the softening point is 40-50 ℃.

The fourth aspect of the invention also provides a preparation method of the road asphalt, which comprises the following steps:

adding coal pitch, petroleum pitch and the modifier mother liquor into a reaction kettle, and stirring for 1-10 hours at the temperature of 100-180 ℃ and preferably at the temperature of 120-160 ℃ at the stirring speed of 500-4000 revolutions per minute to obtain a road pitch product.

The modifier mother liquor prepared by the method can be used for modifying finished road asphalt, building asphalt and petroleum fraction heavy distillate oil.

The modifier mother liquid of the invention is that phthalic aldehyde compound has two active aldehyde groups, and can perform nucleophilic addition and graft polymerization reaction with anthracene oil fraction, especially O-containing heterocyclic compound and S-containing heterocyclic compound, etc., and polyphosphoric acid is used to further perform condensation modification on the modified anthracene oil, especially two-step method is used to modify anthracene oil, so that anthracene oil reaches proper condensation degree. The mother liquid of the modifier is matched with petroleum asphalt and coal asphalt to prepare road asphalt, so that the colloid structure of a road asphalt product is more reasonable, the high and low temperature performances of the asphalt are enhanced, and the toxicity of the asphalt is reduced.

Detailed Description

The technical solutions of the present invention are described in detail below with reference to examples, which are only used for illustrating the present invention and should not be construed as limiting the scope of the present invention. In the invention, the parts are parts by weight, and the wt% is mass fraction.

Example 1

Adding 90 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 10 parts of terephthalaldehyde and 3 parts of potassium bisulfate, heating, controlling the reaction temperature to be 200 ℃, stirring for 3 hours at the stirring speed of 500 revolutions per minute, and obtaining the modified anthracene oil A1.

84 parts of modified anthracene oil is added into a reaction kettle, 0.9 part of polyphosphoric acid (the concentration of polyphosphoric acid is 110wt percent, the same is applied below) is added, the temperature is heated to 110 ℃, and the mixture is stirred for 2 hours. And continuously heating to about 160 ℃, adding 1.8 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.

12 parts of SBS (star structure, molecular weight of 15 ten thousand, the same below) is added into the modified anthracene oil A1, and the mixture is heated to 150 ℃ and stirred for 5 hours to obtain the modifier mother liquor A2.

Example 2

Adding 94 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 13 parts of terephthalaldehyde and 2 parts of trifluoromethanesulfonic acid, heating, controlling the reaction temperature to be 245 ℃, stirring for 3 hours at the stirring speed of 500 rpm, and obtaining modified anthracene oil A3.

Adding 81 parts of modified anthracene oil into a reaction kettle, adding 0.4 part of polyphosphoric acid, heating to 100 ℃, and stirring for 2 hours. And continuously heating to about 150 ℃, adding 1.1 part of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.

Adding 14 parts of SBS into the modified anthracene oil A3, heating to 155 ℃, and stirring for 6 hours to obtain the modifier mother liquor A4.

Example 3

Adding 86 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 7 parts of terephthalaldehyde and 3 parts of potassium bisulfate, heating, controlling the reaction temperature to be 175 ℃, stirring for 3 hours at the stirring speed of 500 rpm, and obtaining the modified anthracene oil A5.

Adding 84 parts of modified anthracene oil into a reaction kettle, adding 0.9 part of polyphosphoric acid, heating to 110 ℃, and stirring for 2 hours. And continuously heating to about 160 ℃, adding 2.1 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.

Adding 10 parts of SBS into the modified anthracene oil A5, heating to 150 ℃, and stirring for 6 hours to obtain the modifier mother liquor A6.

Example 4

60 parts of petroleum asphalt M1 (the content of asphaltene is 8 wt%) with the softening point of 45 ℃ and 20 parts of coal asphalt N1 (the content of asphaltene is 24 wt%) with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor A2 are added, the rotating speed of a stirrer is 2500 revolutions per minute, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Example 5

68 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 36 parts of coal asphalt N2 (the content of asphaltene is 20 wt%) with the softening point of 78 ℃ are heated to 120 ℃, 18 parts of modifier mother liquor A2 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Example 6

52 parts of petroleum asphalt M2 (the content of asphaltene is 9 wt%) with the softening point of 47 ℃ and 10 parts of coal asphalt N3 (the content of asphaltene is 22 wt%) with the softening point of 82 ℃ are heated to 160 ℃, 10 parts of modifier mother liquor A4 are added, the rotating speed of a stirrer is 2500 revolutions per minute, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Example 7

68 parts of petroleum asphalt M3 (the content of asphaltene is 6 wt%) with the softening point of 43 ℃ and 20 parts of coal asphalt N2 with the softening point of 78 ℃ are heated to 120 ℃, 10 parts of modifier mother liquor A6 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Comparative example 1

Adding 84 parts of anthracene oil with the distillation range of 320-360 ℃ into a reaction kettle, adding 0.9 part of polyphosphoric acid, heating to 110 ℃, and stirring for 2 hours. And continuously heating to 160 ℃, adding 1.8 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.

And adding 12 parts of SBS into the modified mother liquor intermediate, heating to 150 ℃, and stirring for 5 hours to obtain the modifier mother liquor DA 1.

60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to about 140 ℃, 14 parts of modifier mother liquor DA1 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Comparative example 2

84 parts of modified anthracene oil A1 obtained in example 1 are added into a reaction kettle, 12 parts of SBS are added, the temperature is heated to 150 ℃, and the mixture is stirred for 5 hours to obtain modifier mother liquor DA 2.

60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor DA2 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Comparative example 3

84 parts of modified anthracene oil A1 obtained in example 1 was put into a reaction kettle, 2.7 parts of polyphosphoric acid and 12 parts of SBS were added, the mixture was heated to 160 ℃ and stirred for 2 hours to obtain modifier mother liquor DA 3.

60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal asphalt N1 with the softening point of 86 ℃ are heated to 140 ℃, 14 parts of modifier mother liquor DA3 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Comparative example 4

Adding 81 parts of furfural aromatic hydrocarbon extract oil into a reaction kettle, adding 0.4 part of polyphosphoric acid, heating to about 100 ℃, and stirring for 2 hours. And continuously heating to 150 ℃, adding 1.1 parts of polyphosphoric acid, and stirring for 1 hour to obtain a modified mother liquor intermediate.

And adding 14 parts of SBS into the modified mother liquor intermediate, heating to 155 ℃, and stirring for 5 hours to obtain the modifier mother liquor DA 4.

52 parts of petroleum asphalt M2 with the softening point of 47 ℃ and 10 parts of coal pitch N3 with the softening point of 82 ℃ are heated to 160 ℃, 10 parts of modifier mother liquor DA4 are added, the rotating speed of a stirrer is 2500 rpm, and the mixture is stirred for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product.

Comparative example 5

60 parts of petroleum asphalt M1 with the softening point of 45 ℃ and 20 parts of coal pitch N1 with the softening point of 86 ℃ are heated to about 140 ℃, 10.4 parts of anthracene oil, 1.2 parts of terephthalaldehyde, 0.3 part of potassium hydrogen sulfate, 0.4 part of polyphosphoric acid and 1.7 parts of SBS are added, and stirring is carried out, wherein the rotating speed of a stirrer is 2500 revolutions per minute, and stirring is carried out for 2 hours. And discharging after the stirring process is finished, and cooling to room temperature to obtain the target product. The starting materials were the same as in examples 1 and 4.

TABLE 1 Properties of road asphalt products obtained in examples and comparative examples

Numbering	Example 4	Example 5	Example 6	Example 7	Comparative example 1
						Penetration at 25 ℃ of 1/10mm	64	63	68	65	73
Softening point, DEG C	51.5	51.8	50.4	50.6	48.0
						Ductility, cm at 10 ℃	102	92	112	95	70
Fluoranthene removal rate%	53	46	54	43	9

TABLE 2 Properties of the road asphalt product obtained in the comparative example

Numbering	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
					Penetration at 25 ℃ of 1/10mm	81	68	72	68
Softening point, DEG C	46.0	49.8	47.0	48.5
					Ductility, cm at 10 ℃	78	82	50	71
Fluoranthene removal rate%	30	31	3	26

Claims

1. The modifier mother liquor comprises the following raw materials in parts by weight:

78-94 parts of modified anthracene oil;

0.4-3.5 parts of polyphosphoric acid;

4-20 parts of SBS;

the modified anthracene oil is obtained by modifying anthracene oil with phthalaldehyde compounds;

the preparation method of the modifier mother liquor comprises the following steps:

(1) adding the modified anthracene oil into a reaction kettle, adding part of polyphosphoric acid, heating, raising the temperature, controlling the reaction temperature to be 80-140 ℃, and stirring;

(2) heating continuously, adding the rest polyphosphoric acid, controlling the reaction temperature to be 120-220 ℃, and stirring to obtain a modified mother liquor intermediate;

(3) and adding SBS into the reaction kettle, controlling the temperature of the reaction kettle to be 120-180 ℃, and stirring to obtain the modifier mother liquor.

2. The modifier mother liquor as set forth in claim 1, wherein: the using amount of the modified anthracene oil is 80-92 parts; the dosage of the polyphosphoric acid is 0.8-3.2 parts; the amount of SBS is 6-18 parts.

3. The modifier mother liquor as set forth in claim 1, wherein: the modified anthracene oil comprises the following raw materials in parts by weight:

75-98 parts of anthracene oil;

2-25 parts of phthalaldehyde compound;

0.5-5 parts of a catalyst.

4. The modifier mother liquor as set forth in claim 3, wherein: the using amount of the anthracene oil is 85-95 parts; the dosage of the phthalaldehyde compound is 5-15 parts; the amount of the catalyst is 1-4 parts.

5. Modifier liquor as claimed in claim 1 or 3, wherein: the distillation range of the anthracene oil is 300-385 ℃.

6. Modifier liquor as claimed in claim 1 or 3, wherein: the distillation range of the anthracene oil is 320-360 ℃.

7. Modifier liquor as claimed in claim 1 or 3, wherein: the phthalaldehyde compound is one or a mixture of terephthalaldehyde, m-phthalaldehyde and o-phthalaldehyde.

8. The modifier mother liquor as set forth in claim 3, wherein: the catalyst is one or a mixture of more of trifluoromethanesulfonic acid, potassium bisulfate and concentrated sulfuric acid.

9. The modifier mother liquor as set forth in claim 1 or 3, wherein the modified anthracene oil is prepared by a process comprising: adding anthracene oil into a reaction kettle, adding a phthalaldehyde compound and a catalyst, heating, raising the temperature, controlling the reaction temperature to be 150-270 ℃, stirring for 0.5-5.0 hours, and stirring at the speed of 200-1000 rpm to obtain the modified anthracene oil.

10. The modifier mother liquor as claimed in claim 9, wherein the reaction temperature is controlled to 160 to 260 ℃.

11. The modifier mother liquor as set forth in claim 1, wherein: the molecular weight of SBS is 10-20 ten thousand, and it is linear structure or star structure.

12. The modifier mother liquor as set forth in claim 1, wherein: the polyphosphoric acid concentration of the polyphosphoric acid is 105-116 wt%.

13. The method for preparing the modifier mother liquor as claimed in any one of claims 1 to 12, comprising:

14. The method of claim 13, wherein: adding polyphosphoric acid in the steps (1) and (2) according to the mass ratio of 1: 3-2: 3.

15. the method of claim 13, wherein: in the step (1), the reaction temperature is controlled to be 90-130 ℃.

16. The method of claim 13, wherein: and (2) controlling the reaction temperature to be 140-180 ℃.

17. The method of claim 13, wherein: and (3) controlling the temperature of the reaction kettle to be 140-160 ℃.

18. A method according to any of claims 13 to 17, wherein: stirring for 0.5-5.0 hours in the step (1), and stirring at a speed of 200-1000 rpm; stirring for 0.5-5.0 hours in the step (2), and stirring at a speed of 200-2000 rpm; and (4) stirring for 1-10 hours at a stirring speed of 2000-6000 rpm.

19. The road asphalt comprises the following raw materials in parts by weight:

5-40 parts of coal tar pitch,

50-70 parts of petroleum asphalt,

8-20 parts of modifier mother liquor as claimed in any one of claims 1-12.

20. The road asphalt of claim 19, wherein: the coal pitch is medium-temperature coal pitch with the asphaltene content of less than 30wt%, and the softening point is 72-95 ℃; the content of asphaltene in the petroleum asphalt is less than 10wt%, and the softening point is 40-50 ℃.

21. A process for producing the road asphalt of any one of claims 19 to 20, comprising:

adding coal pitch, petroleum pitch and the modifier mother liquor as claimed in any one of claims 1 to 12 into a reaction kettle, and stirring for 1 to 10 hours at a stirring speed of 500 to 4000 revolutions per minute at a temperature of 100 to 180 ℃ in the reactor to obtain a road pitch product.

22. The method of claim 21, wherein: the temperature of the reactor is 120-160 ℃.