Composite reactive warm-mix deodorizing additive, composite reactive warm-mix deodorized asphalt and preparation method therefor

Abstract

Disclosed in the present invention are a composite reactive warm-mix deodorizing additive, composite reactive warm-mix deodorized asphalt and a preparation method therefor. Raw materials of the composite reactive warm-mix deodorizing additive disclosed by the present invention include the following components in percentage by mass: 60-90% of a low-molecular-weight wax having a relative molecular weight of 200-5000, 10-30% of a surfactant, 1-15% of a higher-alcohol organic compound, 1-15% of a phytol-based organic compound, 1-5% of nano calcium carbonate, 1-5% of zinc oxide, and 1-5% of stearic acid. When applied to composite reactive warm-mix deodorized asphalt, the composite reactive warm-mix deodorizing additive of the present invention can significantly reduce irritating odors and harmful gas emissions generated from asphalt during production and construction.

Description

Composite reaction type warm-mix odorless agent, composite reaction type warm-mix odorless asphalt and preparation method thereof TECHNICAL FIELD

[0001] The present application relates to a composite reaction type warm-mix odorless agent, a composite reaction type warm-mix odorless asphalt and a preparation method thereof. BACKGROUND

[0002] The development background of the warm-mix odorless asphalt is mainly to solve the environmental pollution problem existing in the production and construction process of traditional asphalt. Due to the high temperature effect, the traditional hot-mix asphalt will release harmful smoke and produce irritating odor to the air during storage, transportation and construction, which not only pollutes the environment, but also may affect the health of construction personnel and surrounding residents.

[0003] With the increasingly stringent environmental protection requirements and the proposal of the "double carbon" target, the asphalt industry is under pressure to provide green and environmentally friendly products. Therefore, the development of warm-mix odorless asphalt has become an important task of the industry. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the problems of existing asphalt, such as releasing harmful smoke and irritating odor to the air, and to provide a composite reaction type warm-mix odorless agent, a composite reaction type warm-mix odorless asphalt and a preparation method thereof. The composite reaction type warm-mix odorless asphalt prepared by using the composite reaction type warm-mix odorless agent of the present application can significantly reduce the irritating odor and harmful gas emission generated during the production and construction of asphalt.

[0005] The present application uses a composite reaction type warm-mix odorless agent to prepare a composite reaction type warm-mix odorless asphalt. The composite reaction type warm-mix odorless agent combines the functions of warm-mixing agent and odorless agent. The advantage is that instead of modifying by a single odorless agent or a single warm-mixing agent, the composite reaction type warm-mix odorless agent can reduce the temperature of asphalt during chemical reaction, thereby greatly reducing various toxic organic compounds contained in asphalt and asphalt fumes, achieving the dual environmental protection effect of warm-mixing agent and odorless agent. The composite reaction type warm-mix odorless asphalt of the present application not only can effectively reduce environmental pollution, improve construction working environment and simplify construction working process, but also has no great difference in performance from ordinary asphalt or modified asphalt, but can greatly reduce harmful gas emission during mixing process.

[0006] Specifically, the present application solves the above technical problems by the following technical solutions.

[0007] In a first aspect, the present application provides a composite reaction type warm-mixing odorless agent, raw materials of which include the following ingredients in the following mass percentage: 60-90% low molecular weight wax with a relative molecular weight of 200-5000, 10-30% surfactant, 1-15% high carbon alcohol organic matter, 1-15% plant alcohol organic matter, 1-5% nano calcium carbonate, 1-5% zinc oxide and 1-5% stearic acid.

[0008] In some embodiments, the low molecular weight wax is selected from at least one of Fischer-Tropsch wax and polyethylene wax.

[0009] In some embodiments, the low molecular weight wax has a penetration (25℃) ≤5 1 / 10mm and a melting point ≤105℃.

[0010] In some embodiments, the Fischer-Tropsch wax is white granules with a kinematic viscosity of 30-50 mm 2 / s.

[0011] In some embodiments, the polyethylene wax is white powder with a kinematic viscosity of 40-60 mm 2 / s.

[0012] The surfactant can be a surfactant commonly used in the asphalt field, which is selected from at least one of an anionic surfactant, a non-ionic surfactant, and a cationic surfactant. The cationic surfactant is preferably a quaternary ammonium salt type cationic surfactant, such as dimethyl bis-hexadecyl ammonium chloride. The anionic surfactant is preferably a sulfonate type anionic surfactant, such as sodium dodecyl benzene sulfonate. The non-ionic surfactant is preferably a fatty acid polyoxyethylene ester, such as lauric acid polyoxyethylene ester. In some embodiments, the surfactant is preferably selected from at least one of sodium dodecyl benzene sulfonate, lauric acid polyoxyethylene ester, and dimethyl bis-hexadecyl ammonium chloride.

[0013] The high carbon alcohol organic matter is a saturated monohydric alcohol containing a waxy solid with more than twelve carbon atoms. In some embodiments, the high carbon alcohol organic matter is selected from at least one of lauryl alcohol, coconut alcohol, and myristyl alcohol.

[0014] In some embodiments, the plant alcohol organic matter is an alcohol extracted from a plant, selected from at least one of β-phenyl ethanol, geraniol, linalool, and benzyl alcohol.

[0015] In some embodiments, the nano calcium carbonate is white powder.

[0016] In some embodiments, the nano calcium carbonate has a particle size of 20-100 nm.

[0017] In some embodiments, the nano calcium carbonate has a purity of ≥98%.

[0018] In some embodiments, the zinc oxide is a white powder.

[0019] In some embodiments, the particle size of the zinc oxide is ≤ 10 nm.

[0020] In some embodiments, the purity of the zinc oxide is ≥ 99.9%.

[0021] In some embodiments, the stearic acid is a white waxy flaky crystalline.

[0022] In some embodiments, the melting point of the stearic acid is < 69°C.

[0023] In some embodiments, the flash point of the stearic acid is ≥ 220°C.

[0024] In some embodiments, the content of the low molecular wax is 60-65%, for example, 60%, 62%, or 65%.

[0025] In some embodiments, the content of the surfactant is 12-20%, for example, 12%, 15%, 18%, or 20%.

[0026] In some embodiments, the content of the high carbon alcohol organic matter is 5-10%, for example, 7%.

[0027] In some embodiments, the content of the plant alcohol organic matter is 3-8%, for example, 5%.

[0028] In some embodiments, the content of the nano calcium carbonate is 2-4%, for example, 3%.

[0029] In some embodiments, the content of the zinc oxide is 2-4%, for example, 3%.

[0030] In some embodiments, the content of the stearic acid is 2-4%, for example, 2%.

[0031] In some embodiments, the composite reactive warm-mixing odorless agent comprises the following ingredients with the following mass percentage contents: 65% low molecular wax, 15% surfactant, 7% high carbon alcohol organic matter, 5% plant alcohol organic matter, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0032] In some embodiments, the low molecular wax is polyethylene wax, the surfactant is polyoxyethylene laurate and sodium dodecyl benzene sulfonate, the high carbon alcohol organic matter is lauryl alcohol, and the plant alcohol organic matter is linalool.

[0033] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 65% polyethylene wax, 7% polyoxyethylene laurate, 8% sodium dodecyl benzene sulfonate, 7% lauryl alcohol, 5% linalool, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0034] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 62% low molecular wax, 18% surfactant, 7% high carbon alcohol organic, 5% plant alcohol organic, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0035] In some embodiments, the low molecular wax is Fischer-Tropsch wax, the surfactant is sodium dodecyl benzene sulfonate, the high carbon alcohol organic is lauryl alcohol, and the plant alcohol organic is beta-phenyl ethanol.

[0036] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 62% Fischer-Tropsch wax, 18% sodium dodecyl benzene sulfonate, 7% lauryl alcohol, 5% beta-phenyl ethanol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0037] In some embodiments, the low molecular wax is polyethylene wax, the surfactant is dimethyl bis-hexadecyl ammonium chloride and sodium dodecyl benzene sulfonate, the high carbon alcohol organic is myristyl alcohol, and the plant alcohol organic is benzyl alcohol.

[0038] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 62% polyethylene wax, 12% dimethyl bis-hexadecyl ammonium chloride, 6% sodium dodecyl benzene sulfonate, 7% myristyl alcohol, 5% benzyl alcohol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0039] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 60% low molecular wax, 20% surfactant, 7% high carbon alcohol organic, 5% plant alcohol organic, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0040] In some embodiments, the low molecular wax is Fischer-Tropsch wax, the surfactant is fatty acid polyoxyethylene ester, the high carbon alcohol organic is coconut alcohol, and the plant alcohol organic is beta-myrcene.

[0041] In some embodiments, the complex reactive warm mix deodorant includes the following ingredients in the following mass percentage: 60% Fischer-Tropsch wax, 20% fatty acid polyoxyethylene ester, 7% coconut alcohol, 5% myrcene, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0042] In a second aspect, the present application provides a method for preparing the above-mentioned composite reaction-type warm-mixing odorless agent, comprising sequentially mixing the above-mentioned zinc oxide, stearic acid, low-molecular wax, surfactant, high-carbon alcohol organic matter, plant alcohol organic matter and nano calcium carbonate. The low-molecular wax, surfactant, high-carbon alcohol organic matter, plant alcohol organic matter, nano calcium carbonate, zinc oxide and stearic acid are as described in the first aspect of the present application.

[0043] In some embodiments, the method comprises the following steps:

[0044] (1) mixing stearic acid with zinc oxide to obtain a mixture 1;

[0045] (2) mixing low-molecular wax with the mixture 1 to obtain a mixture 2;

[0046] (3) mixing surfactant with the mixture 2 to obtain a mixture 3;

[0047] (4) mixing high-carbon alcohol organic matter and plant alcohol organic matter with the mixture 3 in batches to obtain a mixture 4;

[0048] (5) mixing nano calcium carbonate with the mixture 4;

[0049] Preferably, each mixing is followed by stirring to mix uniformly, and the reaction is preferably carried out in a reaction kettle.

[0050] In some embodiments, the method preheats the reaction kettle to 75-85°C, preferably to 85°C.

[0051] In some embodiments, in step (1), the stearic acid and zinc oxide are added to the reaction kettle and stirred at a speed of 300-500 rpm, the temperature is maintained at 75-85°C, and the stirring is continued for 1.5-2 h until the zinc oxide and stearic acid completely react to form zinc stearate, preferably the stirring is carried out at a speed of 300 rpm, the temperature of the reaction kettle is maintained at 85°C, and the stirring is continued for 1.5 h.

[0052] In some embodiments, in step (2), the mixing is adding low-molecular wax to the mixture 1; preferably, in step (2), the temperature of the reaction kettle is increased to 110-120°C, and after the low-molecular wax is added, the stirring is carried out at a speed of 500-600 rpm for 10-15 min, preferably the temperature of the reaction kettle is increased to 120°C, and the stirring is carried out at a speed of 500 rpm for 15 min.

[0053] In some embodiments, in step (3), the mixing is adding surfactant to the mixture 2; preferably, in step (3), after the surfactant is added, the stirring is carried out at a speed of 300-500 rpm for 10-20 min, preferably the stirring is carried out at a speed of 300 rpm for 20 min.

[0054] In some embodiments, the mixing in step (4) is adding the high carbon alcohol organic and the plant alcohol organic into mixture 3 in batches; preferably the high carbon alcohol organic and the plant alcohol organic are added in step (4) in two batches respectively, wherein preferably 50% of the added amount is added each time; preferably after each addition, stirring at a speed of 300-500 rpm for 5-10 min, more preferably stirring at a speed of 300 rpm for 10 min.

[0055] In some embodiments, the mixing in step (5) is adding the nano calcium carbonate into mixture 4; preferably after adding the nano calcium carbonate in step (5), stirring at a speed of 300 rpm-500 rpm for 10-15 min, preferably stirring at a speed of 300 rpm for 10 min.

[0056] In a third aspect, the present application provides a composite reaction type warm-mixing odorless asphalt, which is composed of the following components: base asphalt, styrene-butadiene-styrene block copolymer (SBS), naphthenic oil, deoiled asphalt (DOA), and composite reaction type warm-mixing odorless agent. The composite reaction type warm-mixing odorless agent is as described in the first aspect of the present application.

[0057] In some embodiments, the content of the base asphalt is 80-85%, for example 80%, 83% or 84%, of the composite reaction type warm-mixing odorless asphalt.

[0058] In some embodiments, the content of the styrene-butadiene-styrene block copolymer is 1-6%, for example 3% or 4%, of the composite reaction type warm-mixing odorless asphalt.

[0059] In some embodiments, the content of the naphthenic oil is 3-5%, for example 3% or 5%, of the composite reaction type warm-mixing odorless asphalt.

[0060] In some embodiments, the content of the deoiled asphalt (DOA) is 6-10%, for example 6.6%, 6.7% or 6.8%, of the composite reaction type warm-mixing odorless asphalt.

[0061] In some embodiments, the content of the composite reaction type warm-mixing odorless agent is 2.3-4.6%, for example 3.2%, 3.3% or 4.4%, of the composite reaction type warm-mixing odorless asphalt.

[0062] In some embodiments, the composite reaction type warm-mixing odorless asphalt is characterized by comprising the following ingredients, the percentages being mass percentages: base asphalt 80-85%, styrene-butadiene-styrene block copolymer 1-6%, naphthenic oil 3-5%, deoiled asphalt (DOA) 6-10%, and composite reaction type warm-mixing odorless agent 2.3-4.6%.

[0063] In some embodiments, the base asphalt is No. 70 base asphalt, such as commonly available Panjin No. 70 asphalt, Zhenhai No. 70 asphalt, South Korea SK No. 70 asphalt, preferably Zhenhai No. 70 asphalt.

[0064] In some embodiments, the styrene-butadiene-styrene block copolymer has a relative molecular weight of 800-300 thousand, preferably Baoling Petrochemical YH792E type SBS.

[0065] In some embodiments, the naphthenic oil has a flash point > 190°C, a kinematic viscosity > 155, preferably Karamay KN4010 type naphthenic oil.

[0066] In some embodiments, the deoiled asphalt has a saturates content of 13-18%, an aromatic content of 24-32%, a gum content of 37-48%, and an asphaltene content of 8-12%, preferably Hengli deoiled asphalt.

[0067] In some embodiments, the composite reaction-type warm-mix odorless asphalt comprises Zhenhai No. 70 asphalt as the base asphalt, Baoling Petrochemical YH792E type SBS as the styrene-butadiene-styrene block copolymer, Karamay KN4010 type naphthenic oil as the naphthenic oil, and Hengli deoiled asphalt as the deoiled asphalt.

[0068] In some embodiments, the composite reaction-type warm-mix odorless asphalt comprises the following ingredients in the following mass percentage contents: 83% base asphalt, 4% styrene-butadiene-styrene block copolymer, 3% naphthenic oil, 6.8% deoiled asphalt, and 3.2% composite reaction-type warm-mix odorless agent.

[0069] In some embodiments, the composite reaction-type warm-mix odorless asphalt comprises the following ingredients in the following mass percentage contents: 84% base asphalt, 3% styrene-butadiene-styrene block copolymer, 3% naphthenic oil, 6.7% deoiled asphalt, and 3.3% composite reaction-type warm-mix odorless agent.

[0070] In some embodiments, the composite reaction-type warm-mix odorless asphalt comprises the following ingredients in the following mass percentage contents: 80% base asphalt, 4% styrene-butadiene-styrene block copolymer, 5% naphthenic oil, 6.6% deoiled asphalt, and 4.4% composite reaction-type warm-mix odorless agent.

[0071] In some embodiments, the composite reaction-type warm-mix odorless asphalt comprises the following ingredients in the following mass percentage contents: 80% base asphalt, 4% styrene-butadiene-styrene block copolymer, 5% naphthenic oil, 7.1% deoiled asphalt, and 3.9% composite reaction-type warm-mix odorless agent.

[0072] In some embodiments, the complex reactive warm-mixing odorless asphalt comprises ingredients in the following mass percentage contents: 83% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 3% Karamay KN4010 naphthenic oil, 6.8% Hengli deoiled asphalt, and 3.2% complex reactive warm-mixing odorless agent.

[0073] In some embodiments, the complex reactive warm-mixing odorless asphalt comprises ingredients in the following mass percentage contents: 84% Zhenhai No. 70 asphalt, 3% Balin Petrochemical YH792E SBS, 3% Karamay KN4010 naphthenic oil, 6.7% Hengli deoiled asphalt, and 3.3% complex reactive warm-mixing odorless agent.

[0074] In some embodiments, the complex reactive warm-mixing odorless asphalt comprises ingredients in the following mass percentage contents: 80% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 5% Karamay KN4010 naphthenic oil, 6.6% Hengli deoiled asphalt, and 4.4% complex reactive warm-mixing odorless agent.

[0075] In some embodiments, the complex reactive warm-mixing odorless asphalt comprises ingredients in the following mass percentage contents: 80% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 5% Karamay KN4010 naphthenic oil, 7.1% Hengli deoiled asphalt, and 3.9% complex reactive warm-mixing odorless agent.

[0076] In a fourth aspect, the present application provides a method for preparing the complex reactive warm-mixing odorless asphalt described above, comprising the following steps:

[0077] S1, obtaining a styrene-butadiene-styrene block copolymer modified asphalt by using a high-speed shearing method with base asphalt and styrene-butadiene-styrene block copolymer as raw materials;

[0078] S2, adding deoiled asphalt to the mixture obtained in S1 and uniformly stirring;

[0079] S3, adding naphthenic oil to the mixture obtained in S2 and uniformly stirring;

[0080] S4, adding a complex reactive warm-mixing odorless agent to the mixture obtained in S3 and uniformly stirring;

[0081] S5, stirring the mixture obtained in S4 to obtain the complex reactive warm-mixing odorless asphalt.

[0082] In some embodiments, the S1 is at 130-150℃ for 30-60 min, then at a shear rate of 8000-10000 r / min and 150-170℃ for 30-60 min, and finally at 150-160℃ for 60-120 min; preferably at 150℃ for 50 min, then at a shear rate of 8000 r / min and 170℃ for 40 min, and finally at 160℃ for 70 min.

[0083] In some embodiments, the S2 is at a reaction temperature of 100-120℃ for 10-30 min, preferably at 120℃ for 20 min.

[0084] In some embodiments, the S3 is at a reaction temperature of 100-120℃ for 10-30 min, preferably at 120℃ for 20 min.

[0085] In some embodiments, the S4 is at a reaction temperature of 100-120℃ for 10-30 min, preferably at 120℃ for 20 min.

[0086] In some embodiments, the S5 is at 120-160℃ for 0.5-1 h with stirring, preferably at 120℃ for 0.5 h.

[0087] On the basis of common knowledge in the art, the above-mentioned preferred conditions can be combined arbitrarily, i.e. to obtain each preferred example of the present application.

[0088] The reagents and raw materials used in the present application are commercially available.

[0089] The positive progress effect of the present application is that:

[0090] The composite reaction type warm-mix odorless asphalt prepared by using the composite reaction type warm-mix odorless agent has no great difference in performance from ordinary asphalt or modified asphalt, the penetration thereof is between 40-60 1 / 10mm, the softening point thereof is ≥60℃, and all can meet the technical requirements, but the rotary viscosity thereof is below 1.6 Pa.s, which is lower than that of ordinary asphalt, and the storage temperature can be reduced by 10℃, thereby reducing the emission. Specifically, the H2S, NO, CO and VOCs emission indexes of the composite reaction type warm-mix odorless asphalt prepared by using the composite reaction type warm-mix odorless agent are all significantly reduced compared with the asphalt without adding the warm-mix agent or the odorless agent, and are also obviously reduced compared with the asphalt adding ordinary odorless agent and warm-mix agent, that is, the use of the composite reaction type warm-mix odorless agent of the present application can effectively reduce environmental pollution. Moreover, the composite reaction type warm-mix odorless asphalt prepared by using the composite reaction type warm-mix odorless agent can also improve the olfactory sense of the asphalt, thereby improving the working environment. In addition, the composite reaction type warm-mix odorless asphalt prepared by using the composite reaction type warm-mix odorless agent simplifies the working operation process.

[0091] DETAILED DESCRIPTION

[0092] The present application is further illustrated by the following examples, but the present application is not limited to the scope of the examples. The experimental methods in the following examples without specific conditions are selected according to the conventional methods and conditions, or according to the commodity instruction.

[0093] Preparation of the composite reaction type warm-mix odorless agent

[0094] Synthesis Example 1:

[0095] The reaction kettle is preheated to 50℃. 62% of the relative molecular weight is 200-5000, the penetration (25℃) is ≤5 1 / 10mm, the melting point is ≤105℃, the rotary viscosity is 30-50 mm 2Fischer-Tropsch wax (s) was poured into a preheated reaction kettle as a base component. 18% sodium dodecyl benzene sulfonate was slowly added while stirring at 300 rpm for 5 min to help the surfactant disperse in the low molecular wax. 7% lauryl alcohol and 5% beta-phenylethanol were added to the reaction kettle in sequence, and after each addition, stirring was continued at 300 rpm for 10 min to ensure that these components were uniformly dispersed in the mixture. 3% nano calcium carbonate (particle size 20-100 nm) and 3% zinc oxide (particle size ≤10 nm) were added according to the formula, and stirring was continued at 300 rpm for 10 min to ensure uniform dispersion of these inorganics. 2% stearic acid was added, and after stirring at 300 rpm for 5 min, the stirring speed was increased to 500 rpm, and stirring was continued for 15 min to ensure complete mixing of all components. After the heater was turned off, the mixture was naturally cooled to room temperature (about 25°C) under stirring, and then the stirring was stopped, and the prepared composite warm-mix deodorant was taken out of the reaction kettle, and the preparation was completed.

[0096] Synthesis Example 2-5:

[0097] The composite reaction-type warm-mix deodorant of Synthesis Example 2-4 was prepared in the same way, with the mass percentage content of each component being as follows:

[0098] Synthesis Example 2:

[0099] 60% Fischer-Tropsch wax, 20% fatty acid polyoxyethylene ester, 7% coconut alcohol, 5% geraniol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0100] Synthesis Example 3:

[0101] 65% polyethylene wax (relative molecular mass 200-5000, penetration (25°C) ≤5 1 / 10 mm, melting point ≤105°C, rotary viscosity 40-60 mm 2 / s), 7% fatty acid polyoxyethylene ester, 8% sodium dodecyl benzene sulfonate, 7% lauryl alcohol, 5% linalool, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0102] Synthesis Example 4:

[0103] 62% polyethylene wax, 12% dimethyl bis-hexadecyl ammonium chloride, 6% sodium dodecyl benzene sulfonate, 7% myristyl alcohol, 5% benzyl alcohol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

[0104] Synthesis Example 5:

[0105] 50% Fischer-Tropsch wax, 48% sodium dodecyl benzene sulfonate, 0.2% lauryl alcohol, 0.2% beta-phenylethanol, 0.2% nano calcium carbonate, 0.2% zinc oxide, and 0.2% stearic acid.

[0106] Preparation of complex reaction type warm-mix odorless asphalt

[0107] Example 1

[0108] A styrene-butadiene-styrene block copolymer modified asphalt was obtained by high-speed shearing method with 83% Zhenhai No. 70 asphalt and 4% Balin Petrochemical YH792E type SBS as raw materials, wherein it was continuously stirred at 150℃ for 50 min, then at a shearing rate of 8000 r / min and 170℃ for 40 min, and finally at 160℃ for 70 min; 6.8% Hengli deoiled asphalt was added and uniformly stirred, and continuously stirred at a reaction temperature of 120℃ for 20 min; 3% Karamay KN4010 type naphthenic oil was added and uniformly stirred, and continuously stirred at a reaction temperature of 120℃ for 20 min; 3.2% complex reaction type warm-mix odorless agent of synthesis example 1 was added and uniformly stirred, and continuously stirred at a reaction temperature of 120℃ for 20 min; continuously stirred at 120℃ for 0.5 h, and a reaction type warm-mix odorless SBS modified asphalt was obtained.

[0109] Examples 2-4 and comparative examples 1-4

[0110] Examples 2-3 and comparative examples 1-4 were prepared in the same way, wherein the mass percentage content of the components in each example and comparative example was as follows:

[0111] Example 2

[0112] 84% Zhenhai No. 70 asphalt, 3% Balin Petrochemical YH792E type SBS, 3% Karamay KN4010 type naphthenic oil, 6.7% Hengli deoiled asphalt and 3.3% complex reaction type warm-mix odorless agent.

[0113] Example 3

[0114] 80% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E type SBS, 5% Karamay KN4010 type naphthenic oil, 6.6% Hengli deoiled asphalt and 4.4% complex reaction type warm-mix odorless agent.

[0115] Example 4

[0116] 80% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E type SBS, 5% Karamay KN4010 type naphthenic oil, 7.1% Hengli deoiled asphalt and 3.9% complex reaction type warm-mix odorless agent.

[0117] Comparative example 1

[0118] 83% Zhenhai No. 70 asphalt, 6% Balin Petrochemical YH792E type SBS, 5% Karamay KN4010 type naphthenic oil and 6% Hengli deoiled asphalt.

[0119] Comparative Example 2:

[0120] 82% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 4% Karamay KN4010 naphthenic oil, 9% Hengli deoiled asphalt, and 1% composite reaction type warm-mix odorless agent (synthesis example 1).

[0121] Comparative Example 3:

[0122] 83% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 3% Karamay KN4010 naphthenic oil, 6.8% Hengli deoiled asphalt, 2.6% warm-mix agent (Fischer-Tropsch wax with a molecular weight of 200-5000), and 0.6% odorless agent (lauryl alcohol).

[0123] Comparative Example 4:

[0124] 84% Zhenhai No. 70 asphalt, 4% Balin Petrochemical YH792E SBS, 3% Karamay KN4010 naphthenic oil, 6.8% Hengli deoiled asphalt, and 3.2% composite reaction type warm-mix odorless agent (synthesis example 5).

[0125] Test item table

[0126] Test item Unit Technical requirement Test method Penetration (25℃) 0.1 mm 40~60 T 0604-2011 Softening point TR&B ℃ ≥ 65 T 0606-2011 Rotational viscosity (135℃) Pa.s ≤ 3 T 0625-2011

[0127] Table 1

[0128] Index Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Penetration 50 53 51 53 52 53 54 54 Softening point 73 70 71 26 96 62 65 61 Rotational viscosity 1.5 1.4 1.6 1.5 2.9 2.1 2.0 1.8 Storage temperature reduction 10 10 10 10 10 10

[0129] As can be seen from Table 1, in Examples 1 to 4 of the present application, after the addition of the composite reaction type warm-mix odorless agent of the present application, the composite reaction type warm-mix odorless asphalt obtained has a penetration, a softening point, and a rotational viscosity that all meet the technical requirements, and the rotational viscosity is as low as 1.6 Pa.s or lower measured by the method of T 0625-2011, and the storage temperature can be reduced by 10℃. In contrast, in Comparative Examples 1, 3-4 that do not add the composite reaction type warm-mix odorless agent of the present application, the rotational viscosity exceeds 1.8 Pa.s, and the storage temperature of Comparative Examples 1, 2 cannot be reduced or is only reduced by 7℃.

[0130] It can be seen that the composite reaction type warm-mixed odorless asphalt of the embodiment can have lower rotary viscosity than the comparative examples and can reduce the storage temperature, thereby reducing emissions, while keeping the performance such as penetration and softening point within the technical requirement range.

[0131] Examples 1 to 4 and Comparative Examples 1 to 4 of the present application were evaluated by the Japanese six-level classification method for odor intensity

[0132] Intensity index 0 odorless 1 can barely feel the odor 2 odor is very weak but can distinguish its nature 3 can easily feel the odor 4 strong odor 5 unbearable extremely strong odor

[0133] Table 2

[0134] Case Intensity Example 1 Example 2 Example 3 Example 4 Comparative Example 4 Comparative Example 3 Comparative Example 2 Comparative Example 1

[0135] As can be seen from Table 2, in Examples 1 to 4 of the present application, after adding the composite reaction type warm-mixed odorless agent of the present application, the composite reaction type warm-mixed odorless asphalt obtained has an intensity of 1 evaluated by the Japanese six-level classification method for odor intensity, and can barely feel the odor. In contrast, in Comparative Example 1 in which the composite reaction type warm-mixed odorless agent of the present application is not added, the test result is as high as 4, i.e. a strong odor can be felt, and in Comparative Examples 2-4, the test result is as high as 3, i.e. the odor can be easily felt.

[0136] As can be seen, the composite reaction type warm-mixed odorless asphalt of the embodiment has a Japanese six-level classification method for odor intensity evaluation result superior to that of the comparative examples by adding the composite reaction type warm-mixed odorless agent of the present application, indicating that the composite reaction type warm-mixed odorless asphalt of the present application has improved olfactory organoleptic properties, thereby improving the working environment.

[0137] Table 3 (detection standard T / SMHTA004-2023)

[0138] Emission index H2S / ppm NO / ppm CO / ppm VOCs / (mg / kg) Example 1 47.2 10.5 37.2 87.6 Example 2 42.1 7.6 45.6 90.3 Example 3 49.5 12.7 48.9 88.5 Example 4 45.2 9.4 36.1 84 Comparative Example 1 114.2 46.9 104.7 194.6 Comparative Example 2 78.2 34.2 67.4 121 Comparative Example 3 57.9 14.6 58.5 104.1 Comparative Example 4 64.8 24.1 76.3 134.4

[0139] As can be seen from Table 3, in Examples 1 to 4 of the present application, after adding the composite reactive warm-mix odorless agent of the present application, the composite reactive warm-mix odorless asphalt obtained has H2S emission less than 50 ppm, NO emission less than 13 ppm, CO emission less than 49 ppm and VOCS emission less than 91 ppm. In contrast, in Comparative Example 1 without adding the composite reactive warm-mix odorless agent of the present application, the H2S emission is as high as 114.2 ppm, the NO emission is as high as 46.9 ppm, the CO emission is as high as 104.7 ppm and the VOCS emission is as high as 194.6 ppm, all of which are significantly higher than the emissions of the Examples by more than 2 times. The emissions in Comparative Examples 2 to 4 are also significantly higher than those in Examples 1 to 4.

[0140] It can be seen that the composite reactive warm-mix odorless asphalt of the Examples has lower H2S, NO, CO and VOCS emissions by adding the composite reactive warm-mix odorless agent of the present application, indicating that the composite reactive warm-mix odorless asphalt of the present application can reduce emissions and thus effectively reduce environmental pollution.

Claims

1. A complex reaction-type warm-mixing odorless agent, characterized by, The raw materials of the composite reaction type warm-mixing odorless agent include the following ingredients with the following mass percentage contents: 60-90% low molecular wax with a relative molecular mass of 200-5000, 10-30% surfactant, 1-15% high carbon alcohol organic matter, 1-15% plant alcohol organic matter, 1-5% nano calcium carbonate, 1-5% zinc oxide and 1-5% stearic acid.

2. The complex reactive warm-mixing tasteless agent according to claim 1, characterized in that, It satisfies one or more of the following conditions: (1) the low molecular wax is selected from at least one of Fischer-Tropsch wax and polyethylene wax; the Fischer-Tropsch wax is preferably white granules, and the kinematic viscosity thereof is 30-50 mm 2 / s; the polyethylene wax is preferably white powder, and the kinematic viscosity thereof is 40-60 mm 2 / s; (2) The penetration (25℃) of the low molecular wax is ≤5 1 / 10 mm, and the melting point is ≤105℃; (3) The surfactant is selected from one or more of anionic surfactant, non-ionic surfactant and cationic surfactant; the cationic surfactant is preferably a quaternary ammonium salt type cationic surfactant, such as dimethyl bis-hexadecyl ammonium chloride; the anionic surfactant is preferably a sulfonate type anionic surfactant, such as sodium dodecyl benzene sulfonate; the non-ionic surfactant is preferably a fatty acid polyoxyethylene ester, such as lauric acid polyoxyethylene ester; the surfactant is preferably selected from at least one of sodium dodecyl benzene sulfonate, lauric acid polyoxyethylene ester and dimethyl bis-hexadecyl ammonium chloride; (4) The high carbon alcohol organic matter is a saturated monohydric alcohol containing a waxy solid with more than twelve carbon atoms, and is preferably selected from at least one of lauryl alcohol, coconut alcohol and myristyl alcohol; (5) The plant alcohol organic matter is an alcohol extracted from a plant, and is preferably selected from at least one of β-phenyl ethanol, geraniol, linalool and benzyl alcohol; (6) The nano calcium carbonate is a white powder; (7) The particle size of the nano calcium carbonate is 20-100 nm; (8) The purity of the nano calcium carbonate is ≥98%; (9) The zinc oxide is a white powder; (10) The particle size of the zinc oxide is ≤10 nm; (11) The purity of the zinc oxide is ≥99.9%; (12) The stearic acid is a white waxy small flake crystalline body; (13) The melting point of the stearic acid is <69℃; (14) The flash point of the stearic acid is ≥220℃; (15) The content of the low molecular wax is 60-65%, such as 60%, 62% or 65%; (16) The content of the surfactant is 12-20%, such as 12%, 15%, 18% or 20%; (17) The content of the high carbon alcohol organic matter is 5-10%, such as 7%; (18) The content of the plant alcohol organic matter is 3-8%, such as 5%; (19) The content of the nano calcium carbonate is 2-4%, such as 3%; (20) The content of the zinc oxide is 2-4%, such as 3%; (21) The content of the stearic acid is 1-3%, such as 2%.

3. The complex reactive warm mix odorless agent according to claim 1, characterized in that, It satisfies one of the following conditions: (1) The composite reaction type warm-mixing odorless agent includes the following ingredients with the following mass percentage contents: 65% low molecular wax, 15% surfactant, 7% high carbon alcohol organic matter, 5% plant alcohol organic matter, 3% nano calcium carbonate, 3% zinc oxide and 2% stearic acid. Preferably, the low molecular wax is polyethylene wax, the surfactant is a combination of polyoxyethylene laurate and sodium dodecyl benzene sulfonate, the high carbon alcohol organic matter is lauryl alcohol, and the plant alcohol organic matter is linalool; For example, the composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 65% polyethylene wax, 7% polyoxyethylene laurate, 8% sodium dodecyl benzene sulfonate, 7% lauryl alcohol, 5% linalool, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid. (2) The composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 62% low molecular wax, 18% surfactant, 7% high carbon alcohol organic matter, 5% plant alcohol organic matter, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid. Preferably, the low molecular wax is Fischer-Tropsch wax, the surfactant is sodium dodecyl benzene sulfonate, the high carbon alcohol organic matter is lauryl alcohol, and the plant alcohol organic matter is β-phenylethanol. Or the low molecular wax is polyethylene wax, the surfactant is dimethyl bis-hexadecyl ammonium chloride and sodium dodecyl benzene sulfonate, the high carbon alcohol organic matter is myristyl alcohol, and the plant alcohol organic matter is benzyl alcohol. For example, the composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 62% Fischer-Tropsch wax, 18% sodium dodecyl benzene sulfonate, 7% lauryl alcohol, 5% β-phenylethanol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid. Or the composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 62% polyethylene wax, 12% dimethyl bis-hexadecyl ammonium chloride, 6% sodium dodecyl benzene sulfonate, 7% myristyl alcohol, 5% benzyl alcohol, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid. (3) The composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 60% low molecular wax, 20% surfactant, 7% high carbon alcohol organic matter, 5% plant alcohol organic matter, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid. Preferably, the low molecular wax is Fischer-Tropsch wax, the surfactant is fatty acid polyoxyethylene ester, the high carbon alcohol organic matter is coconut alcohol, and the plant alcohol organic matter is β-myrcene. For example, the composite reactive warm-mixing odorless agent comprises the following ingredients in mass percentage: 60% Fischer-Tropsch wax, 20% fatty acid polyoxyethylene ester, 7% coconut alcohol, 5% myrcene, 3% nano calcium carbonate, 3% zinc oxide, and 2% stearic acid.

4. A method of preparing the complex reactive warm-mixing tasteless agent according to any one of claims 1 to 3, characterized in that, The method comprises sequentially mixing zinc oxide, stearic acid, low molecular wax, surfactant, high carbon alcohol organic matter, plant alcohol organic matter, and nano calcium carbonate; preferably, the method comprises the following steps: (1) mixing stearic acid and zinc oxide to obtain a mixture 1; (2) mixing low molecular wax and the mixture 1 to obtain a mixture 2; (3) mixing surfactant and the mixture 2 to obtain a mixture 3; (4) mixing high carbon alcohol organic matter and plant alcohol organic matter into the mixture 3 in batches to obtain a mixture 4; (5) mixing nano calcium carbonate and the mixture 4; Preferably, each mixture is stirred to be uniformly mixed, and the reaction is preferably carried out in a reaction kettle.

5. The method of claim 4, wherein, It meets one or more of the following conditions: (1) the method preheats the reactor to 75-85°C, preferably to 85°C; (2) in step (1), the stearic acid and zinc oxide are added to the reactor and stirred at a speed of 300-500 rpm, maintaining 75-85°C, and the stirring is continued for 1.5-2 h until the zinc oxide and stearic acid completely react to form zinc stearate, preferably at a stirring speed of 300 rpm, and the reactor temperature is maintained at 85°C, and the stirring is continued for 1.5 h; (3) in step (2), the mixing is adding low molecular wax to mixture 1; preferably in step (2), the temperature of the reactor is increased to 110-120°C, and after the low molecular wax is added, the stirring is continued at a speed of 500-600 rpm for 10-15 min, preferably the temperature of the reactor is increased to 120°C, and the stirring is continued at a speed of 500 rpm for 15 min; (4) in step (3), the mixing is adding surfactant to mixture 2; preferably in step (3), after the surfactant is added, the stirring is continued at a speed of 300-500 rpm for 10-20 min, preferably at a speed of 300 rpm for 20 min; (5) in step (4), the mixing is adding high-carbon alcohol organic matter and plant alcohol organic matter to mixture 3 in batches; preferably in step (4), the high-carbon alcohol organic matter and plant alcohol organic matter are added in two portions, and preferably 50% of the added amount is added each time; preferably after each addition, the stirring is continued at a speed of 300-500 rpm for 5-10 min, more preferably at a speed of 300 rpm for 10 min; (6) in step (5), the mixing is adding nano calcium carbonate to mixture 4; preferably in step (5), after the nano calcium carbonate is added, the stirring is continued at a speed of 300-500 rpm for 10-15 min, preferably at a speed of 300 rpm for 10 min.

6. A complex reactive warm mix odorless agent, characterized by, Prepared by the method of claims 4-5.

7. A compound reaction warm mix odorless asphalt, characterized in that, The composite reactive warm-mixing odorless asphalt comprises the composite reactive warm-mixing odorless agent prepared by the method of claims 4-5.

8. The compound reaction-type warm-mix odorless asphalt according to claim 7, characterized in that, The composite reactive warm-mixing odorless asphalt comprises: base asphalt, styrene-butadiene-styrene block copolymer, naphthenic oil, deoiled asphalt (DOA), and composite reactive warm-mixing odorless agent; The content of the base asphalt is preferably 80-85%, for example 80%, 83% or 84%; the content of the styrene-butadiene-styrene block copolymer is preferably 1-6% of the composite reaction type warm-mix odorless asphalt, for example 3% or 4%; the content of the naphthenic oil is preferably 3-5% of the composite reaction type warm-mix odorless asphalt, for example 3% or 5%; the content of the deoiled asphalt (DOA) is preferably 6-10% of the composite reaction type warm-mix odorless asphalt, for example 6.6%, 6.7% or 6.8%; the content of the composite reaction type warm-mix odorant is preferably 2.3-4.6% of the composite reaction type warm-mix odorless asphalt, for example 3.2%, 3.3% or 4.4%; preferably the composite reaction type warm-mix odorless asphalt contains the following ingredients in the following mass percentages: base asphalt 80-85%, styrene-butadiene-styrene block copolymer 1-6%, naphthenic oil 3-5%, deoiled asphalt (DOA) 6-10%, composite reaction type warm-mix odorant 2.3-4.6%; The base asphalt is preferably No. 70 base asphalt, for example Panjin No. 70 asphalt, Zhenhai No. 70 asphalt, South Korea SK No. 70 asphalt, more preferably Zhenhai No. 70 asphalt; preferably the relative molecular weight of the styrene-butadiene-styrene block copolymer is 800-300 thousand, more preferably YH792E type SBS of Baling Petrochemical; the flash point of the naphthenic oil is preferably > 190°C, and the kinematic viscosity is preferably > 155, more preferably Karamay KN4010 type naphthenic oil; preferably the deoiled asphalt has a saturates content of 13-18%, an aromatic content of 24-32%, a gum content of 37-48% and an asphaltene content of 8-12%, more preferably Hengli deoiled asphalt; preferably the base asphalt in the composite reaction type warm-mix odorless asphalt is Zhenhai No. 70 asphalt, the styrene-butadiene-styrene block copolymer is YH792E type SBS of Baling Petrochemical, the naphthenic oil is Karamay KN4010 type naphthenic oil, and the deoiled asphalt is Hengli deoiled asphalt; It is also preferred that the composite reaction type warm-mix odorless asphalt comprises the following ingredients in the following mass percentages: (1) 83% base asphalt, 4% styrene-butadiene-styrene block copolymer, 3% naphthenic oil, 6.8% deoiled asphalt and 3.2% composite reaction type warm-mix odorant; for example 83% Zhenhai No. 70 asphalt, 4% YH792E type SBS of Baling Petrochemical, 3% Karamay KN4010 type naphthenic oil, 6.8% Hengli deoiled asphalt and 3.2% composite reaction type warm-mix odorant; (2) 84% base asphalt, 3% styrene-butadiene-styrene block copolymer, 3% naphthenic oil, 6.7% deoiled asphalt and 3.3% composite reaction type warm-mix odorant; for example 84% Zhenhai No. 70 asphalt, 3% YH792E type SBS of Baling Petrochemical, 3% Karamay KN4010 type naphthenic oil, 6.7% Hengli deoiled asphalt and 3.3% composite reaction type warm-mix odorant; (3) 80% base asphalt, 4% styrene-butadiene-styrene block copolymer, 5% naphthenic oil, 6.6% deoiled asphalt, and 4.4% complex reactive warm-mixing odorless agent; for example, 80% Zhenhai No. 70 asphalt, 4% SBS of YH792E type of Balin Petrochemical, 5% naphthenic oil of KN4010 type of Karamay, 6.6% deoiled asphalt of Hengli, and 4.4% complex reactive warm-mixing odorless agent; or (4) 80% base asphalt, 4% styrene-butadiene-styrene block copolymer, 5% naphthenic oil, 7.1% deoiled asphalt, and 3.9% complex reactive warm-mixing odorless agent; for example, 80% Zhenhai No. 70 asphalt, 4% SBS of YH792E type of Balin Petrochemical, 5% naphthenic oil of KN4010 type of Karamay, 7.1% deoiled asphalt of Hengli, and 3.9% complex reactive warm-mixing odorless agent.

9. A method of making the complex reactive warm mix odor-free asphalt according to any one of claims 7-8, characterized in that, The method comprises the following steps: S1, obtaining styrene-butadiene-styrene block copolymer modified asphalt by high-speed shearing method with base asphalt and styrene-butadiene-styrene block copolymer as raw materials; S2, adding deoiled asphalt to the mixture obtained in S1 and uniformly stirring; S3, adding naphthenic oil to the mixture obtained in S2 and uniformly stirring; S4, adding complex reactive warm-mixing odorless agent to the mixture obtained in S3 and uniformly stirring; S5, stirring the mixture obtained in S4 to obtain the complex reactive warm-mixing odorless asphalt.

10. The method of claim 9, wherein, It meets one or more of the following conditions: (1) S1 is at 130-150°C for 30-60 min, then at a shearing rate of 8000-10000 r / min and 150-170°C for 30-60 min, and finally at 150-160°C for 60-120 min; preferably at 150°C for 50 min, then at a shearing rate of 8000 r / min and 170°C for 40 min, and finally at 160°C for 70 min; (2) S2 is at a reaction temperature of 100-120°C for 10-30 min, preferably at 120°C for 20 min; (3) S3 is at a reaction temperature of 100-120°C for 10-30 min, preferably at 120°C for 20 min; (4) S4 is at a reaction temperature of 100-120°C for 10-30 min, preferably at 120°C for 20 min; (5) S5 is stirred at 120-160°C for 0.5-1 h, preferably at 120°C for 0.5 h.