Emulsifier for asphalt and preparation method and application thereof

Abstract

The present invention provides a method for preparing an asphalt emulsifier, the method comprising: reacting dichloropropanol still residue with an organic amine to form an intermediate reaction mixture; and then mixing the intermediate reaction mixture with calcium oxide. The present invention also provides an emulsifier prepared by the method, a method for emulsifying asphalt using the emulsifier, and an emulsified asphalt composition prepared thereby. The method of the present invention can fully reuse the dichloropropanol still residue under mild conditions in a simple and low-cost method, greatly eliminating environmental pollution, and preparing an asphalt emulsifier with extremely excellent performance.

Description

Technical Field

[0001] The invention relates to the preparation of organic chemical products, and in particular to a preparation process of an emulsifier. Background Art

[0002] The glycerol process for producing dichloropropane or epichlorohydrin is a method widely used throughout the world, which generally comprises the following steps: first, crude glycerol is subjected to optional purification, such as neutralization, dehydration, rectification, decolorization, desalination, recovery of glycerol from heavy components, etc., to produce refined glycerol; next, the refined glycerol is used as a raw material for chlorination, such as reacting glycerol with hydrogen chloride gas under the action of a carboxylic acid catalyst to generate a reaction mixture, wherein the mixture mainly comprises products such as monochloropropanediol and dichloropropane, and also comprises various by-products, such as organic acid glycerides, glycerol oligomers, etc.; the third step is to rectify the reaction mixture, such as Figure 1 As shown, a rectification treatment is carried out in a rectification tower, dichloropropanol is obtained at the top of the tower, and dichloropropanol still residue is obtained at the bottom of the tower; the dichloropropanol can be directly used as the final product, or optionally in the fourth step, the dichloropropanol is saponified to generate a further product, epichlorohydrin. The dichloropropanol still residue produced by the above-mentioned rectification treatment ("dichloropropanol still residue" is a common name in the art) is a liquid containing various components, which belongs to hazardous waste. Generally, its treatment method is to treat it as hazardous waste by high-temperature pyrolysis and incineration, which has high treatment costs and causes secondary pollution to the environment, which is not conducive to environmental protection. With the progress of the glycerol method for producing dichloropropanol / epichlorohydrin, a large amount of high-risk waste is generated every year. This field is eager to develop a technology to reuse the dichloropropanol still residue as much as possible in a low-cost and simple way, turning waste into treasure while eliminating the impact on the environment.

[0003] In addition, with the development of highway construction and maintenance, the use of road asphalt has greatly increased. Emulsified asphalt has been increasingly widely used in highway construction due to its fast construction, simple process, resource conservation and low pollution. Emulsified asphalt can be used at room temperature, eliminating the heating step before construction, reducing fuel usage and environmental pollution. The key material of emulsified asphalt is asphalt emulsifier. People have been looking for asphalt emulsifiers with excellent emulsification properties and low cost.

[0004] Based on the above-mentioned problems existing in the art, the inventors of the present application have conducted a lot of research and successfully developed a method for treating the dichloropropanol still residue to obtain an asphalt emulsifier with excellent performance. The method can completely reuse the dichloropropanol still residue under mild conditions in a simple and low-cost manner, greatly eliminating environmental pollution, and preparing an asphalt emulsifier with extremely excellent performance, which unexpectedly solves all technical problems in the art. Summary of the invention

[0005] The first aspect of the present invention provides a method for preparing an asphalt emulsifier, the method comprising:

[0006] Step 1: reacting the dichloropropanol still residue with an organic amine to form an intermediate reaction mixture;

[0007] Step 2: mixing the intermediate reaction mixture with calcium oxide.

[0008] According to one embodiment of the first aspect of the present invention, the dichloropropane kettle residue is a waste material generated by producing dichloropropane or epichlorohydrin from glycerol, and the production of dichloropropane or epichlorohydrin from glycerol comprises the following steps:

[0009] (i) chlorinating glycerol as a raw material to generate a mixture containing dichloropropane;

[0010] (ii) subjecting the mixture containing dichloropropane to distillation and purification to generate separated dichloropropane and dichloropropane still residue;

[0011] Optionally (iii) saponifying the separated dichloropropanol to produce epichlorohydrin;

[0012] The dichloropropanol still residue is not further separated or purified before step 1.

[0013] According to another embodiment of the first aspect of the present invention, the organic amine is one or more (C2-C18) alkyl dimethyl tertiary amines.

[0014] According to another embodiment of the first aspect of the present invention, in the step 1, the weight ratio of the dichloropropanol still residue to the organic amine is 1:0.5 to 1:1.5.

[0015] According to another embodiment of the first aspect of the present invention, the weight ratio of the dichloropropanol still residue to the calcium oxide is 100:2 to 100:5.

[0016] According to another embodiment of the first aspect of the present invention, the step 1 is performed at a temperature of 100-150° C. for 3-5 hours.

[0017] According to another embodiment of the first aspect of the present invention, the step 2 is performed at a temperature of 0-150° C. for 1-2 hours.

[0018] According to another embodiment of the first aspect of the present application, all of the dichloropropanol still residue undergoes step one and step two to prepare the asphalt emulsifier.

[0019] The second aspect of the present invention provides an emulsifier for asphalt, which is prepared by the method of the present invention.

[0020] A third aspect of the present invention provides a method for emulsifying asphalt, the method comprising the following steps:

[0021] (I) preparing an emulsified soap solution using an emulsifier, wherein the emulsifier is prepared by the method of the present invention;

[0022] (ii) mixing the emulsified soap solution with the asphalt while mixing or grinding.

[0023] The fourth aspect of the present invention provides an emulsified asphalt composition, characterized in that it is prepared by the method of the present invention, and / or the composition comprises the emulsifier of the present invention, and small emulsified asphalt particles dispersed in the composition.

[0024] In the following detailed description section, the process and design of the present application are described in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 An exemplary formation process of dichloropropanol still bottoms used in the present application is shown;

[0026] Figure 2 A flow chart of a method for preparing an asphalt emulsifier according to one embodiment of the present application is shown. DETAILED DESCRIPTION

[0027] "Range" disclosed herein is in the form of lower limit and upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundary of a particular range. All ranges that can be defined in this way are inclusive of end values ​​and combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, a range of 60-120 and 80-110 is listed for a particular parameter, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0028] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in this document, and "0-5" is just an abbreviation of these numerical combinations.

[0029] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined with each other to form a new technical solution.

[0030] In the present invention, unless otherwise specified, all technical features and preferred features mentioned herein can be combined with each other to form a new technical solution.

[0031] In the present invention, if there is no special explanation, the "including" mentioned herein means open or closed. For example, the "including" may mean that other components not listed may also be included, or only the listed components may be included.

[0032] In the present invention, when describing the spatial relationship of a specific component or object relative to other components or objects, the terms "inside", "outside", "above", "below", etc. are used to indicate that the former is located inside, outside, above or below the latter, and the two may be in direct contact, or be separated by a certain distance or separated by a third component or object.

[0033] It should be emphasized that what is shown in the drawings and described below are only some specific embodiments of the present invention, and the protection scope of the present invention is not limited to these specific embodiments. The protection scope of the present invention is defined by the claims of the present invention, and may include any technical solution within the scope of the claims, including but not limited to further improvements and substitutions to these specific embodiments.

[0034] The above has described the process of producing dichloropropanol or epichlorohydrin by the glycerol process and the process of generating dichloropropanol still residue in the process. According to a non-limiting embodiment of the present application, the dichloropropanol still residue may contain the following components: monochloro fatty acid glyceride, dichloro fatty acid glyceride, fatty acid glyceride, 3-chloro-1,2-propylene glycol, sodium chloride, tar, etc.

[0035] One of the inventive points of the present invention is that the dichloropropanol still residue can be used in its entirety for synthesizing an asphalt emulsifier by the method of the present invention without further separation and purification to remove one or more components therein; in other words, before step 1 of the method of the present invention, the dichloropropanol still residue flowing out from the bottom of the distillation tower is not further separated and purified. The method of the present invention can achieve direct and convenient waste utilization of the dichloropropanol still residue, and can achieve 100% waste utilization of the dichloropropanol still residue.

[0036] like Figure 2 As shown, the method of the present application includes step 1: reacting the dichloropropanol still residue with an organic amine to form an intermediate reaction mixture; and step 2: mixing the intermediate reaction mixture with calcium oxide to prepare an emulsifier for asphalt.

[0037] According to one embodiment of the present application, step one and step two are strictly performed in sequence according to the steps, specifically, step one is performed first, and then step two, the order of adding the organic amine and calcium oxide cannot be reversed, and these two components cannot be added to the dichloropropanol kettle residue at the same time.

[0038] According to one embodiment of the present application, the organic amine used in the step 1 is one or more (C2-C18) alkyl dimethyl tertiary amines, such as (C4-C16) alkyl dimethyl tertiary amines, or (C6-C14) alkyl dimethyl tertiary amines, or (C8-C12) alkyl dimethyl tertiary amines. According to a specific embodiment of the present application, the organic amine is selected from one or more of the following: tetradecyl dimethyl tertiary amine, pentadecyl dimethyl tertiary amine, hexadecyl dimethyl tertiary amine, heptadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, octadecyl dimethyl tertiary amine, or any combination thereof. The above-mentioned "octadecyl dimethyl tertiary amine" means a mixture of octadecyl dimethyl tertiary amine and hexadecyl dimethyl tertiary amine, wherein the weight ratio of octadecyl dimethyl tertiary amine to hexadecyl dimethyl tertiary amine can be 1:10 to 10:1, for example, 1:9 to 9:1, or 1:8 to 8:1, or 1:7 to 7:1, or 1:6 to 6:1, or 1:5 to 5:1, or 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1, or 2:3 to 3:2, or 1:1.5 to 1:1, or within the numerical range obtained by combining any two of the above end values.

[0039] According to one embodiment of the present application, the weight ratio of the dichloropropanol still residue to the organic amine is 1:0.5 to 1:1.5, for example, it can be 1:0.6 to 1:1.4, or 1:0.7 to 1:1.3, or 1:0.8 to 1:1.2, or 1:0.9 to 1:1.1, or 1:1 to 1:1.05, or it can be within the numerical range obtained by combining any two of the above end values.

[0040] According to one embodiment of the present application, in the step 1, the dichloropropanol still residue and the organic amine are mixed at a temperature of 100-150° C. for 3-5 hours; for example, the temperature range may be 110-150° C., or 120-150° C., or 130-150° C., or 140-150° C., or may be within the numerical range obtained by combining any two of the above end values; the mixing time may be 3.5-4.5 hours, for example, 3-4 hours, or 3.2-3.5 hours, or may be within the numerical range obtained by combining any two of the above end values.

[0041] In the subsequent second step, the material that has undergone step 1 is mixed with calcium oxide. According to one embodiment of the present application, in step 2, only calcium oxide is added to the material obtained in step 1 without adding other components.

[0042] According to one embodiment of the present application, the weight ratio of the dichloropropanol still residue to the calcium oxide is 100:2 to 100:5, for example, 100:3 to 100:4, or within the numerical range obtained by combining any two of the above end values.

[0043] According to one embodiment of the present application, in the step 2, the material treated in the step 1 is mixed with the calcium oxide at a temperature of 0-150°C for 1-2 hours; for example, the temperature range can be 10-120°C, or 15-100°C, or 20-80°C, or 25-60°C, or 30-50°C, or 35-40°C, or can be within the numerical range obtained by combining any two of the above end values; the mixing time can be 1-1.5 hours.

[0044] According to one embodiment of the present application, the emulsifier of the present invention is prepared by the above method, and the emulsifier can be used for the emulsification of asphalt. For example, the emulsification may include the following steps: (I) preparing an emulsified soap solution using the emulsifier; (ii) mixing the emulsified soap solution with asphalt while mixing or grinding. For example, according to one embodiment of the present application, the concentration of the emulsified soap solution prepared by the emulsifier is 0.1-20% by weight, based on the total weight of the emulsified soap solution, for example, the concentration of the emulsified soap solution can be 0.2-18% by weight, for example, 0.5-16% by weight, or 0.8-12% by weight, or 1-10% by weight, or 1.2-8% by weight, or 1.5-6% by weight, or 1.8-5% by weight, or 2-4% by weight, or 2.2-3% by weight, or 2.5-2.8% by weight, or can be within the numerical range obtained by combining any two of the above end values.

[0045] According to one embodiment of the present application, the pH value of the emulsified soap solution can be adjusted to 0-5, such as 0.5-4, or 1-3, or 1.2-2, or within the range of values ​​obtained by combining any two of the above end values, using a pH adjuster (such as an inorganic acid or an inorganic base).

[0046] The mixing of the emulsified soap liquid and the asphalt can be carried out using suitable grinding, crushing or stirring equipment, for example, in a colloid mill. According to one embodiment of the present application, the emulsified soap liquid is added to the colloid mill, and the temperature in the colloid mill is maintained at 70-80°C, the asphalt to be emulsified is heated to melt (for example, above 120°C), the melted asphalt is added to the soap liquid in the colloid mill, and ground, crushed or stirred at a temperature of 70-80°C to form emulsified asphalt. .

[0047] Any type of asphalt can be selected as needed. Before emulsification, the solid asphalt can be heated to melt and then mixed with the emulsified soap solution.

[0048] According to one embodiment of the present application, the weight ratio between the asphalt and the emulsified soap solution can be 5:1 to 1:5, for example, 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, or 3:2 to 1:1, or can be within the numerical range obtained by combining any two of the above end values.

[0049] The advantages achieved by the present invention include:

[0050] ● The present invention converts all the originally harmful high-risk waste of dichloropropanol kettle residue into emulsifiers, solving the problems of difficult treatment of dichloropropanol as hazardous waste and serious environmental pollution, saving energy and reducing emissions, and turning waste into treasure;

[0051] ●The emulsifier preparation process is simple, the reaction conditions are mild, no three wastes are generated, and the production cost is low;

[0052] ●The emulsifier has extremely excellent emulsifying properties and is suitable for asphalt of various compositions and sources.

[0053] Example

[0054] The preferred embodiments of the present invention are specifically listed in the following examples, but it should be understood that the protection scope of the present application is not limited thereto. Any equivalent changes or modifications made according to the essence of the present application should be included in the protection scope of the present application.

[0055] The dichloropropane kettle residue used in the following examples comes from the glycerol process production line of epichlorohydrin by Wilmar Surfactant Materials (Lianyungang) Co., Ltd., which contains monochloroglyceryl fatty acid ester, dichloroglyceryl fatty acid ester, fatty acid glyceryl ester, 3-chloro-1,2-propylene glycol, sodium chloride, tar, etc.

[0056] The octadecyl dimethyl tertiary amine (wherein the weight ratio of octadecyl dimethyl tertiary amine to hexadecyl dimethyl tertiary amine is 40:60) and tetradecyl dimethyl tertiary amine were purchased from Clariant Wilmar Fatty Amines (Lianyungang) Co., Ltd.; the calcium oxide and magnesium oxide were chemically pure; the water was deionized water; and the asphalt was Maoming Petrochemical Donghai brand asphalt provided by Maoming Weilong Petrochemical Company.

[0057] The colloid mill used is the LT-RH Longteng emulsified asphalt testing machine provided by Xinxiang Longteng Road Materials Co., Ltd.

[0058] Embodiment 1:

[0059] Into a 500ml four-necked flask equipped with a stirrer and a heating jacket, 100g of the dichloropropanol still residue and 127g of octadecadecyldimethylamine were added, the contents of the flask were heated to 150°C and stirred at this temperature for 4h, 3.5g of calcium oxide powder was added thereto, and stirring was continued at 150°C for 1h to obtain an emulsifier.

[0060] Preparation and performance testing of emulsified asphalt:

[0061] Weigh 5g of the above emulsifier, add it to 195g of water, dissolve it and prepare it into soap solution, adjust the pH value of the soap solution to about 2 with 36% hydrochloric acid, pour the soap solution into the colloid mill, heat it to about 70°C, weigh 300g of 90# asphalt, heat the asphalt to 120°C to melt it into a black liquid, start the colloid mill, and slowly pour the melted liquid asphalt into the colloid mill for emulsification. After all the asphalt is poured in, continue emulsification for 1-2 minutes and then turn off the colloid mill to obtain emulsified asphalt. The performance of the emulsified asphalt is tested according to the test method of "JTG E20-2011 Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering", and the results are shown in Table 1.

[0062] Table 1 Emulsified asphalt performance test results

[0063]

[0064] From the above experimental results, it can be seen that the emulsifier of Example 1 has good emulsification ability for asphalt, the prepared emulsified asphalt has good storage stability, and the product meets the index requirements.

[0065] Embodiment 2:

[0066] Into a 500ml four-necked flask equipped with a stirrer and a heating jacket, 100g of the dichloropropanol still residue and 93g of tetradecyldimethylamine were added, the contents of the flask were heated to 150°C, and stirring was continued at this temperature for 3h, and then 3.6g of calcium oxide powder was added thereto, and stirring was continued at 150°C for 1h to obtain an emulsifier.

[0067] Preparation and performance testing of emulsified asphalt:

[0068] Weigh 5g of the above emulsifier, add it to 195g of water, dissolve it and prepare it into soap solution, adjust the pH value of the soap solution to about 2 with 36% hydrochloric acid, pour the soap solution into the colloid mill, heat it to about 70°C, weigh 300g of 90# asphalt, heat the asphalt to 120°C to melt it into a black liquid, start the colloid mill, and slowly pour the melted liquid asphalt into the colloid mill for emulsification. After all the asphalt is poured in, continue emulsification for 1-2 minutes and then turn off the colloid mill to obtain emulsified asphalt. The performance of the emulsified asphalt is tested according to the test method of "JTG E20-2011 Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering", and the results are shown in Table 2.

[0069] Table 2 Emulsified asphalt performance test results

[0070]

[0071]

[0072] It can be seen from the above experimental results that the emulsifier prepared in this embodiment has good emulsification ability for asphalt, the prepared emulsified asphalt has good storage stability, and the product meets the index requirements.

[0073] Comparative Example 1

[0074] In this comparative example, an attempt was made to prepare an emulsifier without addition of calcium oxide.

[0075] Into a 500 ml four-necked flask equipped with a stirrer and a heating jacket, 100 g of dichloropropanol still residue and 127 g of octadecadecyl dimethyl tertiary amine were added, the contents of the flask were heated to 150° C., and stirring was continued at this temperature for 5 hours to obtain an emulsifier.

[0076] When the emulsified asphalt was prepared using the above emulsifier under the same conditions as in Example 1, obvious stratification occurred after 2 hours of standing, and a stable emulsified asphalt could not be formed.

[0077] Comparative Example 2

[0078] In this comparative example, sodium hydroxide solid was used instead of calcium oxide solid to prepare the emulsifier.

[0079] Into a 500ml four-necked flask equipped with a stirrer and a heating jacket, 100g of the dichloropropanol still residue and 127g of octadecadecyldimethylamine were added, the contents of the flask were heated to 150°C, and stirring was continued at this temperature for 4h, and then 5g of solid sodium hydroxide powder was added thereto, and stirring was continued at 150°C for 1h to obtain an emulsifier.

[0080] When the emulsified asphalt was prepared using the above emulsifier under the same conditions as in Example 1, obvious stratification occurred after 2 hours of standing, and a stable emulsified asphalt could not be formed.

[0081] Comparative Example 3

[0082] In the comparative example, the emulsifier was prepared by adding calcium oxide and tertiary amine simultaneously.

[0083] Into a 500 ml four-necked flask equipped with a stirrer and a heating jacket, 100 g of dichloropropanol still residue, 127 g of octadecadecyl dimethyl tertiary amine and 3.5 g of calcium oxide powder were added, the contents of the flask were heated to 150° C., and stirred continuously at this temperature for 5 h to obtain an emulsifier.

[0084] When the emulsified asphalt was prepared using the above emulsifier under the same conditions as in Example 1, obvious stratification occurred after 2 hours of standing, and a stable emulsified asphalt could not be formed.

[0085] Comparative Example 4

[0086] In this comparative example, magnesium oxide solids were used instead of calcium oxide solids to prepare the emulsifier.

[0087] Into a 500ml four-necked flask equipped with a stirrer and a heating jacket, 100g of the dichloropropanol still residue and 127g of octadecadecyldimethylamine were added, the contents of the flask were heated to 150°C, and stirring was continued at this temperature for 4h, and then 5g of magnesium oxide solid powder was added thereto, and stirring was continued at 150°C for 1h to obtain an emulsifier.

[0088] When the emulsified asphalt was prepared using the above emulsifier under the same conditions as in Example 1, obvious stratification occurred after 2 hours of standing, and a stable emulsified asphalt could not be formed.

Claims

1. A method for preparing an asphalt emulsifier, the method comprising: Step 1: reacting the dichloropropanol still residue with an organic amine to form an intermediate reaction mixture; Step 2: mixing the intermediate reaction mixture with calcium oxide; The dichloropropane kettle residue is waste generated by producing dichloropropane or epichlorohydrin from glycerol, and the production of dichloropropane or epichlorohydrin from glycerol comprises the following steps: (i) chlorinating glycerol as a raw material to generate a mixture containing dichloropropane; (ii) subjecting the mixture containing dichloropropane to distillation and purification to generate separated dichloropropane and dichloropropane still residue; Optionally, (iii) saponifying the separated dichloropropanol to produce epichlorohydrin; The organic amine is one or more (C2-C18) alkyl dimethyl tertiary amines; The weight ratio of the dichloropropanol still residue to the organic amine is 1:0.5 to 1:1.

5.

2. The method according to claim 1, characterized in that The dichloropropanol still residue is not further separated or purified before step 1.

3. The method according to claim 1, characterized in that The weight ratio of the dichloropropanol still residue to the calcium oxide is 100:2 to 100:

5.

4. The method according to claim 1, characterized in that The step 1 is carried out at a temperature of 100-150° C. for 3-5 hours; the step 2 is carried out at a temperature of 0-150° C. for 1-2 hours.

5. The method according to claim 1, characterized in that All of the dichloropropanol kettle residue is subjected to step one and step two to prepare the asphalt emulsifier.

6. An emulsifier for asphalt, prepared by the method according to any one of claims 1 to 5.

7. A method for emulsifying asphalt, the method comprising the following steps: (I) preparing an emulsified soap solution using an emulsifier, wherein the emulsifier is prepared by the method according to any one of claims 1 to 5, or the emulsifier is the emulsifier according to claim 6; (ii) mixing the emulsified soap solution with the asphalt while mixing or grinding.

8. An emulsified asphalt composition, characterized in that It is prepared by the method described in claim 7, and / or the composition comprises an emulsifier prepared by the method described in any one of claims 1 to 5 or the emulsifier described in claim 6, and emulsified asphalt particles dispersed in the composition.

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