Environment-friendly coal water slurry additive and preparation method thereof

Abstract

The present application relates to the technical field of coal fuel, and discloses an environment-friendly water coal slurry additive and a preparation method thereof.The structural formula of the environment-friendly water coal slurry additive provided by the present application is: The environment-friendly water coal slurry additive provided by the present application has good universality, can be applied to low-rank coal, medium-rank coal and high-rank coal, and has good dispersibility and high dispersion stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coal fuel, in particular to an environmentally-friendly coal water slurry additive and a preparation method thereof. BACKGROUND

[0002] The coal water slurry is a new type of coal-based liquid fuel with low pollution and high efficiency and strong fluidity, which can replace heavy oil to alleviate energy shortage and other problems. The coal water slurry is processed by taking coal and water as main raw materials, and in the processing process, in order to ensure the rheological property and stability of the coal water slurry, a certain chemical additive must be added. According to the functions of the chemical additives used for slurry preparation, the chemical additives can be divided into dispersants, stabilizers and auxiliary chemical reagents (defoaming agents, pH value adjusting agents, etc.), among which the dispersant is the most important chemical additive.

[0003] According to the charges on the molecular chain of the dispersant, the dispersant can be divided into nonionic dispersant, anionic dispersant, cationic dispersant and amphoteric dispersant. The dispersant has a high cost and is the main part of the slurry preparation cost. Considering the cost performance, the anionic dispersant is the preferred additive for slurry preparation at present, and the commonly used ones include lignin dispersant, humic acid dispersant, naphthalene sulfonate dispersant and polycarboxylate dispersant. Among them, the polycarboxylate dispersant is concerned by people due to its environmental protection and high efficiency.

[0004] However, the existing polycarboxylate dispersant has the problems of poor universality and poor dispersibility for coal types, and based on this, it becomes a technical problem to be solved by the person skilled in the art to provide a polycarboxylate dispersant for coal water slurry with good universality and good dispersibility. SUMMARY

[0005] The purpose of the present application is to provide an environmentally-friendly coal water slurry additive and a preparation method thereof, which has good universality and good dispersibility.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] One of the technical schemes of the present application is as follows:

[0008] An environmentally-friendly coal water slurry additive has the following structural formula:

[0009]

[0010] In the formula, a=1-3, b=2-5, and c=8-15.

[0011] R is selected from one of C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C7-C10 alkyl-substituted phenyl.

[0012] As preferred, in the formula, a = 1-2, b = 2-4, c = 10-15;

[0013] R is selected from methyl, hexyl, cyclopentane, cyclohexyl, propylene, methylphenyl or ethylphenyl.

[0014] The typical structure of the environment-friendly coal water slurry additive includes:

[0015]

[0016]

[0017] The second technical scheme of the present application is:

[0018] The preparation method of the environment-friendly coal water slurry additive includes the following steps:

[0019] 1) mixing methacrylic acid and alcohol, esterification reaction to obtain methacrylic ester;

[0020] 2) mixing dibutyl fumarate, methacrylic ester obtained in step 1) and methacrylic acid, polymerization reaction to obtain the environment-friendly coal water slurry additive.

[0021] Further, in step 1), the alcohol is ROH.

[0022] In the formula, R is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C7-C10 alkyl-substituted phenyl.

[0023] Further, in step 1), the molar ratio of methacrylic acid and alcohol is 1:(1.5-2).

[0024] Further, in step 1), the esterification reaction is specifically: using p-toluenesulfonic acid as a catalyst, reacting at 60-80℃ for 4-6h.

[0025] Further, in step 2), the molar ratio of dibutyl fumarate, methacrylic ester and methacrylic acid is (1-3):(2-5):(8-15).

[0026] Further, in step 2), the polymerization reaction is specifically: first heating the methacrylic ester obtained in step 1) to 70-90℃, then controlling the dropping speed to 20-30d / min, dropping dibutyl fumarate, methacrylic acid and initiator into the methacrylic ester, after the dropping is completed, heating to 120-160℃, and polymerizing for 4-6h.

[0027] Further, the initiator is BPO.

[0028] The synthetic route of the above-mentioned environment-friendly coal water slurry additive is as follows:

[0029] (1)

[0030] (2)

[0031] The third technical scheme of the present application is:

[0032] The above-mentioned environment-friendly coal water slurry additive is applied to preparation of coal water slurry.

[0033] Compared with the prior art, the present application has the beneficial effects that:

[0034] The coal water slurry additive provided by the present application can effectively increase the negative value of zeta potential, reduce the shielding effect of negative charges on the surface of coal particles, form a stable diffuse double electric layer, and thus effectively improve the stability of the coal water slurry system.

[0035] The coal water slurry prepared by the coal water slurry additive provided by the present application has only a small amount of precipitation after standing for 7 days, and has good stability, so the coal water slurry additive provided by the present application has good dispersion stability. DETAILED DESCRIPTION

[0036] The various illustrative embodiments of the present application are now described in detail. The detailed description should be considered in connection with the drawings, not as a limitation of the present application. It is understood that the terms described in the present application are only for describing the particular embodiments, and are not intended to limit the present application.

[0037] In addition, for the numerical range in the present application, it is understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between any stated value or stated range and any other stated value or intermediate value in the stated range is also included in the present application. The upper limit and the lower limit of these smaller ranges can be independently included or excluded from the range.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, preferred methods and materials are described. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict, the content of the specification will control.

[0039] Many modifications and variations of the present application described in the specification are possible without departing from the scope or spirit of the application. Other implementations of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The specification and examples are illustrative only.

[0040] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean inclusion, but not limited to, the listed material or list of materials.

[0041] In the following examples, a preparation method of an environmentally friendly coal water slurry additive includes the following steps:

[0042] 1) According to the molar ratio of methacrylic acid and alcohol is 1: (1.5-2), methacrylic acid and alcohol are mixed, toluenesulfonic acid is used as a catalyst, and esterification reaction is carried out at 60-80℃ for 4-6h to obtain methacrylic acid ester;

[0043] In the formula, R is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C7-C10 alkyl substituted phenyl;

[0044] 2) According to the molar ratio of fumaric acid dibutyl ester, methacrylic acid ester and methacrylic acid is (1-3):(2-5):(8-15), the methacrylic acid ester obtained in step 1) is heated to 70-90℃, then the dropping speed is controlled to be 20-30d / min, fumaric acid dibutyl ester, methacrylic acid and initiator are added dropwise into the methacrylic acid ester, after the dropping is completed, the temperature is raised to 120-160℃, and polymerization reaction is carried out for 4-6h to obtain the environmentally friendly coal water slurry additive;

[0045] In the formula, R is selected from C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C7-C10 alkyl substituted phenyl;

[0046] Example 1

[0047] An environmentally friendly coal water slurry additive

[0048] 1) According to the molar ratio of methacrylic acid and alcohol is 1: (1.5-2), methacrylic acid and alcohol are mixed, toluenesulfonic acid is used as a catalyst, and esterification reaction is carried out at 60-80℃ for 4-6h to obtain methacrylic acid ester;

[0049] 2) According to the molar ratio of fumaric acid dibutyl ester, methacrylic acid ester and methacrylic acid is (1-3):(2-5):(8-15), the methacrylic acid ester obtained in step 1) is heated to 70-90℃, then the dropping speed is controlled to be 20-30d / min, fumaric acid dibutyl ester, methacrylic acid and initiator are added dropwise into the methacrylic acid ester, after the dropping is completed, the temperature is raised to 120-160℃, and polymerization reaction is carried out for 4-6h to obtain the environmentally friendly coal water slurry additive;

[0050] The synthetic route of Example 1 is shown as follows:

[0051] (1)

[0052] (2)

[0053] Example 2

[0054] An environmentally friendly coal water slurry additive

[0055] 1) According to the molar ratio of methacrylic acid and methanol is 1:1.5, methacrylic acid and methanol are mixed, toluene-p-sulfonic acid is used as catalyst, esterification reaction is carried out at 60℃ for 4h, and methyl methacrylate is obtained;

[0056] 2) According to the molar ratio of dibutyl fumarate, methyl methacrylate and methacrylic acid is 2:4:12, the methyl methacrylate obtained in step 1) is heated to 75℃, then the drop rate is controlled to be 20d / min, the dibutyl fumarate, the methacrylic acid and the initiator BPO are added dropwise into the methyl methacrylate, after the dropwise addition is completed, the temperature is raised to 130℃, and the polymerization reaction is carried out for 5.5h, and the environmentally friendly coal water slurry additive is obtained.

[0057] The synthetic route of Example 2 is shown as follows:

[0058] (1)

[0059] (2)

[0060] Example 3

[0061] An environmentally friendly coal water slurry additive

[0062] 1) According to the molar ratio of methacrylic acid and hexanol is 1:1.8, methacrylic acid and hexanol are mixed, toluene-p-sulfonic acid is used as catalyst, esterification reaction is carried out at 70℃ for 4h, and methyl methacrylate is obtained;

[0063] 2) According to the molar ratio of dibutyl fumarate, methyl methacrylate and methacrylic acid is 1:2:10, the methyl methacrylate obtained in step 1) is heated to 80℃, then the drop rate is controlled to be 25d / min, the dibutyl fumarate, the methacrylic acid and the initiator BPO are added dropwise into the methyl methacrylate, after the dropwise addition is completed, the temperature is raised to 150℃, and the polymerization reaction is carried out for 5h, and the environmentally friendly coal water slurry additive is obtained.

[0064] The synthetic route of Example 3 is shown as follows:

[0065] (1)

[0066] (2)

[0067] Example 4

[0068] An environmentally-friendly coal water slurry additive

[0069] 1) According to the molar ratio of methacrylic acid and hexanol is 1:1.8, methacrylic acid and hexanol are mixed, toluene-p-sulfonic acid is used as catalyst, esterification reaction is carried out at 70℃ for 4h, and hexyl methacrylate is obtained;

[0070] 2) According to the molar ratio of dibutyl fumarate, hexyl methacrylate and methacrylic acid is 2:3:15, the hexyl methacrylate obtained in step 1) is heated to 80℃, then the drop rate is controlled to 30d / min, the dibutyl fumarate, methacrylic acid and initiator BPO are added to the hexyl methacrylate, after the drop is completed, the temperature is raised to 160℃, and the polymerization reaction is carried out for 4h, and the environmentally-friendly coal water slurry additive is obtained.

[0071] The synthesis route of Example 4 is shown as follows:

[0072] (1)

[0073] (2)

[0074] Example 5

[0075] An environmentally-friendly coal water slurry additive

[0076] 1) According to the molar ratio of methacrylic acid and cyclopentanol is 1:1.5, methacrylic acid and cyclopentanol are mixed, toluene-p-sulfonic acid is used as catalyst, esterification reaction is carried out at 80℃ for 5h, and cyclopentyl methacrylate is obtained;

[0077] 2) According to the molar ratio of dibutyl fumarate, cyclopentyl methacrylate and methacrylic acid is 1:4:13, the cyclopentyl methacrylate obtained in step 1) is heated to 90℃, then the drop rate is controlled to 25d / min, the dibutyl fumarate, methacrylic acid and initiator BPO are added to the cyclopentyl methacrylate, after the drop is completed, the temperature is raised to 160℃, and the polymerization reaction is carried out for 5h, and the environmentally-friendly coal water slurry additive is obtained.

[0078] The synthesis route of Example 5 is shown as follows:

[0079] (1)

[0080] (2)

[0081] Example 6

[0082] An environmentally-friendly coal water slurry additive

[0083] 1) according to the molar ratio of methacrylic acid and cyclopentanol 1:1.5, methacrylic acid and cyclopentanol are mixed, toluenesulfonic acid is used as catalyst, esterification reaction is carried out at 80℃ for 5h, to obtain cyclopentyl methacrylate;

[0084] 2) according to the molar ratio of dibutyl fumarate, cyclopentyl methacrylate and methacrylic acid 2:3:11, cyclopentyl methacrylate obtained in step 1) is heated to 90℃, then the drop rate is controlled at 22d / min, dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into the cyclopentyl methacrylate, after the dropwise addition is completed, the temperature is raised to 150℃, and the polymerization reaction is carried out for 6h, to obtain the environmentally friendly coal water slurry additive.

[0085] The synthetic route of example 6 is shown as follows:

[0086] (1) (2)

[0088] Example 7

[0089] An environmentally friendly coal water slurry additive

[0090] 1) according to the molar ratio of methacrylic acid and cyclopentanol 1:1.5, methacrylic acid and cyclopentanol are mixed, toluenesulfonic acid is used as catalyst, esterification reaction is carried out at 80℃ for 5h, to obtain cyclopentyl methacrylate;

[0091] 2) according to the molar ratio of dibutyl fumarate, cyclopentyl methacrylate and methacrylic acid 2:3:11, cyclopentyl methacrylate obtained in step 1) is heated to 90℃, then the drop rate is controlled at 22d / min, dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into the cyclopentyl methacrylate, after the dropwise addition is completed, the temperature is raised to 150℃, and the polymerization reaction is carried out for 6h, to obtain the environmentally friendly coal water slurry additive.

[0092] The synthetic route of example 7 is shown as follows:

[0093] (1)

[0094] (2)

[0095] Example 8

[0096] An environmentally friendly coal water slurry additive

[0097] 1) according to the molar ratio of methacrylic acid and allyl alcohol 1:1.7, methacrylic acid and allyl alcohol are mixed, esterification is carried out at 80°C for 5h with p-toluenesulfonic acid as catalyst, to obtain allyl methacrylate;

[0098] 2) according to the molar ratio of dibutyl fumarate, allyl methacrylate and methacrylic acid 2:2:14, the allyl methacrylate obtained in step 1) is heated to 70°C, then the drop rate is controlled at 20d / min, and the dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into the allyl methacrylate, after the dropwise addition is completed, the temperature is raised to 125°C, and the polymerization reaction is carried out for 5h to obtain the environmentally friendly coal water slurry additive.

[0099] The synthetic route of example 8 is shown as follows:

[0100] (1)

[0101] (2)

[0102] Example 9

[0103] An environmentally friendly coal water slurry additive

[0104] 1) according to the molar ratio of methacrylic acid and p-methyl phenol 1:1.6, methacrylic acid and p-methyl phenol are mixed, esterification is carried out at 60°C for 4h with p-toluenesulfonic acid as catalyst, to obtain p-methyl phenol methacrylate;

[0105] 2) according to the molar ratio of dibutyl fumarate, p-methyl phenol methacrylate and methacrylic acid 1:3:14, the p-methyl phenol methacrylate obtained in step 1) is heated to 90°C, then the drop rate is controlled at 30d / min, and the dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into the p-methyl phenol methacrylate, after the dropwise addition is completed, the temperature is raised to 160°C, and the polymerization reaction is carried out for 4h to obtain the environmentally friendly coal water slurry additive.

[0106] The synthetic route of example 9 is shown as follows:

[0107] (1)

[0108] (2)

[0109] Example 10

[0110] An environmentally friendly coal water slurry additive

[0111] 1) according to the molar ratio of methacrylic acid and p-methylphenol is 1:1.6, methacrylic acid and methylphenol are mixed, esterification is carried out at 60°C for 4h with p-toluene sulfonic acid as catalyst, and p-methylphenol methacrylate is obtained;

[0112] 2) according to the molar ratio of dibutyl fumarate, p-methylphenol methacrylate and methacrylic acid is 2:2:15, p-methylphenol methacrylate obtained in step 1) is heated to 90°C, then the dropping speed is controlled to be 30d / min, dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into p-methylphenol methacrylate, after the addition is completed, the temperature is raised to 150°C, and polymerization is carried out for 5.5h, and the environmentally friendly water coal slurry additive is obtained.

[0113] The synthetic route of example 10 is shown as follows:

[0114] (1)

[0115] (2)

[0116] Example 11

[0117] An environmentally friendly water coal slurry additive

[0118] 1) according to the molar ratio of methacrylic acid and p-ethylphenol is 1:1.8, methacrylic acid and ethylphenol are mixed, esterification is carried out at 60°C for 4.5h with p-toluene sulfonic acid as catalyst, and p-ethylphenol methacrylate is obtained;

[0119] 2) according to the molar ratio of dibutyl fumarate, p-ethylphenol methacrylate and methacrylic acid is 1:4:12, p-ethylphenol methacrylate obtained in step 1) is heated to 85°C, then the dropping speed is controlled to be 25d / min, dibutyl fumarate, methacrylic acid and initiator BPO are added dropwise into p-ethylphenol methacrylate, after the addition is completed, the temperature is raised to 155°C, and polymerization is carried out for 4h, and the environmentally friendly water coal slurry additive is obtained.

[0120] The synthetic route of example 11 is shown as follows:

[0121] (1)

[0122] (2)

[0123] Example 12

[0124] An environmentally friendly water coal slurry additive

[0125] 1) according to the molar ratio of methacrylic acid and p-ethylphenol is 1:1.8, methacrylic acid and ethyl phenol are mixed, esterification is carried out at 60 DEG C for 4.5h with p-toluenesulfonic acid as catalyst, and p-ethylphenol methacrylate is obtained;

[0126] 2) according to the molar ratio of dibutyl fumarate, p-ethylphenol methacrylate and methacrylic acid is 2:4:15, p-ethylphenol methacrylate obtained in step 1) is heated to 85 DEG C, then the dropping speed is controlled at 20d / min, dibutyl fumarate, methacrylic acid and initiator BPO are added into p-ethylphenol methacrylate, after the addition is completed, the temperature is raised to 140 DEG C, and polymerization is carried out for 6h, and the environment-friendly coal water slurry additive is obtained.

[0127] The synthetic route of example 12 is shown as follows:

[0128] (1)

[0129] (2)

[0130] Effect verification

[0131] According to the percentage of coal 70wt.%, water 29wt.% and coal water slurry additive 1wt.%, coal water slurry is prepared by taking A, B, C, D, E, F three kinds of coal and the coal water slurry additive prepared in examples 1-12 as raw materials;

[0132] The coal sample analysis of A, B, C three kinds of coal is shown in table 1;

[0133] Table 1 coal sample analysis

[0134]

[0135] The zeta potential of the coal particle surface in the coal water slurry is detected, and the zeta potential detection results of the coal particle surface are shown in table 2;

[0136] Table 2 zeta potential detection results of the coal particle surface

[0137]

[0138]

[0139] From the data in table 2, it can be seen that no matter low-rank coal, medium-rank coal or high-rank coal, the negative value of zeta potential is increased after the addition of the coal water slurry additive provided by the application, which shows that the hydrophobic end in the coal water slurry additive provided by the application is effectively adsorbed on the coal particle surface, reduces the shielding effect of the negative charge on the coal particle surface, forms a stable diffuse double layer, effectively enhances the electrostatic repulsion between the coal particles, and thus improves the stability of the coal water slurry system.

[0140] The prepared water coal slurry is placed for 7 days, and the stability of the water coal slurry is observed, and the detection results of the stability of the water coal slurry are shown in Table 3.

[0141] Table 3: Detection results of the stability of the water coal slurry

[0142]

[0143]

[0144] From the data in Table 2, it can be seen that, whether it is low-rank coal, medium-rank coal or high-rank coal, after the water coal slurry additive provided by the present application is added, the prepared water coal slurry only produces a small amount of precipitation after being placed for 7 days, and has good stability, so the water coal slurry additive provided by the present application has good dispersion stability.

[0145] It should be finally pointed out that: the above examples are only used to illustrate the technical solutions of the present application but not to limit it, although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that: the specific embodiments of the present application can still be modified or replaced by the equivalent, without departing from the spirit and scope of the present application, any modification or equivalent replacement thereof should be covered in the protection scope of the claims of the present application.

Claims

1. An environmentally friendly coal-water slurry additive, characterized in that, The structural formula of the environmentally friendly coal-water slurry additive is: In the formula, a = 1 to 3, b = 2 to 5, and c = 8 to 15; R is selected from one of C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl, or C7-C10 alkyl-substituted phenyl.

2. A method for preparing an environmentally friendly coal-water slurry additive as described in claim 1, characterized in that, Includes the following steps: 1) Mix methacrylic acid and alcohol, and esterify them to obtain methacrylate; 2) Mix dibutyl fumarate, methacrylate obtained in step 1), and methacrylic acid, and polymerize them to obtain the environmentally friendly coal-water slurry additive.

3. The preparation method according to claim 2, characterized in that, In step 1), the alcohol is ROH; In the formula, R is selected from one of C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 alkenyl or C7-C10 alkyl-substituted phenyl.

4. The preparation method according to claim 2, characterized in that, In step 1), the molar ratio of methacrylic acid and alcohol is 1:(1.5-2).

5. The preparation method according to claim 2, characterized in that, In step 1), the esterification reaction specifically involves reacting at 60–80°C for 4–6 hours using p-toluenesulfonic acid as a catalyst.

6. The preparation method according to claim 2, characterized in that, In step 2), the molar ratio of dibutyl fumarate, methacrylate and methacrylic acid is (1-3):(2-5):(8-15).

7. The preparation method according to claim 2, characterized in that, In step 2), the polymerization reaction is specifically as follows: first, the methacrylate obtained in step 1) is heated to 70-90°C, then the dropping rate is controlled at 20-30 drops / min, and dibutyl fumarate, methacrylic acid and initiator are added dropwise to the methacrylate. After the addition is completed, the temperature is raised to 120-160°C, and the polymerization reaction is carried out for 4-6 hours.

8. The preparation method according to claim 7, characterized in that, The initiator is BPO.

9. The application of the environmentally friendly coal-water slurry additive as described in claim 1 in the preparation of coal-water slurry.

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