Environment-friendly coal water slurry additive and preparation method thereof

Abstract

The invention relates to the technical field of coal fuel, and discloses an environment-friendly coal water slurry additive and a preparation method thereof. The environment-friendly coal water slurry additive provided by the invention has a structural formula of # imgabs0. The environment-friendly coal water slurry additive provided by the invention is good in universality, can be applied to low-rank coal, medium-rank coal and high-rank coal, and is good in dispersity and high in dispersion stability.

Description

Technical Field

[0001] The present invention relates to the technical field of coal fuel, and more particularly, to an environmentally friendly water coal slurry additive and a preparation method thereof. Background Art

[0002] Water coal slurry is a new type of coal-based liquid fuel with low pollution, high efficiency and strong fluidity, which can replace heavy oil to alleviate problems such as energy shortage. Water coal slurry is mainly made of coal and water through a certain process. During the processing, due to the hydrophobicity of coal, in order to ensure the rheology and stability of water coal slurry, certain chemical additives must be added. According to the different functions of the chemical additives used in pulping, the chemical additives can be divided into dispersants, stabilizers and auxiliary chemical reagents (defoamers, pH regulators, etc.). Among them, the dispersant is the most important chemical additive.

[0003] According to the charge situation on the molecular chain of the dispersant, the dispersant can be divided into non-ionic dispersants, anionic dispersants, cationic dispersants and amphoteric dispersants. The dispersant has a high cost and is the main part of the pulping cost. Considering the cost performance, the anionic dispersant is currently the preferred additive for pulping. Commonly used ones include lignin-based dispersants, humic acid-based dispersants, naphthalene sulfonate-based dispersants, polycarboxylate-based dispersants, etc.; among them, the polycarboxylate-based dispersant has attracted much attention due to its environmental protection, high efficiency and other advantages.

[0004] However, the existing polycarboxylate-based dispersants have problems such as poor general applicability to coal types and poor dispersibility. Based on this, providing a polycarboxylate-based water coal slurry dispersant with good general applicability and good dispersibility has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

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

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] An environmentally friendly water coal slurry additive, the structural formula of which is:

[0009]

[0010] In the formula, a = 1 - 3, b = 2 - 5, 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] Preferably, in the formula, a = 1 - 2, b = 2 - 4, c = 10 - 15;

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

[0014] A typical structure of an environmentally friendly coal water slurry additive of the present invention includes:

[0015]

[0016]

[0017] The second technical solution of the present invention:

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

[0019] 1) Mix methacrylic acid and alcohol, carry out an esterification reaction to obtain methacrylate;

[0020] 2) Mix dibutyl fumarate, the methacrylate obtained in step 1) and methacrylic acid, carry out a polymerization reaction to obtain the environmentally friendly coal water slurry additive.

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

[0022] In the formula, R is selected from one of 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 to 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 °C for 4 - 6 h.

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

[0026] Further, in step 2), the polymerization reaction is specifically: first heat the methacrylate obtained in step 1) to 70 - 90 °C, then control the dropping rate to 20 - 30 d / min, drop dibutyl fumarate, methacrylic acid and an initiator into the methacrylate, and after the dropping is completed, raise the temperature to 120 - 160 °C and carry out a polymerization reaction for 4 - 6 h.

[0027] Even further, the initiator is BPO.

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

[0029] (1)

[0030] (2)

[0031] The third technical solution of the present invention:

[0032] The application of the above-mentioned environmentally friendly coal water slurry additive in the preparation of coal water slurry.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

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

[0035] After standing for 7 days, the coal water slurry prepared from the coal water slurry additive provided by the present invention has only a small amount of precipitation and has good stability. Therefore, the coal water slurry additive provided by the present invention has good dispersion stability. Detailed implementation manners

[0036] Now, various exemplary implementation manners of the present invention will be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation manners of the present invention. It should be understood that the terms described in the present invention are only for describing specific implementation manners and are not used to limit the present invention.

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

[0038] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0039] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the specification of the present invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0040] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

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

[0042] 1) Mix methacrylic acid and an alcohol in a molar ratio of 1:(1.5 - 2), use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 - 80 °C for 4 - 6 h to obtain a methacrylate;

[0043] Wherein, the alcohol is ROH, and in the formula, R is selected from one of C1 - C6 alkyl, C3 - C6 cycloalkyl, C3 - C6 alkenyl, or C7 - C10 alkyl-substituted phenyl;

[0044] 2) According to a molar ratio of dibutyl fumarate, methacrylate, and methacrylic acid of (1 - 3):(2 - 5):(8 - 15), first heat the methacrylate obtained in step 1) to 70 - 90 °C, then control the dropping rate to 20 - 30 d / min, and dropwise add dibutyl fumarate, methacrylic acid, and an initiator to the methacrylate. After the dropping is completed, raise the temperature to 120 - 160 °C and carry out a polymerization reaction for 4 - 6 h to obtain the environmentally friendly water coal slurry additive;

[0045] Wherein, the initiator is BPO (benzoyl peroxide).

[0046] Example 1

[0047] An environmentally friendly water coal slurry additive

[0048] 1) Mix methacrylic acid and methanol in a molar ratio of 1:1.5, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4 h to obtain methyl methacrylate;

[0049] 2) According to a molar ratio of dibutyl fumarate, methyl methacrylate, and methacrylic acid of 1:2:10, first heat the methyl methacrylate obtained in step 1) to 75 °C, then control the dropping rate to 25 d / min, and dropwise add dibutyl fumarate, methacrylic acid, and the initiator BPO to the methyl methacrylate. After the dropping is completed, raise the temperature to 135 °C and carry out a polymerization reaction for 5 h to obtain the environmentally friendly water coal slurry additive.

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

[0051] (1)

[0052] (2)

[0053] Example 2

[0054] An environment-friendly water coal slurry additive

[0055] 1) Mix methacrylic acid and methanol according to a molar ratio of 1:1.5, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4 h to obtain methyl methacrylate;

[0056] 2) According to a molar ratio of dibutyl fumarate, methyl methacrylate and methacrylic acid of 2:4:12, first heat the methyl methacrylate obtained in step 1) to 75 °C, then control the dropping rate at 20 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the methyl methacrylate. After the dropping is completed, raise the temperature to 130 °C and carry out a polymerization reaction for 5.5 h to obtain the environment-friendly water coal slurry additive.

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

[0058] (1)

[0059] (2)

[0060] Example 3

[0061] An environment-friendly water coal slurry additive

[0062] 1) Mix methacrylic acid and hexanol according to a molar ratio of 1:1.8, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 70 °C for 4 h to obtain hexyl methacrylate;

[0063] 2) According to a molar ratio of dibutyl fumarate, hexyl methacrylate and methacrylic acid of 1:2:10, first heat the hexyl methacrylate obtained in step 1) to 80 °C, then control the dropping rate at 25 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the hexyl methacrylate. After the dropping is completed, raise the temperature to 150 °C and carry out a polymerization reaction for 5 h to obtain the environment-friendly water coal slurry additive.

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

[0065] (1)

[0066] (2)

[0067] Example 4

[0068] An environmentally friendly water coal slurry additive

[0069] 1) Mix methacrylic acid and hexanol in a molar ratio of 1:1.8, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 70 °C for 4 h to obtain hexyl methacrylate;

[0070] 2) According to the molar ratio of dibutyl fumarate, hexyl methacrylate and methacrylic acid of 2:3:15, first heat the hexyl methacrylate obtained in step 1) to 80 °C, then control the dropping rate at 30 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the hexyl methacrylate. After the dropping is completed, raise the temperature to 160 °C and carry out a polymerization reaction for 4 h to obtain the environmentally friendly water coal slurry additive.

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

[0072] (1)

[0073] (2)

[0074] Example 5

[0075] An environmentally friendly water coal slurry additive

[0076] 1) Mix methacrylic acid and cyclopentanol in a molar ratio of 1:1.5, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 80 °C for 5 h to obtain cyclopentyl methacrylate;

[0077] 2) According to the molar ratio of dibutyl fumarate, cyclopentyl methacrylate and methacrylic acid of 1:4:13, first heat the cyclopentyl methacrylate obtained in step 1) to 90 °C, then control the dropping rate at 25 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the cyclopentyl methacrylate. After the dropping is completed, raise the temperature to 160 °C and carry out a polymerization reaction for 5 h to obtain the environmentally friendly water coal slurry additive.

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

[0079] (1)

[0080] (2)

[0081] Example 6

[0082] An environmentally friendly water coal slurry additive

[0083] 1) Mix methacrylic acid and cyclopentanol according to a molar ratio of 1:1.5, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 80 °C for 5 h to obtain cyclopentyl methacrylate;

[0084] 2) According to a molar ratio of dibutyl fumarate, cyclopentyl methacrylate, and methacrylic acid of 2:3:11, first heat the cyclopentyl methacrylate obtained in step 1) to 90 °C, then control the dropping rate at 22 d / min, and dropwise add dibutyl fumarate, methacrylic acid, and initiator BPO to the cyclopentyl methacrylate. After the dropping is completed, raise the temperature to 150 °C and carry out a polymerization reaction for 6 h to obtain the environmentally friendly water coal slurry additive.

[0085] The synthesis route of Example 6 is as follows:

[0086] (1)

[0087] (2)

[0088] Example 7

[0089] An environmentally friendly water coal slurry additive

[0090] 1) Mix methacrylic acid and cyclohexanol according to a molar ratio of 1:1.7, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 80 °C for 5 h to obtain cyclohexyl methacrylate;

[0091] 2) According to a molar ratio of dibutyl fumarate, cyclohexyl methacrylate, and methacrylic acid of 2:2:12, first heat the cyclohexyl methacrylate obtained in step 1) to 85 °C, then control the dropping rate at 20 d / min, and dropwise add dibutyl fumarate, methacrylic acid, and initiator BPO to the cyclohexyl methacrylate. After the dropping is completed, raise the temperature to 145 °C and carry out a polymerization reaction for 6 h to obtain the environmentally friendly water coal slurry additive.

[0092] The synthesis route of Example 7 is as follows:

[0093] (1)

[0094] (2)

[0095] Example 8

[0096] An environmentally friendly water coal slurry additive

[0097] 1) Mix methacrylic acid and allyl alcohol in a molar ratio of 1:1.7, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 80 °C for 5 h to obtain allyl methacrylate;

[0098] 2) According to the molar ratio of dibutyl fumarate, allyl methacrylate and methacrylic acid of 2:2:14, first heat the allyl methacrylate obtained in step 1) to 70 °C, then control the dropping rate at 20 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the allyl methacrylate. After the dropping is completed, raise the temperature to 125 °C and carry out a polymerization reaction for 5 h to obtain the environmentally friendly water coal slurry additive.

[0099] The synthesis route of Example 8 is as follows:

[0100] (1)

[0101] (2)

[0102] Example 9

[0103] An environmentally friendly water coal slurry additive

[0104] 1) Mix methacrylic acid and p-methylphenol in a molar ratio of 1:1.6, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4 h to obtain p-methylphenyl methacrylate;

[0105] 2) According to the molar ratio of dibutyl fumarate, p-methylphenyl methacrylate and methacrylic acid of 1:3:14, first heat the p-methylphenyl methacrylate obtained in step 1) to 90 °C, then control the dropping rate at 30 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the p-methylphenyl methacrylate. After the dropping is completed, raise the temperature to 160 °C and carry out a polymerization reaction for 4 h to obtain the environmentally friendly water coal slurry additive.

[0106] The synthesis route of Example 9 is as follows:

[0107] (1)

[0108] (2)

[0109] Example 10

[0110] An environmentally friendly water coal slurry additive

[0111] 1) Mix methacrylic acid and p - methylphenol according to a molar ratio of 1∶1.6, use p - toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4 h to obtain p - methylphenyl methacrylate;

[0112] 2) According to a molar ratio of dibutyl fumarate, p - methylphenyl methacrylate and methacrylic acid of 2∶2∶15, first heat the p - methylphenyl methacrylate obtained in step 1) to 90 °C, then control the dropping rate at 30 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the p - methylphenyl methacrylate. After the dropping is completed, raise the temperature to 150 °C and carry out a polymerization reaction for 5.5 h to obtain the environmentally friendly coal water slurry additive.

[0113] The synthesis route of Example 10 is as follows:

[0114] (1)

[0115] (2)

[0116] Example 11

[0117] An environmentally friendly coal water slurry additive

[0118] 1) Mix methacrylic acid and p - ethylphenol according to a molar ratio of 1∶1.8, use p - toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4.5 h to obtain p - ethylphenyl methacrylate;

[0119] 2) According to a molar ratio of dibutyl fumarate, p - ethylphenyl methacrylate and methacrylic acid of 1∶4∶12, first heat the p - ethylphenyl methacrylate obtained in step 1) to 85 °C, then control the dropping rate at 25 d / min, and drop dibutyl fumarate, methacrylic acid and initiator BPO into the p - ethylphenyl methacrylate. After the dropping is completed, raise the temperature to 155 °C and carry out a polymerization reaction for 4 h to obtain the environmentally friendly coal water slurry additive.

[0120] The synthesis route of Example 11 is as follows:

[0121] (1)

[0122] (2)

[0123] Example 12

[0124] An environmentally friendly coal water slurry additive

[0125] 1) Mix methacrylic acid and p-ethylphenol according to a molar ratio of 1:1.8, use p-toluenesulfonic acid as a catalyst, and carry out an esterification reaction at 60 °C for 4.5 h to obtain p-ethylphenyl methacrylate;

[0126] 2) According to a molar ratio of dibutyl fumarate, p-ethylphenyl methacrylate, and methacrylic acid of 2:4:15, first heat the p-ethylphenyl methacrylate obtained in step 1) to 85 °C, and then control the dropping rate to 20 d / min. Drop dibutyl fumarate, methacrylic acid, and initiator BPO into p-ethylphenyl methacrylate. After the dropping is completed, raise the temperature to 140 °C and carry out a polymerization reaction for 6 h to obtain the environmentally friendly coal water slurry additive.

[0127] The synthesis route of Example 12 is as follows:

[0128] (1)

[0129] (2)

[0130] Effect verification

[0131] Prepare a coal water slurry according to the percentages of 70 wt.% coal, 29 wt.% water, and 1 wt.% coal water slurry additive, using three kinds of coals A, B, C, D, E, F and the coal water slurry additives prepared in Examples 1 to 12 as raw materials;

[0132] The coal sample analyses of three kinds of coals A, B, and C are shown in Table 1;

[0133] Table 1 Coal sample analysis

[0134]

[0135] Detect the zeta potential on the surface of coal particles in the coal water slurry, and the detection results of the zeta potential on the surface of coal particles are shown in Table 2;

[0136] Table 2 Detection results of zeta potential on the surface of coal particles

[0137]

[0138]

[0139] It can be seen from the data in Table 2 that whether it is low-rank coal, medium-rank coal or high-rank coal, after adding the coal water slurry additive provided by the present invention, the negative value of the zeta potential has increased. This indicates that the hydrophobic end in the coal water slurry additive provided by the present invention is effectively adsorbed on the surface of coal particles, reducing the shielding effect of negative charges on the surface of coal particles, forming a stable diffusion double layer, and effectively enhancing the electrostatic repulsion between coal particles, thereby improving the stability of the coal water slurry system.

[0140] Let the prepared water coal slurry stand for 7 days, and observe the stability of the water coal slurry. The test results of the stability of the water coal slurry are shown in Table 3;

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

[0142]

[0143]

[0144] As can be seen from the data in Table 2, whether it is low-rank coal, medium-rank coal or high-rank coal, after adding the water coal slurry additive provided by the present invention, most of the prepared water coal slurries only produce a small amount of precipitation after standing for 7 days, and have good stability. Therefore, the water coal slurry additive provided by the present invention has good dispersion stability.

[0145] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications or equivalent replacements can still be made to the specific embodiments of the present invention, and any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall be covered by the protection scope of the claims of the present invention.

Claims

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

2. A preparation method of the environment-friendly water coal slurry additive as described in claim 1, characterized in that, It includes the following steps: 1) Mix methacrylic acid and alcohol, and carry out an esterification reaction to obtain methacrylate; 2) Mix dibutyl fumarate, the methacrylate obtained in step 1) and methacrylic acid, and carry out a polymerization reaction to obtain the environment-friendly water coal 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 to alcohol is 1:(1.5 - 2).

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

6. The preparation method according to claim 2, wherein 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: first heat the methacrylate obtained in step 1) to 70 - 90 °C, then control the dropping rate to be 20 - 30 d / min, drop dibutyl fumarate, methacrylic acid and an initiator into the methacrylate. After the dropping is completed, raise the temperature to 120 - 160 °C and carry out a polymerization reaction for 4 - 6 h.

8. The preparation method according to claim 7, wherein, The initiator is BPO.

9. Use of an environment-friendly water coal slurry additive as described in claim 1 in the preparation of water coal slurry.

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