A novel naphthol distillation residue modified coal water slurry modifier and preparation method thereof

Abstract

The invention relates to the technical field of coal-water slurry, with an IPC classification number of C08F, and specifically relates to a novel naphthol distillation residue modified coal-water slurry modifier and a preparation method thereof. The raw materials for preparing the novel naphthol distillation residue modified coal-water slurry modifier include, by weight, 1-10 parts of distillation-rectification residue, 0.2-1 parts of silane coupling agent, 80-120 parts of water, 20-45 parts of anionic surfactant, 10-20 parts of phenol, 3-10 parts of alkaline compound, 10-35 parts of formic aldehyde, and 1-2 parts of auxiliary agent. The preparation method comprises: adding a silane coupling agent to the distillation-rectification residue in a heated molten state for blending and modification, adding an anionic surfactant and stirring and mixing, adding formic acid aldehyde to prepare a small monomer, adding water, phenol, and liquid sodium hydroxide into a flask, adding the remaining formic acid aldehyde, and adding the small monomer and an auxiliary agent for mixing, so as to prepare a novel naphthol distillation residue modified coal water slurry modifier, which has the advantages of good dispersibility, high stability, low viscosity, good fluidity, good practicality, low energy consumption, and the like.

Description

Technical Field

[0001] The invention relates to the technical field of coal-water slurry, with an IPC classification number of C08F, and in particular to a novel naphthol distillation residue-modified coal-water slurry modifier and a preparation method thereof. Background Art

[0002] Coal-water slurry is a coal-water solid-liquid dispersion system prepared by physical methods using coal, water and a small amount of chemical additives. It has good rheological properties, stability and thixotropy. Compared with petroleum, its preparation process is simple and the cost is low. It is widely used as a substitute for oil.

[0003] However, in the process of coal-water slurry preparation, it is difficult to prepare a coal-water slurry with good stability and fluidity because the coal particles are extremely fine and have a large specific surface area, and they are very easy to aggregate in the slurry and cause precipitation. By adding a dispersant, the coal-water interface properties can be changed, the hydrophilicity of the coal particle surface can be improved, and the coal particles can be evenly dispersed in the water, so that the prepared coal-water slurry modifier has good dispersibility.

[0004] Patent CN109913281A discloses a method for preparing a sodium lignin sulfonate dispersant and a coal-slime water slurry, wherein a sulfonate is reacted with water and dried and concentrated to obtain a sodium lignin sulfonate dispersant with waste utilization and good stability, but its dispersibility and stability are poor.

[0005] Patent CN101543744 discloses a multi-component composite water-coal slurry dispersant and its application. The solid water-coal dispersant is prepared by uniformly mixing components such as naphthalene sulfonate, polyaminocarboxylate, polymethacrylate, lignin sulfonate, carbonate and the like in different weight ratios. The solid water-coal dispersant has excellent properties such as low material consumption and moderate viscosity, but its fluidity is poor. Summary of the invention

[0006] In order to solve the above problems, the first aspect of the present invention provides a novel naphthol distillation residue modified coal-water slurry modifier, the preparation raw materials of which, in parts by weight, include 1-10 parts of distillation-rectification residue, 0.2-1 parts of silane coupling agent, 80-120 parts of water, 20-45 parts of anionic surfactant, 10-20 parts of phenol, 3-10 parts of alkaline compound, 10-35 parts of formic aldehyde, and 1-2 parts of auxiliary agent.

[0007] As a preferred technical solution, the distillation-rectification residue is blended and modified with a silane coupling agent;

[0008] As a preferred technical solution, the silane coupling agent is one of vinyl triethoxy silane, vinyl trimethoxy silane, and vinyl tri (β-methoxyethoxy) silane;

[0009] As a more preferred technical solution, the silane coupling agent is vinyl triethoxy silane;

[0010] As a preferred technical solution, the anionic surfactant is one of carboxylate type, sulfonate type, sulfate type, and phosphate type anionic surfactant;

[0011] As a preferred technical solution, the sulfonate type anionic surfactant is one of sodium p-toluenesulfonate, sodium 1-propanesulfonate, sodium dodecylsulfonate, sodium dodecylbenzenesulfonate, sodium octadecylbenzenesulfonate, N-methyloleamide taurate, succinate sulfonate or a combination thereof;

[0012] As a more preferred technical solution, the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, and the mass ratio thereof is 1-1.6:2.3-3.4;

[0013] As a preferred technical solution, the alkaline compound is an aqueous solution of sodium hydroxide with a concentration of 2.4-4.13wt%;

[0014] As a preferred technical solution, the formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 8-14.5wt%;

[0015] As a preferred technical solution, the auxiliary agent is one of isomeric decanol polyoxyethylene ether, isomeric undecanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, isotridecanol polyoxyethylene polyoxypropylene ether or a combination thereof;

[0016] As a more preferred technical solution, the auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio thereof is 0.5-1.2:1.4-2.7.

[0017] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0018] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 1-10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 0.2-1 parts of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping a portion of formic acid aldehyde thereto, controlling the dripping time to be about 40 min-1 h, and continuing to stir for 1 h after the dripping is completed, and using it as a small monomer for standby use;

[0019] (2) Add water to another reaction device, heat to 40-50°C, then add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide according to the ratio at 60°C, and then slowly add the remaining mass parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 1.5-2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 93-96°C and keep warm for 3-6 hours, add the remaining water, and stir to mix evenly.

[0020] Beneficial Effects

[0021] (1) A novel naphthol distillation residue modified coal water slurry modifier is prepared by mixing distillation-rectification residue, silane coupling agent, anionic surfactant, and formic acid aldehyde, and then adding water, phenol, liquid sodium hydroxide, remaining formic acid aldehyde, and auxiliary agent. The novel naphthol distillation residue modified coal water slurry modifier has the advantages of good dispersibility, high stability, low viscosity, good fluidity, good practicality, and low energy consumption.

[0022] (2) The present invention can improve the stability of the obtained naphthol distillation residue modified coal water slurry modifier by adding a silane coupling agent, especially when the silane coupling agent is vinyl triethoxysilane, it can better cooperate with anionic surfactants and additives to improve the stability of the obtained novel naphthol distillation residue modified coal water slurry modifier. The reason may be that vinyl triethoxysilane contains three hydrolyzable ethoxy groups and also has a vinyl group that has a strong affinity or reactivity with polymer molecules. The active groups in vinyl triethoxysilane can react with the hydroxyl groups on the surface of the particles contained in the distillation-rectification residue to form a chemical bond, and vinyl triethoxysilane also contains a vinyl group that can react with the polymer to form a chemical bond, which can cooperate with anionic surfactants, additives, etc., so that the distillation-rectification residue is coupled with the anionic active agent and the additive in the form of a chemical bond through the silane coupling agent, thereby reducing the precipitation of substances in the naphthol distillation residue.

[0023] (3) The present invention can improve the dispersibility of the prepared naphthol distillation residue modified coal water slurry modifier by adding anionic surfactants, especially when the anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, and the mass ratio thereof is 1-1.6:2.3-3.4, the surface tension thereof can be reduced during use, thereby improving the dispersion effect of the naphthol distillation residue modified coal water slurry modifier. The reason may be that sodium dodecylbenzene sulfonate is a long-chain structure, and the non-polar lipophilic hydrophobic group at one end can react with the hydrophobic group of the particles contained in the naphthol distillation-rectification residue, while the polar hydrophilic group at the other end of sodium dodecylbenzene sulfonate can adsorb the particles contained in the naphthol distillation-rectification residue, and react with polar water molecules, reduce the contact angle between the naphthol distillation-rectification residue and water, and increase its wettability. Sodium p-methylphenyl sulfonate is a short-chain structure, and the synergistic effect with sodium dodecylbenzene sulfonate can better adsorb the particles contained in the naphthol distillation-rectification residue, further improving the dispersibility of the obtained naphthol distillation residue modified coal water slurry modifier. In addition, the long-chain structure of sodium dodecylbenzene sulfonate and the short-chain structure of sodium p-methylphenyl sulfonate are fully extended in the naphthol distillation residue modified coal water slurry modifier, forming a good spatial position effect, so that the naphthol distillation residue modified coal water slurry modifier forms a stable and uniformly dispersed solution.

[0024] (4) The present invention adds an auxiliary agent, which works synergistically with an anionic surfactant to help prepare a naphthol distillation residue modified coal water slurry modifier with a certain degree of branching, further reduce the surface tension of the obtained naphthol distillation residue modified coal water slurry modifier, and improve the dispersion effect of the naphthol distillation residue modified coal water slurry modifier. In particular, the auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio thereof is 0.5-1.2:1.4-2.7. The obtained naphthol distillation residue modified coal water slurry modifier has excellent dispersibility. The reason may be that both isotridecyl polyoxyethylene ether and isotridecyl polyoxyethylene polyoxypropylene ether are long-chain polymers with branched structures. After the two are compounded, it is easier to reach the minimum concentration of surfactant that forms micelles, and can better react with the hydrophobic groups of the particles contained in the naphthol distillation-rectification residue. In addition, the excellent dispersing effect possessed by the synergistic effect between the compounded benzenesulfonate, the distillation-rectification residue modified by blending with a silane coupling agent, and the functional additives can effectively adsorb the tiny particles contained in the naphthol distillation-rectification residue, and generate electrostatic repulsion to disperse them, avoid sedimentation and coarsening, effectively reduce the viscosity of the high-concentration coal-water slurry, improve its fluidity, improve its performance, and reduce energy consumption.

[0025] (5) The present invention is to treat the distillation-rectification residue in a heated molten state, and then pass it through a silane coupling agent to

[0026] The mixture is blended and modified, an anionic surfactant is added and stirred, and then formic aldehyde is added dropwise to prepare a small monomer. Water, phenol, and liquid sodium hydroxide are added to a flask, the remaining formic aldehyde is added dropwise, and the small monomer and additives are added and mixed to prepare a new naphthol distillation residue modified coal water slurry modifier, which has the advantages of good dispersibility, high stability, low viscosity, good fluidity, good practicality, and low energy consumption. DETAILED DESCRIPTION

[0027] Example 1

[0028] Example 1 provides a novel naphthol distillation residue-modified coal-water slurry modifier, the raw materials for its preparation, in parts by weight, include 1 part of distillation-rectification residue, 0.2 parts of silane coupling agent, 80 parts of water, 20 parts of anionic surfactant, 10 parts of phenol, 3 parts of alkaline compounds, 10 parts of formic aldehyde, and 1 part of auxiliary agent.

[0029] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0030] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0031] The anionic surfactant is a sulfonate type anionic surfactant;

[0032] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 1:2.3. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0033] The alkaline compound is an aqueous solution of sodium hydroxide with a concentration of 2.4 wt%;

[0034] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 8wt%;

[0035] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 0.5:1.4. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, which is purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1, which is purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0036] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0037] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 1 part of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 0.2 parts of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 4 parts of formic acid aldehyde thereto, controlling the dripping time to be 40 minutes, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0038] (2) Add 60 parts of water to another reaction device, heat to 40°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 6 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 1.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 93°C and keep warm for 3 hours, add 20 parts of water, and stir to mix evenly.

[0039] Example 2

[0040] Example 2 provides a new type of naphthol distillation residue modified coal slurry modifier, the preparation raw materials of which, in parts by weight, include 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formic aldehyde, and 2 parts of auxiliary agent.

[0041] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0042] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0043] The anionic surfactant is a sulfonate type anionic surfactant;

[0044] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 1.6:3.4. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0045] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 4.13wt%;

[0046] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 14.5wt%;

[0047] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 1.2:2.7. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1.

[0048] Purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0049] The weight ratio of the Chinese herbal medicine to the wax matrix is ​​115:20;

[0050] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0051] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 1 part of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 14 parts of formic acid aldehyde thereto, controlling the dripping time to be 1 hour, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0052] (2) Add 90 parts of water to another reaction device, heat to 50°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 21 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 96°C and keep warm for 6 hours, add 30 parts of water, and stir to mix evenly.

[0053] Example 3

[0054] Example 3 provides a novel naphthol distillation residue-modified coal-water slurry modifier, the raw materials for its preparation, in parts by weight, include 6 parts of distillation-rectification residue, 0.5 parts of silane coupling agent, 100 parts of water, 30 parts of anionic surfactant, 15 parts of phenol, 6 parts of alkaline compound, 20 parts of formic aldehyde, and 1.5 parts of auxiliary agent.

[0055] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0056] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0057] The anionic surfactant is a sulfonate type anionic surfactant;

[0058] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 1.3:2.7. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0059] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 3.1wt%;

[0060] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 11wt%;

[0061] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 0.8:2.0. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1, purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0062] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0063] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 6 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 0.5 parts of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 8 parts of formic acid aldehyde thereto, controlling the dripping time to be about 50 minutes, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0064] (2) Add 75 parts of water to another reaction device, heat to 45°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide according to the ratio at 60°C, and then slowly add 12 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.0 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 94°C and keep warm for 4.5 hours, add 25 parts of water, and stir to mix evenly.

[0065] Comparative Example 1

[0066] Comparative Example 1 provides a new type of naphthol distillation residue modified coal-water slurry modifier, the preparation raw materials of which, in parts by weight, include 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formic aldehyde, and 2 parts of auxiliary agent.

[0067] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0068] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0069] The anionic surfactant sodium secondary alkyl sulfonate, CAS No. 68188-18-1, was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.;

[0070] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 4.13wt%;

[0071] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 14.5wt%;

[0072] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 1.2:2.7. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, which is purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1, which is purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0073] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0074] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 1 part of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 14 parts of formic acid aldehyde thereto, controlling the dripping time to be 1 hour, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0075] (2) Add 90 parts of water to another reaction device, heat to 50°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 21 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 96°C and keep warm for 6 hours, add 30 parts of water, and stir to mix evenly.

[0076] Comparative Example 2

[0077] Comparative Example 2 provides a new type of naphthol distillation residue modified coal-water slurry modifier, the preparation raw materials of which, in parts by weight, include 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formic aldehyde, and 2 parts of auxiliary agent.

[0078] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0079] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0080] The anionic surfactant is a sulfonate type anionic surfactant;

[0081] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 0.4:1.8. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0082] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 4.13wt%;

[0083] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 14.5wt%;

[0084] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 1.2:2.7. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, which is purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1, which is purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0085] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0086] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 1 part of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 14 parts of formic acid aldehyde thereto, controlling the dripping time to be 1 hour, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0087] (2) Add 90 parts of water to another reaction device, heat to 50°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 21 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 96°C and keep warm for 6 hours, add 30 parts of water, and stir to mix evenly.

[0088] Comparative Example 3

[0089] Comparative Example 3 provides a new type of naphthol distillation residue modified coal-water slurry modifier, the preparation raw materials of which, in parts by weight, include 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formic aldehyde, and 2 parts of auxiliary agent.

[0090] The distillation-rectification residue is blended and modified by a silane coupling agent;

[0091] The silane coupling agent is vinyl triethoxysilane, CAS No. 78-08-0, purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0092] The anionic surfactant is a sulfonate type anionic surfactant;

[0093] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 1.6:3.4. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0094] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 4.13wt%;

[0095] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 14.5wt%;

[0096] The auxiliary agent is octylphenol polyoxyethylene ether, CAS No. 9036-19-5, purchased from Sigma-Aldrich (Shanghai) Co., Ltd.

[0097] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0098] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 1 part of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 14 parts of formic acid aldehyde thereto, controlling the dripping time to be 1 hour, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0099] (2) Add 90 parts of water to another reaction device, heat to 50°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 21 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 96°C and keep warm for 6 hours, add 30 parts of water, and stir to mix evenly.

[0100] Comparative Example 4

[0101] Comparative Example 4 provides a new type of naphthol distillation residue modified coal-water slurry modifier, the preparation raw materials of which, in parts by weight, include 10 parts of distillation-rectification residue, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formic aldehyde, and 2 parts of auxiliary agent.

[0102] The anionic surfactant is a sulfonate type anionic surfactant;

[0103] The sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, with a mass ratio of 1.6:3.4. The CAS number of sodium p-toluenesulfonate is 657-84-1, purchased from Beijing Bailingwei Technology Co., Ltd., and the CAS number of sodium dodecylbenzenesulfonate is 25155-30-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0104] The alkaline compound is an aqueous solution of sodium hydroxide, and its concentration is 4.13wt%;

[0105] The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 14.5wt%;

[0106] The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, with a mass ratio of 1.2:2.7. The CAS number of isotridecyl alcohol polyoxyethylene ether is 69011-36-5, which is purchased from Nantong Chenrun Chemical Co., Ltd., and the CAS number of isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1, which is purchased from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.

[0107] The second aspect of the present invention provides a method for preparing a novel naphthol distillation residue modified coal water slurry modifier, comprising the following steps:

[0108] (1) The distillation-rectification residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 10 parts of the distillation-rectification residue into a four-necked flask, heating to 125° C. to melt, adding 1 part of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping 14 parts of formic acid aldehyde thereto, controlling the dripping time to be 1 hour, and continuing to stir for 1 hour after the dripping is completed, and using it as a small monomer for standby use;

[0109] (2) Add 90 parts of water to another reaction device, heat to 50°C, add phenol according to the ratio, continue heating, add an aqueous solution of sodium hydroxide at 60°C according to the ratio, and then slowly add 21 parts of formic acid aldehyde, control the dropping speed, and complete the dropping within 2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80°C. After the dropping is completed, add the small monomer and functional additive obtained in step 1, and start heating. Heat to 96°C and keep warm for 6 hours, add 30 parts of water, and stir to mix evenly.

[0110] Performance Testing

[0111] A new type of naphthol distillation residue modified coal-water slurry modifier prepared in the above Examples 1-3 and Comparative Examples 1-4 was respectively put into the Qinghai Salt Lake coal-water slurry, and the addition amount of this new type of naphthol distillation residue modified coal-water slurry modifier was 0.3% of the Qinghai Salt Lake coal-water slurry. The viscosity, fluidity, dispersibility, stability and other indicators of the Qinghai Salt Lake coal-water slurry were measured. The test results are shown in Table 1.

[0112] Table 1: Viscosity, fluidity, dispersibility and stability test data of Qinghai Salt Lake coal-water slurry when the doping amount of the new naphthol distillation residue modified coal-water slurry modifier is 0.3%.

[0113]

Claims

1. A naphthol distillation residue modified coal water slurry modifier, characterized in that: The raw materials for preparation include, by weight: 1-10 parts of naphthol distillation residue, 0.2-1 parts of silane coupling agent, 80-120 parts of water, 20-45 parts of anionic surfactant, 10-20 parts of phenol, 3-10 parts of alkaline compound, 10-35 parts of formic aldehyde, and 1-2 parts of auxiliary agent; The preparation method of the modifier comprises the following steps: (1) The naphthol distillation residue is blended with a silane coupling agent, specifically comprising the following steps: weighing 1-10 parts of the naphthol distillation residue into a four-necked flask, heating to 125° C. to melt, adding 0.2-1 parts of a silane coupling agent for blending and modification, adding an anionic surfactant for stirring and mixing, slowly dripping a portion of formic acid aldehyde thereto, controlling the dripping time to 40 min-1 h, and continuing to stir for 1 h after the dripping is completed, and using the mixture as a small monomer for standby use; (2) Add water to another reaction device, heat to 40-50 °C, then add phenol according to the ratio, continue heating, add sodium hydroxide aqueous solution according to the ratio at 60 °C, and then slowly add the remaining mass parts of formic aldehyde, control the dropping speed, and complete the dropping within 1.5-2.5 hours. At the same time, control the temperature during the dropping process not to exceed 80 °C. After the dropping is completed, add the small monomer and auxiliary agent obtained in step 1, and start heating, heat to 93-96 °C and keep warm for 3-6 hours, add the remaining water, stir and mix evenly, and obtain; The silane coupling agent is one of vinyl triethoxy silane, vinyl trimethoxy silane and vinyl tri (β-methoxyethoxy) silane; The anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecylbenzenesulfonate, and the mass ratio thereof is 1-1.6:2.3-3.4; The auxiliary agent is one of isomeric decanol polyoxyethylene ether, isomeric undecanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, isotridecanol polyoxyethylene polyoxypropylene ether or a combination thereof; The alkaline compound is an aqueous solution of sodium hydroxide, and the concentration thereof is 2.4-4.13 wt %.

2. A naphthol distillation residue modified coal water slurry modifier according to claim 1, characterized in that, The formic aldehyde is an aqueous solution of formic aldehyde, and its concentration is 8-14.5 wt %.

3. A naphthol distillation residue modified coal water slurry modifier according to claim 1, characterized in that, The auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio thereof is 0.5-1.2:1.4-2.7.

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