Coal combustion dispersant and its application in preparation of high-efficiency coal-saving liquid additive

Abstract

The application discloses a coal combustion dispersant and application thereof in preparation of high-efficiency coal-saving liquid additives. The preparation method of the coal combustion dispersant comprises the following steps: S1. mixing dipentaerythritol, ethylene oxide, a strong base catalyst and a first solvent, and performing a warming reaction to obtain a dendritic polymer; and S2. mixing the dendritic polymer, 1,2-distearylphosphatidylglycerol (sodium salt), a strong acid catalyst, a polymerization inhibitor and a second solvent, and performing a warming reaction to obtain the coal combustion dispersant. The coal combustion dispersant contains an anion group in a molecular structure. The anion group has electrostatic action with metal cations in catalysts, sulfur-fixing agents and rare earth compounds of the high-efficiency coal-saving liquid additives. In addition, hydrogen bond action exists between the dispersants and between the dispersants and other substances. Therefore, the dispersion effect of the coal combustion dispersant is remarkably improved, and the content of combustible components of the high-efficiency coal-saving liquid additives is remarkably reduced, and the combustion efficiency of coal is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coal-saving liquid additives, and particularly relates to a coal combustion dispersant and application thereof in preparation of high-efficiency coal-saving liquid additives. BACKGROUND

[0002] Coal-saving additives refer to a kind of additives for reducing the content of combustible components in combustion products and improving the combustion efficiency of boilers by strengthening combustion, and are widely used in large coal-fired boilers in industrial fields such as power plants, steel plants and cement plants, and are also suitable for household stoves and heating equipment. The use of coal-saving liquid additives can significantly improve the combustion efficiency of coal. Coal-saving liquid additives generally include catalysts, sulfur-fixing agents, rare earth compounds and dispersants. Among them, the dispersant can play the following roles: (1) improving the compatibility of catalysts, sulfur-fixing agents, rare earth compounds and coal particles, enhancing the adsorption capacity, and making the catalysts, sulfur-fixing agents and rare earth compounds uniformly dispersed in the coal; (2) making the catalysts, sulfur-fixing agents and rare earth compounds more easily penetrate into the pores of coal particles, and enhancing the contact area between the catalysts, sulfur-fixing agents, rare earth compounds and coal; (3) preventing the agglomeration of catalysts, sulfur-fixing agents, rare earth compounds and coal particles, promoting their uniform dispersion, and improving the combustion efficiency.

[0003] The existing coal combustion dispersant generally uses neutral surfactants such as polyethylene glycol and polyether. The interaction force between these surfactants and catalysts, sulfur-fixing agents, rare earth compounds and coal particles is weak, and the interaction force between the dispersants is also weak, which leads to poor dispersion effect of the dispersants, and further makes it difficult for the coal-saving liquid additives to significantly improve the combustion efficiency of coal. SUMMARY

[0004] In view of the above deficiencies in the prior art, a coal combustion dispersant is provided. The coal combustion dispersant contains anionic groups in its molecular structure. The anionic groups have electrostatic interaction with metal cations in catalysts, sulfur-fixing agents and rare earth compounds of high-efficiency coal-saving liquid additives. The coal combustion dispersant also contains hydroxyl groups in its molecular structure, and hydrogen bonds exist between the dispersants and between the dispersants and other substances. The interaction force between the dispersants and between the dispersants and other substances is improved, the dispersion effect of the coal combustion dispersant is significantly improved, and the high-efficiency coal-saving liquid additives can significantly reduce the content of combustible components and improve the combustion efficiency of coal.

[0005] The present application aims to provide a preparation method of a coal combustion dispersant, which comprises the following steps:

[0006] S1. Mix dipentaerythritol, ethylene oxide, a strong base catalyst and a first solvent, and react under heating to obtain a dendritic polymer;

[0007] S2. The dendrimer, 1,2-distearoyl-sn-glycerol-3-phosphatidylglycerol (sodium salt), strong acid catalyst, polymerization inhibitor and second solvent are mixed, and the reaction is carried out at an elevated temperature to obtain the coal combustion dispersant.

[0008] The dendrimer obtained by reacting the hydroxyl groups of the dipentaerythritol with the epoxy groups of the ethylene oxide, and the hydroxyl groups of the dendrimer with the hydroxyl groups of the 1,2-distearoyl-sn-glycerol-3-phosphatidylglycerol (sodium salt) are reacted to obtain the coal combustion dispersant having a molecular structure containing hydroxyl groups, ether bonds and anionic groups.

[0009] In some embodiments of the present application, in S1, the molar ratio of the dipentaerythritol to the ethylene oxide is 1:6-12.

[0010] In some embodiments of the present application, in S1, the amount of the basic catalyst is 1000-4000 ppm of the total reaction raw materials.

[0011] In some embodiments of the present application, in S1, the strong base catalyst includes one of potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide, sodium methoxide, sodium ethoxide and sodium isopropoxide.

[0012] In some embodiments of the present application, in S1, the first solvent is at least one selected from dichloromethane, chloroform, tetrahydrofuran, toluene, 1,1-dichloroethane, 1,2-dichloroethane and dimethylbenzene.

[0013] In some embodiments of the present application, in S1, the temperature of the reaction at an elevated temperature is 40-130℃, and the time is 15-25 hours.

[0014] In some embodiments of the present application, in S2, the mass ratio of the dendrimer to the 1,2-distearoyl-sn-glycerol-3-phosphatidylglycerol (sodium salt) is 1:2-3.

[0015] In some embodiments of the present application, in S2, the mass ratio of the dendrimer, the strong acid catalyst and the polymerization inhibitor is 1:0.05-0.1:0.01-0.05.

[0016] In some embodiments of the present application, in S2, the strong acid catalyst is at least one selected from sulfuric acid, phosphoric acid, p-toluenesulfonic acid and methylsulfonic acid.

[0017] In some embodiments of the present application, in S2, the polymerization inhibitor is at least one selected from hydroquinone, methylhydroquinone, tert-butylhydroquinone and 2,6-di-tert-butylhydroquinone.

[0018] In some embodiments of the present application, in S2, the second solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, toluene, 1,1-dichloroethane, 1,2-dichloroethane, and xylene.

[0019] In some embodiments of the present application, in S2, the temperature is raised to 60-130°C, and the reaction is carried out for 4-8 hours.

[0020] Another object of the present application is to provide a coal combustion dispersant prepared by the method.

[0021] Still another object of the present application is to provide a high-efficiency coal-saving liquid additive comprising an effective amount of the coal combustion dispersant.

[0022] In some embodiments of the present application, the coal combustion dispersant is used in an amount of 5-8% by weight in the high-efficiency coal-saving liquid additive.

[0023] In some embodiments of the present application, the high-efficiency coal-saving liquid additive further comprises the following raw materials in the following amounts: manganese acetate / cobalt acetate 5-15%, cerium nitrate 0.5-2%, calcium carbonate 0.1-0.5%, ammonium bicarbonate 0.2-0.5%, vanadium pentoxide 0.1-0.3%, sodium carbonate 2-5%, bentonite 1-3%, calcium chloride 3-5%, urea 1-3%, and the balance of water.

[0024] Still another object of the present application is to provide a method for preparing the high-efficiency coal-saving liquid additive, comprising the following steps:

[0025] (1) adding the balance of water into a reaction kettle, stirring, and adding manganese acetate / cobalt acetate 5-15%, cerium nitrate 0.5-2%, and vanadium pentoxide 0.1-0.3% into the reaction kettle, stirring until completely dissolved, to obtain a mixture A;

[0026] (2) adding calcium carbonate 0.1-0.5%, ammonium bicarbonate 0.2-0.5%, sodium carbonate 2-5%, bentonite 1-3%, calcium chloride 3-5%, and urea 1-3% into the mixture A, continuing to stir, and controlling the reaction temperature to 30-60°C, to obtain a mixture B;

[0027] (3) adding the coal combustion dispersant 1-3% into the mixture B, and stirring at a high speed for 30-60 minutes, to obtain the high-efficiency coal-saving liquid additive.

[0028] Still another object of the present application is to provide a modified coal comprising the high-efficiency coal-saving liquid additive and coal.

[0029] Compared with the prior art, the present application has the following beneficial effects:

[0030] The coal combustion dispersant of the present application contains an anion group in the molecular structure, the anion group has electrostatic interaction with metal cations in catalysts, sulfur-fixing agents, rare earth compounds and other substances of the high-efficiency coal-saving liquid additive, and the coal combustion dispersant contains a hydroxyl group in the molecular structure, hydrogen bond interaction exists between the dispersants and between the dispersants and other substances, the interaction force between the dispersants and between the dispersants and other substances is improved, the dispersion effect of the coal combustion dispersant is significantly improved, and then the content of combustible components of the high-efficiency coal-saving liquid additive is significantly reduced, and the combustion efficiency of coal is improved. DETAILED DESCRIPTION

[0031] In order for those skilled in the art to better understand the technical solutions in the present application, the technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the present application.

[0032] The raw materials used in the present application are all conventional commercial products.

[0033] Embodiment 1

[0034] The present embodiment provides a coal combustion dispersant, and the specific preparation steps are as follows:

[0035] S1. Put dipentaerythritol (25.4 g), sodium hydroxide (0.2 g) and tetrahydrofuran (100 g) into a reflux reactor, mix, stir, heat to 65℃, add ethylene oxide (26.4 g), stir, react for 25 hours, and obtain a dendritic polymer;

[0036] S2. Mix the dendritic polymer (10 g), 1,2-distearyl-sn-glycero-3-phosphoglycerol (sodium salt) (30 g) dissolved in water, p-toluenesulfonic acid (0.5 g), hydroquinone (0.5 g) and tetrahydrofuran (70 g), stir, heat to 65℃ and react for 4 hours. After the reaction is completed, slowly add the reaction crude product into petroleum ether, precipitate and separate out the polymer, and the coal combustion dispersant is obtained. The number average molecular weight of the coal combustion dispersant is 3000-5000 g / mol detected by GPC.

[0037] Embodiment 2

[0038] The present embodiment provides a coal combustion dispersant, and the specific preparation steps are as follows:

[0039] S1. Add dipentaerythritol (25.4 g), sodium hydroxide (0.3 g) and tetrahydrofuran (100 g) into a reflux reactor, mix, stir, heat to 65°C, add oxirane (4.41 g), stir, react for 15 hours to obtain a dendrimer;

[0040] S2. Mix the dendrimer (10 g), 1,2-distearoyl-sn-glycero-3-phosphoglyceride (sodium salt) (20 g) dissolved in water, p-toluenesulfonic acid (1 g), hydroquinone (0.1 g) and tetrahydrofuran (70 g), stir, heat to 65°C and react for 8 hours. After the reaction is completed, slowly add the crude reaction product into petroleum ether to precipitate and separate the polymer to obtain a coal combustion dispersant. The number average molecular weight of the coal combustion dispersant is 3500-5500 g / mol as detected by GPC.

[0041] Example 3

[0042] This example provides a high-efficiency coal-saving liquid additive. The specific preparation steps are as follows:

[0043] (1) Add the remaining water into the reaction kettle in terms of weight percentage, stir, and add manganese acetate / cobalt acetate 5%, cerium nitrate 2% and vanadium pentoxide 0.1% into the reaction kettle, stir until completely dissolved to obtain mixture A;

[0044] (2) Add calcium carbonate 0.5%, ammonium bicarbonate 0.2%, sodium carbonate 5%, bentonite 1%, calcium chloride 5% and urea 1% into mixture A, continue to stir, and control the reaction temperature to 30-60°C to obtain mixture B;

[0045] (3) Add the coal combustion dispersant prepared in Example 1 8% into mixture B, high-speed stir for 30-60 minutes to obtain a high-efficiency coal-saving liquid additive.

[0046] Example 4

[0047] This example provides a high-efficiency coal-saving liquid additive. The specific preparation steps are as follows:

[0048] (1) Add the remaining water into the reaction kettle in terms of weight percentage, stir, and add manganese acetate / cobalt acetate 15%, cerium nitrate 0.5% and vanadium pentoxide 0.3% into the reaction kettle, stir until completely dissolved to obtain mixture A;

[0049] (2) Add calcium carbonate 0.1%, ammonium bicarbonate 0.5%, sodium carbonate 2%, bentonite 3%, calcium chloride 3% and urea 3% into mixture A, continue to stir, and control the reaction temperature to 30-60°C to obtain mixture B;

[0050] (3) In the mixture B, add the coal combustion dispersant prepared in Example 2 5%, high-speed stirring for 30-60 minutes, to obtain the high-efficiency coal-saving liquid additive.

[0051] Comparative Example 1

[0052] This comparative example provides a high-efficiency coal-saving liquid additive, which is only different from Example 3 in that a polyethylene glycol dispersant is used, and the specific preparation steps are as follows:

[0053] (1) Add the remaining water to the reaction kettle in terms of weight percentage, and stir. Add manganese acetate / cobalt acetate 5%, cerium nitrate 2%, and vanadium pentoxide 0.1% to the reaction kettle, and stir until completely dissolved to obtain mixture A;

[0054] (2) Add calcium carbonate 0.5%, ammonium bicarbonate 0.2%, sodium carbonate 5%, bentonite 1%, calcium chloride 5%, and urea 1% to the mixture A, continue to stir, and control the reaction temperature to 30-60°C to obtain mixture B;

[0055] (3) In the mixture B, add polyethylene glycol dispersant with a number average molecular weight of 2000-4000 g / mol 8%, high-speed stirring for 30-60 minutes, to obtain the high-efficiency coal-saving liquid additive.

[0056] Comparative Example 2

[0057] This comparative example provides a high-efficiency coal-saving liquid additive, which is only different from Example 3 in that an octadecanol polyoxyethylene ether dispersant is used, and the specific preparation steps are as follows:

[0058] (1) Add the remaining water to the reaction kettle in terms of weight percentage, and stir. Add manganese acetate / cobalt acetate 5%, cerium nitrate 2%, and vanadium pentoxide 0.1% to the reaction kettle, and stir until completely dissolved to obtain mixture A;

[0059] (2) Add calcium carbonate 0.5%, ammonium bicarbonate 0.2%, sodium carbonate 5%, bentonite 1%, calcium chloride 5%, and urea 1% to the mixture A, continue to stir, and control the reaction temperature to 30-60°C to obtain mixture B;

[0060] (3) In the mixture B, add octadecanol polyoxyethylene ether dispersant with a number average molecular weight of 4000-5000 g / mol 8%, high-speed stirring for 30-60 minutes, to obtain the high-efficiency coal-saving liquid additive.

[0061] Comparative Example 3

[0062] This comparative example provides a high-efficiency coal-saving liquid additive, which is only different from Example 3 in that a polycarboxylate dispersant is used, and the specific preparation steps are as follows:

[0063] (1) adding the rest of water into the reaction kettle by weight percentage, stirring, adding manganese acetate / cobalt acetate 5%, cerium nitrate 2% and vanadium pentoxide 0.1% into the reaction kettle, stirring until completely dissolved, obtaining mixture A;

[0064] (2) adding calcium carbonate 0.5%, ammonium bicarbonate 0.2%, sodium carbonate 5%, bentonite 1%, calcium chloride 5% and urea 1% into mixture A, continuing to stir, controlling the reaction temperature to 30~60℃, obtaining mixture B;

[0065] (3) adding polycarboxylate dispersant with number average molecular weight of 3000~6000g / mol 8% into mixture B, high-speed stirring for 30~60 minutes, obtaining high-efficiency coal-saving liquid additive.

[0066] Combustion experiment:

[0067] When used, 10 kg of high-efficiency coal-saving liquid additive prepared by example 3-4 and comparative example 1-3 is respectively added into water to dilute into 2 tons, the diluted high-efficiency coal-saving liquid additive is respectively sprayed on coal with heat output of 5000 Kcal / kg by using a spraying device for combustion, and the coal consumption of coal added with additive and coal without additive is compared and recorded in table 1.

[0068] Table 1. Combustion efficiency comparison.

[0069]

[0070] As shown in table 1, the coal combustion dispersant of the present application can significantly improve the dispersion of the coal combustion dispersant, and further significantly improve the combustion efficiency of the high-efficiency coal-saving liquid additive.

[0071] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit it, although the present application has been described in detail by comparing the above examples, those skilled in the art should understand that the technical personnel can still modify or replace the specific embodiments of the present application after reading the present application, but these modifications or changes are still within the scope of the present application. The claims of the application are protected.

Claims

1. A method for preparing a coal combustion dispersant, characterized by, The method comprises the following steps: S1. mixing dipentaerythritol, ethylene oxide, strong base catalyst and first solvent, warming and reacting to obtain dendrimer; S2. mixing the dendrimer, 1,2-distearoyl-sn-glycerophosphoglycerol (sodium salt), strong acid catalyst, polymerization inhibitor and second solvent, warming and reacting to obtain coal combustion dispersant.

2. The method of claim 1, wherein the coal combustion dispersant is prepared by the steps of: (a) mixing the dispersant with water to form a mixture; (b) adding the mixture to the coal; and (c) drying the coal. In S1, the molar ratio of the dipentaerythritol to the ethylene oxide is 1:6-12; And / or, the amount of the strong base catalyst is 1000-4000 ppm of the total reaction raw materials; And / or, the strong base catalyst comprises one of potassium hydroxide, sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide, sodium methoxide, sodium ethoxide and sodium isopropoxide; And / or, the first solvent is at least one selected from dichloromethane, chloroform, tetrahydrofuran, toluene, 1,1-dichloroethane, 1,2-dichloroethane and dimethylbenzene; And / or, the temperature of the warming and reacting is 40-130℃, and the time is 15-25 hours.

3. The method of claim 1, wherein the coal combustion dispersant is prepared by the steps of: (a) mixing the dispersant with water; (b) adding the dispersant to the coal; and (c) drying the coal. In S2, the mass ratio of the dendrimer to 1,2-distearoyl-sn-glycerophosphoglycerol (sodium salt) is 1:2-3; And / or, the mass ratio of the dendrimer, strong acid catalyst and polymerization inhibitor is 1:0.05-0.1:0.01-0.

05.

4. The method of claim 1, wherein the coal combustion dispersant is prepared by the steps of: (a) mixing the dispersant with water; (b) adding the dispersant to the coal; and (c) drying the coal. In S2, the strong acid catalyst is at least one selected from sulfuric acid, phosphoric acid, p-toluenesulfonic acid and methylsulfonic acid; And / or, the polymerization inhibitor is at least one selected from hydroquinone, methylhydroquinone, tert-butylhydroquinone and 2,6-di-tert-butylhydroquinone; And / or, the second solvent is at least one selected from dichloromethane, chloroform, tetrahydrofuran, toluene, 1,1-dichloroethane, 1,2-dichloroethane and dimethylbenzene; And / or, the warming and reacting is warming to 60-130℃ and reacting for 4-8 hours.

5. A coal combustion dispersant, characterized by, The coal combustion dispersant is prepared by the method for preparing coal combustion dispersant according to any one of claims 1-4.

6. A highly efficient coal-saving liquid additive, characterized by, The method comprises the following steps:

7. The highly efficient coal-saving liquid additive as claimed in claim 6, wherein the said additive is a mixture of 2-3% of the said compound of formula (I) and 97-98% of the said compound of formula (II). The coal combustion dispersant is prepared by the method for preparing coal combustion dispersant according to any one of claims 1-4.

8. The highly efficient coal-saving liquid additive as claimed in claim 7, wherein the said additive is a mixture of 2-3% of the said compound of formula (I) and 97-98% of the said compound of formula (II). The method comprises the following steps:

9. A process for the preparation of a highly efficient coal-saving liquid additive, characterized by, (1) adding the remaining water into a reaction kettle, stirring, adding manganese acetate / cobalt acetate 5-15%, cerium nitrate 0.5-2% and vanadic oxide 0.1-0.3% into the reaction kettle, stirring until completely dissolved to obtain mixture A; (2) adding calcium carbonate 0.1-0.5%, ammonium bicarbonate 0.2-0.5%, sodium carbonate 2-5%, bentonite 1-3%, calcium chloride 3-5% and urea 1-3% into mixture A, continuing to stir, and controlling the reaction temperature to 30-60℃ to obtain mixture B; ​ (3) In the mixture B, add the coal combustion dispersant of claim 5 1~3%, high-speed stirring 30~60 minutes, get high efficient coal-saving liquid additive.

10. A modified coal, characterized by, Including the high efficient coal-saving liquid additive of any one of claims 6~8 and coal.

Images