Fire coal auxiliary agent, preparation method and application thereof and fire coal

Abstract

The invention relates to a fire coal auxiliary agent, a preparation method and application thereof and fire coal. The coal-fired auxiliary agent comprises the following components: a depolymerization kettle bottom solution, a catalyst and an oxidizing agent, the depolymerization kettle base solution comprises at least one of an acrylic acid heavy component and a butyl acrylate heavy component. According to the fire coal auxiliary agent, through mutual cooperation of all the components, the ignition point of fire coal can be effectively reduced, the burnout point of the fire coal is reduced, and the combustion efficiency of the fire coal is improved. Meanwhile, the acrylic acid heavy component and the butyl acrylate heavy component can be effectively utilized, the economic benefit is improved, and environmental protection is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of resource recycling, and in particular to a coal-burning additive, a preparation method thereof, an application thereof, and coal-burning. Background Art

[0002] Acrylic acid and butyl acrylate are chemical raw materials with wide industrial applications. Industrial acrylic acid and butyl acrylate are produced by distillation and other means using crude acrylic acid and crude butyl acrylate as raw materials, respectively. In the distillation production process, as the distillation continues, acrylic acid heavy components mainly composed of acrylic acid polymers and butyl acrylate heavy components mainly composed of butyl acrylate polymers will continue to accumulate in the bottom of the tower.

[0003] The general method for treating acrylic acid heavy components and butyl acrylate heavy components is direct incineration, but this will lead to environmental pollution and waste of energy.

[0004] Coal is mainly used in thermal power, cement, metallurgy and chemical industries. With the continuous development of industrialization, people's demand for coal is increasing. However, coal is a non-renewable resource and the combustion process is prone to air pollution. Therefore, improving the combustion efficiency of coal can not only reduce costs and generate certain economic benefits, but also reduce air pollution and generate good social benefits. Summary of the invention

[0005] Based on this, it is necessary to provide a coal-burning aid that can improve the coal combustion efficiency, and the coal-burning aid can also effectively utilize the acrylic acid heavy component and the butyl acrylate heavy component. Further, a preparation method, application and coal of the coal-burning aid are provided.

[0006] In a first aspect, the present application provides a coal combustion aid, the components of which include depolymerization kettle bottom liquid, a catalyst and an oxidant; the depolymerization kettle bottom liquid includes at least one of acrylic acid heavy components and butyl acrylate heavy components.

[0007] The coal-burning aid is prepared from the depolymerization kettle bottom liquid of at least one of the acrylic acid heavy component and the butyl acrylate heavy component, a catalyst and an oxidant as raw materials. The components work together to effectively reduce the ignition point of the coal, reduce the burnout point of the coal, and improve the combustion efficiency of the coal. At the same time, the acrylic acid heavy component and the butyl acrylate heavy component can be effectively utilized, thereby improving economic benefits and being beneficial to environmental protection.

[0008] Furthermore, after the heavy components are depolymerized, the remaining or depolymerized light components are basically evaporated and discharged, leaving only the heavy components in the kettle bottom liquid. The kettle bottom liquid is used as the mother liquid of the coal-burning additive, which can provide the calorific value required by the coal-burning additive itself. In addition, the kettle bottom liquid can be solidified only after the light components are evaporated, further improving the stability of the coal-burning additive.

[0009] In some embodiments, the depolymerization kettle bottom liquid includes, by mass percentage, 0% to 98% of acrylic acid polymer, 1% to 14% of maleic anhydride, 0% to 99% of butyl acrylate polymer, and 0% to 5% of butyl butoxypropionate; the acrylic acid polymer and the butyl acrylate polymer are not both 0.

[0010] In some embodiments, the coal combustion aid satisfies one of the following conditions:

[0011] (1) Calculated by mass percentage, the depolymerization kettle bottom liquid comprises 85% to 98% of acrylic acid polymer and 1% to 10% of maleic anhydride;

[0012] (2) Calculated by weight percentage, the depolymerization kettle bottom liquid comprises 90% to 99% of butyl acrylate polymer, 0% to 5% of butyl butoxypropionate and 0% to 4% of maleic anhydride;

[0013] (3) Calculated by mass percentage, the depolymerization kettle bottom liquid includes 25% to 72% of acrylic acid polymer, 1% to 2% of maleic anhydride, 24% to 75% of butyl acrylate polymer and 0% to 5% of butyl butoxypropionate.

[0014] In some embodiments, the coal-burning additive includes, by weight, 50 to 85 parts of the depolymerization kettle bottom liquid, 1 to 30 parts of an oxidant, and 1 to 20 parts of a catalyst.

[0015] In some embodiments, the coal combustion aid further comprises 5 to 10 parts of alkaline inorganic filler by weight.

[0016] In some embodiments, the coal-burning additive includes, by weight, 75 to 85 parts of the depolymerization kettle bottom liquid, 1 to 10 parts of an oxidant, 1 to 5 parts of a catalyst, and 5 to 10 parts of an alkaline inorganic filler.

[0017] In some embodiments, the coal combustion aid satisfies at least one of the following conditions:

[0018] (1) The oxidant is a metal salt;

[0019] (2) The catalyst is a metal oxide;

[0020] (3) The alkaline inorganic filler is at least one selected from calcium oxide, calcium hydroxide, sodium hydroxide and potassium hydroxide.

[0021] In some embodiments, the coal combustion aid satisfies at least one of the following conditions:

[0022] (1) The oxidant is at least one selected from potassium permanganate, sodium nitrate, potassium nitrate and potassium chlorate;

[0023] (2) The catalyst is at least one selected from the group consisting of aluminum oxide, manganese dioxide, magnesium oxide and iron oxide.

[0024] The second aspect of the present application provides a method for preparing a coal combustion aid, comprising the following steps:

[0025] The depolymerization kettle bottom liquid, the catalyst and the oxidant are mixed; the depolymerization kettle bottom liquid comprises at least one of acrylic acid heavy components and butyl acrylate heavy components.

[0026] In some embodiments, the method for preparing the depolymerization kettle bottom liquid comprises:

[0027] At least one of the acrylic acid heavy component and the butyl acrylate heavy component is subjected to a depolymerization reaction under the action of an acidic catalyst to obtain a bottom liquid; the depolymerization reaction pressure is -0.09MPa~0.05MPa, the temperature is 100℃~350℃, and the time is 5h~15h.

[0028] In some embodiments, the acidic catalyst is selected from at least one of methanesulfonic acid, p-toluenesulfonic acid, and sulfuric acid.

[0029] In some embodiments, the following steps are also included:

[0030] After the depolymerization kettle bottom liquid, the catalyst and the oxidant are mixed, the obtained mixture is kept warm for 5 minutes to 10 minutes at a vacuum pressure of 20 KPa to 50 KPa and a temperature of 180° C. to 200° C.

[0031] The third aspect of the present application provides a use of the coal-fired fuel additive described in the first aspect in preparing coal.

[0032] The fourth aspect of the present application provides a coal fuel, comprising a coal substrate and the coal fuel additive described in the first aspect.

[0033] In some embodiments, the mass percentage of the coal-fired auxiliary agent in the coal is 0.2% to 0.5%. DETAILED DESCRIPTION

[0034] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below, and preferred embodiments of the present invention are given. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. It should be understood that the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0036] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0037] Coal-burning additives are additives that can promote the full combustion of coal, play the role of combustion-supporting, energy-enhancing, and coal-saving. They can reduce harmful gas emissions, protect the environment, reduce corporate production costs, and bring huge economic benefits to companies. Compared with solid coal-burning additives, liquid coal-burning additives have higher requirements for sealing in storage and transportation; and liquid coal-burning additives are easily deteriorated or exploded due to temperature, humidity, vibration, etc.

[0038] In one embodiment of the present application, a coal combustion aid is provided, the components of which include depolymerization bottom liquid, a catalyst and an oxidant; the depolymerization bottom liquid includes at least one of acrylic acid heavy components and butyl acrylate heavy components.

[0039] It can be understood that the above-mentioned depolymerization bottom liquid includes the first depolymerization bottom liquid obtained by the recombinant depolymerization of acrylic acid, or includes the second depolymerization bottom liquid obtained by the recombinant depolymerization of butyl acrylate, or includes the third depolymerization bottom liquid obtained by the depolymerization of a mixture of acrylic acid recombinants and butyl acrylate recombinants, or includes a mixed liquid of the above-mentioned first depolymerization bottom liquid and the second depolymerization bottom liquid.

[0040] The coal-burning aid is prepared from the depolymerization kettle bottom liquid of at least one of the acrylic acid heavy component and the butyl acrylate heavy component, a catalyst and an oxidant as raw materials. The components work together to effectively reduce the ignition point of the coal, reduce the burnout point of the coal, and improve the combustion efficiency of the coal. At the same time, the acrylic acid heavy component and the butyl acrylate heavy component can be effectively utilized, thereby improving economic benefits and being beneficial to environmental protection.

[0041] Furthermore, after the heavy components are depolymerized, the remaining or depolymerized light components are basically evaporated and discharged, leaving only the heavy components in the kettle bottom liquid. The kettle bottom liquid is used as the mother liquid of the coal-burning additive, which can provide the calorific value required by the coal-burning additive itself. In addition, the kettle bottom liquid can be solidified only after the light components are evaporated, further improving the stability of the coal-burning additive.

[0042] In some embodiments, the acrylic acid recombinant fraction is a bottoms liquid component of propylene oxidation to produce acrylic acid.

[0043] In some embodiments, the acrylic acid heavy component includes, by weight percentage, 0-1% propionic acid, 0-30% acrylic acid, 1%-25% β-(acryloyloxy)propionic acid, 1%-5% maleic anhydride, and 40%-80% acrylic acid polymer.

[0044] In some embodiments, the recombinant fraction of butyl acrylate is a bottom liquid component of crude butyl acrylate obtained by esterification of acrylic acid and n-butanol in the presence of an acidic catalyst during distillation.

[0045] In some embodiments, the butyl acrylate recombinant component includes, by weight percentage, 0-2% butanol, 0-20% butyl acrylate, 5%-30% butyl butoxypropionate, 0-2% butyl hydroxyacrylate, 0-5% butyl propoxyacrylate, 0-2% maleic anhydride, and 40%-80% butyl acrylate polymer.

[0046] In some embodiments, the depolymerization reactor bottom liquid includes, by weight percentage, 0% to 98% of acrylic acid polymer, 1% to 14% of maleic anhydride, 0% to 99% of butyl acrylate polymer, and 0% to 5% of butyl butoxypropionate; the polymers of acrylic acid and butyl acrylate are not both 0.

[0047] In some embodiments, the depolymerization still bottom liquid includes a third depolymerization still bottom liquid obtained by depolymerizing a mixture of acrylic acid heavy components and butyl acrylate heavy components, wherein the mass ratio of the acrylic acid heavy components to the butyl acrylate heavy components in the mixture is (0.1-10): 1. Preferably, the mass ratio of the acrylic acid heavy components to the butyl acrylate heavy components in the mixture is (0.3-3): 1.

[0048] In some embodiments, the depolymerization kettle bottom liquid includes a mixed liquid of a first depolymerization kettle bottom liquid and a second depolymerization kettle bottom liquid, wherein the mass ratio of the first depolymerization kettle bottom liquid to the second depolymerization kettle bottom liquid is (0.1-10):1. As an example, the mass ratio of the first depolymerization kettle bottom liquid to the second depolymerization kettle bottom liquid can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1. Further, the mass ratio of the first depolymerization kettle bottom liquid to the second depolymerization kettle bottom liquid can be any other ratio within the above range. Preferably, the mass ratio of the first depolymerization kettle bottom liquid to the second depolymerization kettle bottom liquid is (0.8-2):1.

[0049] In some embodiments, the depolymerization reactor bottom liquid includes 85% to 98% of acrylic acid polymer and 1% to 10% of maleic anhydride, calculated by weight percentage.

[0050] In some embodiments, the depolymerization reactor bottom liquid includes 90% to 99% of butyl acrylate polymer, 0 to 5% of butyl butoxypropionate, and 0 to 4% of maleic anhydride, calculated by mass percentage.

[0051] In some embodiments, the depolymerization reactor bottom liquid includes, by weight percentage, 25% to 72% of acrylic acid polymer, 1% to 2% of maleic anhydride, 24% to 75% of butyl acrylate polymer, and 0% to 5% of butyl butoxypropionate.

[0052] In some embodiments, the oxidant is a metal salt. Further, the metal salt oxidant is selected from at least one of potassium permanganate, sodium nitrate, potassium nitrate and potassium chlorate. Preferably, the metal salt oxidant is potassium nitrate.

[0053] In some embodiments, the catalyst is a metal oxide. Further, the metal oxide catalyst is selected from at least one of aluminum oxide, manganese dioxide, magnesium oxide and ferric oxide. Preferably, the metal oxide catalyst is manganese dioxide.

[0054] In some embodiments, the coal-burning aid includes 50 to 85 parts of depolymerization kettle bottom liquid, 1 to 30 parts of oxidant, and 1 to 20 parts of catalyst by weight. The depolymerization kettle bottom liquid in this embodiment refers to at least one of a depolymerization kettle bottom liquid of a mixture of acrylic acid heavy components and butyl acrylate heavy components, a depolymerization kettle bottom liquid of acrylic acid heavy components, and a depolymerization kettle bottom liquid of butyl acrylate heavy components.

[0055] As an example, the mass fraction of the depolymerization kettle bottom liquid in the coal-fired additive can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 73 parts, 75 parts, 78 parts, 80 parts, 82 parts or 85 parts. Further, the mass fraction of the depolymerization kettle bottom liquid can be a range value consisting of any two of the above point values ​​as end values. Preferably, the mass fraction of the depolymerization kettle bottom liquid is 75 parts to 85 parts.

[0056] As an example, the mass fraction of the oxidant in the coal-fired additive can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 25 parts or 30 parts. Further, the mass fraction of the oxidant can be a range value consisting of any two of the above point values ​​as end values. Preferably, the mass fraction of the oxidant is 1 part to 10 parts.

[0057] As an example, the mass fraction of the catalyst in the coal-fired additive can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 15 parts, 18 parts or 20 parts. Further, the mass fraction of the catalyst can be a range value consisting of any two of the above point values ​​as end values. Preferably, the mass fraction of the catalyst is 1 part to 5 parts.

[0058] In some embodiments, the coal-burning aid includes 50 to 85 parts of depolymerization kettle bottom liquid, 1 to 30 parts of oxidant, and 1 to 20 parts of catalyst, and also includes 5 to 10 parts of alkaline inorganic filler. Adding alkaline inorganic filler to the coal-burning aid can improve the strength of the solid coal-burning aid, reduce surface viscosity, and react with acidic substances in the components to neutralize, increase the pH value of the system, reduce the acidity of the system, and reduce corrosion to equipment.

[0059] In some embodiments, the mass fraction of the inorganic filler in the coal combustion additive may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts. Further, the mass fraction of the inorganic filler may be a range value consisting of any two of the above point values ​​as end values.

[0060] In some embodiments, the alkaline inorganic filler is selected from at least one of calcium oxide, calcium hydroxide, sodium hydroxide and potassium hydroxide. Preferably, the alkaline inorganic filler is calcium oxide. Calcium oxide can react with acrylic acid to generate calcium salt, thereby reducing the acidity of the depolymerization kettle bottom liquid. At the same time, calcium oxide has strong hygroscopicity and can absorb the viscous liquid inside acrylic acid and butyl acrylate, thereby enhancing the strength of the coal-burning additive.

[0061] In some embodiments, the coal-burning additive includes, by weight, 75 to 85 parts of depolymerization kettle bottom liquid, 1 to 10 parts of oxidant, 1 to 5 parts of catalyst, and 5 to 10 parts of alkaline inorganic filler.

[0062] In some embodiments, the coal-burning additive includes, by weight percentage, 75% to 85% of depolymerization reactor bottom liquid, 1% to 10% of oxidant, 1% to 5% of catalyst, and 5% to 10% of alkaline inorganic filler.

[0063] In some embodiments, the coal combustion aid is in a solid state under normal temperature conditions. In the present application, normal temperature conditions refer to conditions of 10°C to 40°C.

[0064] In one embodiment of the present application, a method for preparing the above-mentioned coal combustion aid is provided, comprising the following step S10.

[0065] S10, mixing the depolymerization kettle bottom liquid, the catalyst and the oxidant.

[0066] In some embodiments, the method for preparing the depolymerization bottom liquid comprises:

[0067] At least one of acrylic acid heavy components and butyl acrylate heavy components is subjected to a depolymerization reaction under the action of an acidic catalyst to obtain a bottom liquid.

[0068] Some light components and components with lower molecular weight remain in the heavy components of acrylic acid and butyl acrylate, making the heavy components liquid. The light components can be removed after depolymerization, and some polymers can also be decomposed into light components and discharged; at the same time, some polymer components can also be further polymerized, thereby increasing the viscosity of the coal-fired additive and even making the coal-fired additive tend to be solid.

[0069] In some embodiments, the acidic catalyst is selected from at least one of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid. Preferably, the acidic catalyst is p-toluenesulfonic acid.

[0070] In some embodiments, the amount of the acidic catalyst added is 1% to 2% of the total weight of the acrylic acid heavy component and the butyl acrylate heavy component.

[0071] In some embodiments, the pressure of the depolymerization reaction is -0.09 MPa to 0.05 MPa. As an example, the pressure of the depolymerization reaction can be -0.09 MPa, -0.06 MPa, -0.05 MPa, -0.03 MPa, 0 MPa, 0.01 MPa, 0.02 MPa, 0.04 MPa or 0.05 MPa. Further, the pressure of the depolymerization reaction can be a range value consisting of any two of the above point values ​​as end values. Under this pressure condition, the light components obtained after partial residue and depolymerization can be separated from the bottom liquid of the kettle.

[0072] In some embodiments, the temperature of the depolymerization reaction is 100°C to 350°C. As an example, the temperature of the depolymerization reaction can be 100°C, 150°C, 180°C, 200°C, 220°C, 250°C, 260°C, 280°C, 300°C, 310°C, 320°C, 340°C or 350°C. Further, the temperature of the depolymerization reaction can be a range value consisting of any two of the above point values ​​as end values. Preferably, the temperature of the depolymerization reaction is 150°C to 220°C.

[0073] In some embodiments, the time of the depolymerization reaction is 5 hours to 15 hours. As an example, the time of the depolymerization reaction can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours. Further, the time of the depolymerization reaction can be a range value consisting of any two of the above point values ​​as end values.

[0074] In some embodiments, the above preparation method further includes step S20.

[0075] S20, keeping the mixture obtained in step S10 warm for 5 min to 10 min under the conditions of a vacuum pressure of 20 KPa to 50 KPa and a temperature of 180° C. to 200° C. Keeping the mixture warm for 5 min to 10 min under the conditions of 20 KPa to 50 KPa and 180° C. to 200° C. can further remove the residual light components in the mixture and increase the viscosity of the coal-burning additive.

[0076] In some embodiments, the above step S20 can be performed in a twin-screw extruder with a vacuum system and a temperature control system.

[0077] In one embodiment of the present application, the application of the above-mentioned coal-fired fuel additive in the preparation of coal-fired fuel is provided.

[0078] In one embodiment of the present application, a method for preparing coal is provided, comprising the following steps:

[0079] The fuel coal and the coal base are mixed.

[0080] In one embodiment of the present application, a coal fuel is provided, which includes a coal base material and the above-mentioned coal fuel additive.

[0081] In some embodiments, the mass percentage of the coal-fired auxiliary agent in the coal is 0.2% to 0.5%. Preferably, the mass percentage of the coal-fired auxiliary agent in the coal is 0.3%.

[0082] In order to make the purpose, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The embodiments described below are only preferred embodiments of the present invention, which can be used to describe the present invention and cannot be understood as limiting the scope of the present invention. It should be pointed out that any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0083] In order to better illustrate the present invention, the present invention is further described below in conjunction with the embodiments. The following are specific embodiments.

[0084] The component ratios of the acrylic acid heavy component and the butyl acrylate heavy component used in each embodiment and comparative example of the present application are as follows:

[0085] Calculated by mass percentage, the heavy components of acrylic acid include: 1% propionic acid, 25% acrylic acid, 15% β-(acryloyloxy)propionic acid, 3% maleic anhydride and 56% acrylic acid polymer.

[0086] Calculated by mass percentage, the butyl acrylate heavy component includes: 2% butanol, 15% butyl acrylate, 25% butyl butoxypropionate, 1% hydroxy butyl acrylate, 3% propoxy butyl acrylate, 1% maleic anhydride and 53% butyl acrylate polymer.

[0087] Example of preparation of depolymerization reactor bottom liquid:

[0088] Example 1-1, preparation of depolymerization bottom liquid 1 of a mixture of acrylic acid heavy component and butyl acrylate heavy component:

[0089] 49 parts of acrylic acid heavy components and 50 parts of butyl acrylate heavy components were added to the reactor, and then 1 part of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 190°C with stirring, and the pressure in the reactor was maintained at 0.01 MPa, and the depolymerization reaction was carried out for 9 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain a depolymerization reactor bottom liquid 1 of a mixture of acrylic acid heavy components and butyl acrylate heavy components; wherein the depolymerization reactor bottom liquid 1 includes 45%wt% of acrylic acid polymer, 47wt% of butyl acrylate polymer, 3wt% of butyl butoxypropionate and 2wt% of maleic anhydride.

[0090] Example 1-2, preparation of depolymerization bottom liquid 2 of a mixture of acrylic acid heavy components and butyl acrylate heavy components:

[0091] 73 parts of acrylic acid heavy components and 26 parts of butyl acrylate heavy components were added to the reactor, and then 1.0 part of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 210°C with stirring, and the pressure in the reactor was maintained at 0.01MPa, and the depolymerization reaction was carried out for 10 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain butyl acrylate recombinant depolymerization reactor bottom liquid 2; wherein the depolymerization reactor bottom liquid 2 includes 2wt% of butyl butoxypropionate, 2wt% of maleic anhydride, 69% of acrylic acid polymer and 24wt% of butyl acrylate polymer.

[0092] Example 1-3, preparation of depolymerization bottom liquid 3 of a mixture of acrylic acid heavy component and butyl acrylate heavy component:

[0093] 29 parts of acrylic acid heavy components and 69 parts of butyl acrylate heavy components were added to the reactor, and then 2.0 parts of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 210°C with stirring, and the pressure in the reactor was maintained at -0.01MPa, and the depolymerization reaction was carried out for 10 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain acrylic acid heavy components and butyl acrylate recombinant depolymerization reactor bottom liquid 3; wherein the depolymerization reactor bottom liquid includes 25wt% of acrylic acid polymer, 2wt% of maleic anhydride and 70wt% of butyl acrylate polymer.

[0094] Example 1-4, Preparation of Butyl Acrylate Recombination Decomposition Polymerization Still Bottom Liquid 4:

[0095] 99% of butyl acrylate recombinant components were added to the reactor, and then 1 part of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 150°C with stirring, and the pressure in the reactor was maintained at -0.08MPa, and the depolymerization reaction was carried out for 6 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain butyl acrylate recombinant decomposition reactor bottom liquid 4; wherein, the butyl acrylate recombinant decomposition reactor bottom liquid 4 includes a polymer containing 3wt% maleic anhydride and 94wt% butyl acrylate.

[0096] Example 1-5, Preparation of Butyl Acrylate Recombination Decomposition Polymerization Still Bottom Liquid 5:

[0097] 99 parts of butyl acrylate recombinant components were added to the reactor, and then 1.0 parts of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 190°C with stirring, and the pressure in the reactor was maintained at -0.02MPa, and the depolymerization reaction was carried out for 8 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain butyl acrylate recombinant decomposition reactor bottom liquid 5; wherein the butyl acrylate recombinant decomposition reactor bottom liquid 5 includes a polymer containing 1wt% of butyl butoxypropionate, 1% of maleic anhydride and 94wt% of butyl acrylate.

[0098] Example 1-6, Preparation of Butyl Acrylate Recombination Decomposition Polymerization Still Bottom Liquid 6:

[0099] 99 parts of butyl acrylate recombinant components were added to the reactor, and then 1.0 parts of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 210°C with stirring, and the pressure in the reactor was maintained at 0.01 MPa, and the depolymerization reaction was carried out for 10 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain butyl acrylate recombinant decomposition reactor bottom liquid 6; wherein the butyl acrylate recombinant decomposition reactor bottom liquid 6 includes 2wt% of butyl butoxypropionate, 1wt% of maleic anhydride, and 93wt% of butyl acrylate polymer.

[0100] Example 1-7, Preparation of acrylic acid recombinant decomposition reactor bottom liquid 7:

[0101] 99 parts of acrylic acid recombinant components were added to the reactor, and then 1.0 parts of p-toluenesulfonic acid catalyst was added, and the temperature was raised to 190°C with stirring, and the pressure in the reactor was maintained at 0.01 MPa, and the depolymerization reaction was carried out for 9 hours. The oligomers in the reactor were partially depolymerized into light components and evaporated to obtain acrylic acid recombinant depolymerization reactor bottom liquid 7; wherein the acrylic acid recombinant depolymerization reactor bottom liquid 7 includes 91wt% of acrylic acid polymers and 5wt% of maleic anhydride.

[0102] The components of the depolymerization reactor bottom liquid prepared in each example are shown in Table 1.

[0103] Table 1

[0104]

[0105] Application examples of coal burning additives:

[0106] Example 1

[0107] (1) Weigh the raw material components according to the mass ratio: 83 wt% of acrylic acid recombinant decomposition reactor bottom liquid 7, 5 wt% of calcium oxide powder, 10 wt% of potassium nitrate oxidant and 2 wt% of manganese dioxide catalyst.

[0108] (2) Slowly add 5 wt% calcium oxide powder to the 83 wt% acrylic acid recombinant decomposition polymerization bottom liquid 7 at 160°C~180°C under mechanical stirring, and continue stirring for 1.5 hours; then slowly add 10 wt% potassium nitrate oxidant, and continue stirring for 2 hours; then slowly add 2 wt% manganese dioxide catalyst, and continue stirring for 1 hour.

[0109] (3) After the stirring is completed, the above-mentioned mixed material is sent into a twin-screw extruder equipped with a vacuum system and a temperature control system while it is hot, wherein the vacuum pressure of the twin-screw extruder is set to 20 KPa; in the heating section of the twin-screw extruder, the material is heated to 180°C within 7 minutes and then kept at a constant temperature for 6 minutes; in the cooling section, the material is cooled to 80°C within 6 minutes to obtain a solid coal combustion additive.

[0110] (4) The solid coal-burning additive and the coal sample are mixed in a mass ratio of 0.3:99.7 to obtain coal with the coal-burning additive added thereto.

[0111] Example 2

[0112] (1) Weigh the raw material components according to the mass ratio: 83wt% of butyl acrylate recombinant decomposition reactor bottom liquid 4, 5wt% of calcium oxide powder, 10wt% of potassium nitrate oxidant and 2wt% of manganese dioxide catalyst.

[0113] (2) Slowly add 5 wt% calcium oxide powder to the 83 wt% butyl acrylate recombinant decomposition polymerization bottom liquid 4 at 160°C~180°C under mechanical stirring, and continue stirring for 1.5 hours; then slowly add 10 wt% potassium nitrate oxidant, and continue stirring for 2 hours; then slowly add 2 wt% manganese dioxide catalyst, and continue stirring for 1 hour.

[0114] (3) After the stirring is completed, the above-mentioned mixed material is sent into a twin-screw extruder equipped with a vacuum system and a temperature control system while it is hot, wherein the vacuum pressure of the twin-screw extruder is set to 30 KPa; in the heating section of the twin-screw extruder, the material is heated to 200°C within 8 minutes and then kept at a constant temperature for 7 minutes; in the cooling section, the material is cooled to 90°C within 10 minutes to obtain a solid coal combustion additive.

[0115] (4) The solid coal-burning additive and the coal sample are mixed in a mass ratio of 0.3:99.7 to obtain coal with the coal-burning additive added thereto.

[0116] Example 3

[0117] (1) Weigh the raw material components according to the mass ratio: 83 wt% of the depolymerization kettle bottom liquid 1 of the heavy component of acrylic acid and the heavy component of butyl acrylate, 5 wt% of calcium oxide powder, 10 wt% of potassium nitrate oxidant and 2 wt% of manganese dioxide catalyst.

[0118] (2) Slowly add 5 wt% of calcium oxide powder to the depolymerization bottom liquid 1 of 83 wt% acrylic acid heavy component and butyl acrylate heavy component at 160°C~180°C under mechanical stirring, and continue stirring for 1.5 hours; then slowly add 10 wt% of potassium nitrate oxidant, and continue stirring for 2 hours; then slowly add 2 wt% of manganese dioxide catalyst, and continue stirring for 1 hour.

[0119] (3) After the stirring is completed, the above-mentioned mixed material is sent into a twin-screw extruder equipped with a vacuum system and a temperature control system while it is hot, wherein the vacuum pressure of the twin-screw extruder is set to 40 KPa; in the heating section of the twin-screw extruder, the material is heated to 200°C within 8 minutes and then kept at a constant temperature for 7 minutes; in the cooling section, the material is cooled to 90°C within 10 minutes to obtain a solid coal-burning additive.

[0120] (4) The solid coal-burning additive and the coal sample are mixed in a mass ratio of 0.3:99.7 to obtain coal with the coal-burning additive added thereto.

[0121] Example 4

[0122] (1) Weigh the raw material components according to the mass ratio: 83 wt% of butyl acrylate recombinant decomposition reactor bottom liquid 5, 5 wt% of calcium oxide powder, 10 wt% of potassium nitrate oxidant and 2 wt% of manganese dioxide catalyst.

[0123] (2) Slowly add 5 wt% calcium oxide powder to the 83 wt% butyl acrylate recombinant decomposition polymerization bottom liquid 5 at 160°C~180°C under mechanical stirring, and continue stirring for 1.5 hours; then slowly add 10 wt% potassium nitrate oxidant, and continue stirring for 2 hours; then slowly add 2 wt% manganese dioxide catalyst, and continue stirring for 1 hour.

[0124] (3) After the stirring is completed, the above-mentioned mixed material is sent into a twin-screw extruder equipped with a vacuum system and a temperature control system while it is hot, wherein the vacuum pressure of the twin-screw extruder is set to 45 KPa; in the heating section of the twin-screw extruder, the material is heated to 200°C within 8 minutes and then kept at a constant temperature for 7 minutes; in the cooling section, the material is cooled to 90°C within 10 minutes to obtain a solid coal-burning additive.

[0125] (4) The solid coal-burning additive and the coal sample are mixed in a mass ratio of 0.3:99.7 to obtain coal with the coal-burning additive added thereto.

[0126] Example 5

[0127] The preparation method of this embodiment is basically the same as that of embodiment 2, except that the components of the depolymerization bottom liquid in this embodiment are different, and the depolymerization bottom liquid used in this embodiment is the depolymerization bottom liquid 6 of the heavy component of butyl acrylate. The other steps are basically the same as those of embodiment 1.

[0128] Example 6

[0129] (1) Weigh the raw material components according to the mass ratio: 80 wt% of butyl acrylate recombinant decomposition reactor bottom liquid 4, 5 wt% of calcium oxide powder, 10 wt% of potassium nitrate oxidant and 5 wt% of manganese dioxide catalyst.

[0130] (2) Slowly add 5 wt% calcium oxide powder to the 83 wt% butyl acrylate recombinant decomposition polymerization bottom liquid 4 at 160°C~180°C under mechanical stirring, and continue stirring for 1.5 hours; then slowly add 10 wt% potassium nitrate oxidant, and continue stirring for 2 hours; then slowly add 5 wt% manganese dioxide catalyst, and continue stirring for 1 hour.

[0131] (3) After the stirring is completed, the above-mentioned mixed material is sent into a twin-screw extruder equipped with a vacuum system and a temperature control system while it is hot, wherein the vacuum pressure of the twin-screw extruder is set to 50 KPa; in the heating section of the twin-screw extruder, the material is heated to 200°C within 8 minutes and then kept at a constant temperature for 7 minutes; in the cooling section, the material is cooled to 90°C within 10 minutes to obtain a solid coal-burning additive.

[0132] (4) The solid coal-burning additive and the coal sample are mixed in a mass ratio of 0.3:99.7 to obtain coal with the coal-burning additive added thereto.

[0133] Example 7

[0134] The preparation method of this embodiment is basically the same as that of Example 1, the only difference is that the ratio of the solid coal-burning aid is different. Specifically, the ratio of the solid coal-burning aid of this embodiment is: 50wt% of acrylic acid recombinant decomposition reactor bottom liquid 7, 15wt% of calcium oxide powder, 20wt% of potassium nitrate oxidant and 15wt% of manganese dioxide catalyst.

[0135] Example 8

[0136] The preparation method of this embodiment is basically the same as that of Example 1, the only difference is that the ratio of the solid coal-burning aid is different. Specifically, the ratio of the solid coal-burning aid in this embodiment is: 75wt% of acrylic acid recombinant decomposition reactor bottom liquid 7, 10wt% of calcium oxide powder, 10wt% of potassium permanganate oxidant and 5wt% of aluminum oxide catalyst.

[0137] Example 9

[0138] The preparation method of this embodiment is basically the same as that of embodiment 2, except that the ratio of the coal-burning aid is different, and calcium oxide powder is not added in this embodiment. Specifically, the ratio of the coal-burning aid in this embodiment is: 85wt% of butyl acrylate recombinant decomposition reactor bottom liquid 4, 10wt% of potassium nitrate oxidant and 5wt% of manganese dioxide catalyst. The other steps are basically the same as those of embodiment 2.

[0139] Example 10

[0140] The preparation method of this embodiment is basically the same as that of embodiment 3, except that the components of the depolymerization bottom liquid in this embodiment are different, and the depolymerization bottom liquid used in this embodiment is the depolymerization bottom liquid 3 of a mixture of acrylic acid heavy components and butyl acrylate heavy components. The other steps are basically the same as those of embodiment 1.

[0141] Embodiment 11

[0142] The preparation method of this embodiment is basically the same as that of embodiment 3, except that the components of the depolymerization kettle bottom liquid in this embodiment are different. The depolymerization kettle bottom liquid used in this embodiment is a mixture of acrylic acid recombinant depolymerization kettle bottom liquid 7 and butyl acrylate recombinant depolymerization kettle bottom liquid 4 in a mass ratio of 1:3. The other steps are basically the same as those of embodiment 1.

[0143] Comparative Example 1

[0144] The preparation method of this comparative example is basically the same as that of Example 3, except that the composition and ratio of the coal-burning aid are different. Specifically, the ratio of the coal-burning aid in this comparative example is: 100wt% of acrylic acid recombinant component and butyl acrylate recombinant decomposition polymerization kettle bottom liquid 1, without adding other components. The other steps are basically the same as those of Example 3.

[0145] Comparative Example 2

[0146] The preparation method of this comparative example is basically the same as that of Example 3, except that the composition ratio of the coal-burning aid is different. Specifically, the composition ratio of the coal-burning aid in this comparative example is: 29wt% calcium oxide powder, 59wt% potassium nitrate oxidant and 12wt% manganese dioxide catalyst. The other steps are basically the same as those of Example 3.

[0147] Comparative Example 3

[0148] The coal in this comparative example is a blank coal sample to which no coal-burning additives are added.

[0149] The formulations of the coal burning additives prepared in the above examples and comparative examples are shown in Tables 2 and 3.

[0150] Table 2

[0151]

[0152] Table 3

[0153]

[0154] Performance Testing

[0155] The starting ignition point and burnout point of the coal prepared in the above embodiments and comparative examples and the blank coal sample were measured by a thermogravimetric analyzer, with the selection range from room temperature to 950°C and the heating rate of 10°C / min, to analyze the combustion characteristics of the samples.

[0156] Calorific value test: The calorific value of the coal combustion aid prepared in each embodiment and comparative example was tested according to the method specified in GB / T 384-1981 Calorific value determination method for petroleum products.

[0157] The test data of the initial ignition point and the burnout point of the coal in each embodiment and comparative example are shown in Table 4.

[0158] Table 4

[0159]

[0160] In combination with Table 4, by comparing Examples 1 to 9 with Comparative Example 3, it can be seen that whether the solid coal-burning additive prepared by mixing the depolymerization kettle bottom liquid of a single acrylic acid heavy component or a butyl acrylate heavy component with an oxidant and a catalyst and adding it to the coal sample, the combustion characteristics of the coal-burning additive are greatly improved. Among them, the coal-burning additive prepared in Example 3 has an initial ignition point of 479.81°C and a burnout point of 713.89°C, and has a high combustion efficiency.

[0161] Compared with Example 9, the addition of calcium oxide in Example 2 will slightly reduce the calorific value of the coal-fired auxiliary agent itself, but can improve the strength of the solid coal-fired auxiliary agent, and its strong acidity can also be neutralized to reduce corrosion and damage to equipment.

[0162] The coal-burning additive prepared in Comparative Example 1 contains only the depolymerization kettle bottom liquid of the mixture of acrylic acid heavy components and butyl acrylate heavy components. The initial ignition point of the coal prepared therefrom is 483.01°C and the burnout point is 722.46°C, both of which are higher than those in Example 3. This indicates that the combustion efficiency of the coal prepared in Comparative Example 1 is lower than that in Example 3.

[0163] The coal additive prepared in Comparative Example 2 contains only alkaline inorganic fillers, oxidants and catalysts, and the initial ignition point of the coal prepared therefrom is 481.34°C and the burnout point is 719.59°C, both of which are higher than those in Example 3. This indicates that the combustion efficiency of the coal prepared in Comparative Example 1 is lower than that in Example 3.

[0164] Comprehensive analysis shows that the bottom liquid of acrylic acid recombinant depolymerization kettle and the bottom liquid of acrylic acid recombinant depolymerization kettle have a certain promoting effect on coal combustion. When mixed with other oxidants and catalyst substances in a suitable proportion to form solid coal-burning additives, the combustion-supporting properties of coal can be better improved. The addition of calcium oxide powder can greatly reduce the corrosiveness and viscosity of the material and improve the strength of the solid coal-burning additive.

[0165] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0166] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A coal burning aid, characterized in that: The components include depolymerization kettle bottom liquid, catalyst and oxidant; the depolymerization kettle bottom liquid includes at least one of acrylic acid heavy components and butyl acrylate heavy components.

2. The coal burning aid according to claim 1, characterized in that: Calculated by mass percentage, the depolymerization kettle bottom liquid includes 0% to 98% of acrylic acid polymer, 1% to 14% of maleic anhydride, 0% to 99% of butyl acrylate polymer and 0% to 5% of butoxybutyl propionate; the polymer of acrylic acid and the polymer of butyl acrylate are not 0 at the same time.

3. The coal burning aid according to claim 1, characterized in that: The coal-burning additive meets one of the following conditions: (1) Calculated by mass percentage, the depolymerization kettle bottom liquid comprises 85% to 98% of acrylic acid polymer and 1% to 10% of maleic anhydride; (2) Calculated by weight percentage, the depolymerization kettle bottom liquid comprises 90% to 99% of butyl acrylate polymer, 0% to 5% of butyl butoxypropionate and 0% to 4% of maleic anhydride; (3) Calculated by mass percentage, the depolymerization kettle bottom liquid includes 25% to 72% of acrylic acid polymer, 1% to 2% of maleic anhydride, 24% to 75% of butyl acrylate polymer and 0% to 5% of butyl butoxypropionate.

4. The coal burning aid according to any one of claims 1 to 3, characterized in that: In parts by mass, the coal-burning additive includes 50 to 85 parts of the depolymerization kettle bottom liquid, 1 to 30 parts of an oxidant and 1 to 20 parts of a catalyst.

5. The coal burning aid according to claim 4, characterized in that: The coal combustion aid further comprises 5 to 10 parts of alkaline inorganic filler in parts by mass.

6. The coal burning aid according to claim 5, characterized in that: In parts by mass, the coal-burning additive comprises 75 to 85 parts of the depolymerization kettle bottom liquid, 1 to 10 parts of an oxidant, 1 to 5 parts of a catalyst and 5 to 10 parts of an alkaline inorganic filler.

7. The coal burning aid according to any one of claims 1 to 3, 5 to 6, characterized in that: The coal-fired additive meets at least one of the following conditions: (1) The oxidant is a metal salt; (2) The catalyst is a metal oxide; (3) The alkaline inorganic filler is at least one selected from calcium oxide, calcium hydroxide, sodium hydroxide and potassium hydroxide.

8. The coal burning aid according to claim 7, characterized in that: The coal combustion aid meets at least one of the following conditions: (1) The oxidant is at least one selected from potassium permanganate, sodium nitrate, potassium nitrate and potassium chlorate; (2) The catalyst is at least one selected from the group consisting of aluminum oxide, manganese dioxide, magnesium oxide and iron oxide.

9. A method for preparing a coal burning aid, characterized in that: The steps include: The depolymerization kettle bottom liquid, the catalyst and the oxidant are mixed; the depolymerization kettle bottom liquid comprises at least one of acrylic acid heavy components and butyl acrylate heavy components.

10. The method for preparing the coal burning aid according to claim 9, characterized in that: The preparation method of the depolymerization kettle bottom liquid comprises: At least one of the acrylic acid heavy component and the butyl acrylate heavy component is subjected to a depolymerization reaction under the action of an acidic catalyst to obtain a bottom liquid; the depolymerization reaction pressure is -0.09MPa~0.05MPa, the temperature is 100℃~350℃, and the time is 5h~15h.

11. The method for preparing the coal combustion aid according to claim 10, characterized in that: The acidic catalyst is selected from at least one of methanesulfonic acid, p-toluenesulfonic acid and sulfuric acid.

12. The preparation method according to claim 11, characterized in that: The following steps are also included: After the depolymerization kettle bottom liquid, the catalyst and the oxidant are mixed, the obtained mixture is kept warm for 5 minutes to 10 minutes at a vacuum pressure of 20 KPa to 50 KPa and a temperature of 180° C. to 200° C.

13. Use of the coal-burning additive according to any one of claims 1 to 8 in the preparation of coal-burning.

14. A coal-fired fuel, characterized in that: The fuel coal comprises a coal base material and the coal-fired auxiliary agent as described in any one of claims 1 to 8.

15. The coal combustion as claimed in claim 14, characterized in that: The mass percentage of the coal-fired auxiliary agent in the coal-fired fuel is 0.2% to 0.5%.

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