Coal-saving combustion-supporting catalyst for coal-fired boiler and preparation method of coal-saving combustion-supporting catalyst

Abstract

The coal-saving combustion-supporting catalyst is prepared from the following raw materials in parts by mass: 100 parts of water, 8 to 15 parts of organic magnesium salt, 0.1 to 1 part of soluble aluminum salt, 0.1 to 1 part of cerium-containing compound, 0.5 to 3 parts of soluble bivalent manganese salt, 1 to 5 parts of soluble bivalent copper salt, 5 to 10 parts of soluble salt of alkali metal and 0.1 to 1 part of ethylene diamine tetraacetic acid (EDTA) or corresponding metal salt thereof. The invention also provides a preparation method of the coal-saving combustion-supporting catalyst for the coal-fired boiler. The coal-saving combustion-supporting catalyst for the coal-fired boiler has the remarkable advantages of being high in catalytic activity, good in stability, low in cost, environmentally friendly and the like, the combustion efficiency of the coal-fired boiler can be further improved, coal consumption is reduced, pollutant emission is reduced, and the current and future requirements for an efficient and clean coal-fired technology are met.

Description

Technical Field

[0001] The present invention belongs to the field of coal conversion, and in particular relates to a coal-saving combustion-supporting catalyst for a coal-fired boiler and a preparation method thereof. Background Art

[0002] In the energy utilization sector, coal-fired boilers are traditional and widely used thermal energy conversion equipment. Their operating efficiency and environmental performance are directly related to the effective use of energy and the effectiveness of environmental protection. With the continued growth of global energy demand and the increasing awareness of environmental protection, improving the combustion efficiency of coal-fired boilers and reducing pollutant emissions have become urgent technical challenges.

[0003] Currently, a variety of technical approaches exist on the market to improve the combustion efficiency of coal-fired boilers, including but not limited to optimizing boiler design, improving burner structure, and adopting advanced combustion control technologies. However, these approaches are often limited by factors such as high equipment modification costs and the difficulty of technical implementation, making them difficult to rapidly and widely promote.

[0004] In recent years, coal-saving combustion-supporting catalysts, an emerging technology, have gradually attracted industry attention due to their ability to significantly reduce coal consumption, improve combustion efficiency, and reduce pollutant emissions in coal-fired boilers. A variety of coal-saving combustion-supporting catalysts have been developed and applied to coal-fired boilers. These catalysts primarily improve the combustion characteristics of pulverized coal by catalyzing oxidation and promoting combustion reactions, thereby enhancing combustion efficiency.

[0005] However, while existing coal-saving and combustion-supporting catalysts have achieved some success, several issues and shortcomings remain. For example, some catalysts lack sufficient catalytic activity, resulting in limited coal-saving benefits; some catalysts are easily deactivated at high temperatures and exhibit poor stability; and some catalysts have complex and costly preparation processes, making them unsuitable for large-scale industrial production. Furthermore, some catalysts may generate secondary pollution during combustion, adversely impacting the environment.

[0006] In view of the problems and shortcomings of the above-mentioned prior art, the present invention aims to provide a method for preparing a coal-saving combustion-supporting catalyst for coal-fired boilers. The method aims to prepare a coal-saving combustion-supporting catalyst with high catalytic activity, good stability, low cost and environmental protection by optimizing the formula and preparation process of the catalyst, so as to further improve the combustion efficiency of coal-fired boilers, reduce coal consumption, and reduce pollutant emissions, so as to meet the current and future needs for efficient and clean coal-fired technology. Summary of the Invention

[0007] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises the following raw materials, in parts by mass: 100 parts of water, 8-15 parts of an organic magnesium salt, 0.1-1 part of a soluble aluminum salt, 0.1-1 part of a compound containing a cerium element, 0.5-3 parts of a soluble divalent manganese salt, 1-5 parts of a soluble divalent copper salt, 5-10 parts of a soluble salt of an alkali metal, and 0.1-1 part of ethylenediaminetetraacetic acid (EDTA) or a corresponding metal salt thereof.

[0008] Preferably, the organic magnesium salt includes one or more of magnesium propionate and magnesium acetate.

[0009] Preferably, the soluble aluminum salt includes one or more of aluminum sulfate, aluminum chloride, and potassium aluminum sulfate.

[0010] Preferably, the compound containing cerium element includes one or more of cerium sulfate, cerium acetate, and cerium sulfate.

[0011] Preferably, the soluble divalent manganese salt includes one or more of manganese sulfate and manganese chloride.

[0012] Preferably, the soluble divalent copper salt includes one or more of copper chloride and copper sulfate.

[0013] Preferably, the soluble salt of the alkali metal includes one or more of sodium acetate, sodium chloride, and sodium propionate.

[0014] Preferably, the ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt includes one or more of ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, and potassium ethylenediaminetetraacetate.

[0015] Preferably, the raw materials of the coal-saving combustion-supporting catalyst for coal-fired boilers include, by mass, 100 parts of water, 10-13 parts of organic magnesium salt, 0.1-0.5 parts of soluble aluminum salt, 0.5-0.8 parts of compounds containing rare earth elements, 1-2 parts of soluble divalent manganese salt, 3-4 parts of soluble divalent copper salt, 7-8 parts of soluble salt of alkali metal, and 0.1-0.5 parts of ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt.

[0016] More preferably, the raw materials of the coal-saving combustion-supporting catalyst for coal-fired boilers include, by mass, 100 parts of water, 11-12 parts of organic magnesium salt, 0.2-0.3 parts of soluble aluminum salt, 0.6-0.7 parts of a compound containing cerium, 1-2 parts of a soluble divalent manganese salt, 3-3.5 parts of a soluble divalent copper salt, 7.5-8 parts of a soluble salt of an alkali metal, and 0.1-0.3 parts of ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt.

[0017] The present invention also provides a method for preparing a coal-saving combustion-supporting catalyst for a coal-fired boiler, the main steps of which include:

[0018] S1. Add 100 parts by mass of water to the reactor, start stirring and heat to a suitable temperature;

[0019] S2. Add organic magnesium salt, soluble aluminum salt, compound containing cerium, soluble divalent manganese salt, soluble divalent copper salt, soluble salt of alkali metal, ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt in order. Only add the next raw material after each raw material is fully dissolved.

[0020] S3, keeping the mixed solution at a suitable temperature for a period of time;

[0021] S4. Further homogenizing the mixture through ultrasonic treatment to obtain the coal-saving combustion-supporting catalyst for a coal-fired boiler.

[0022] Preferably, in step S1, the temperature is 30-50° C., and the stirring speed is 30-120 rpm.

[0023] Preferably, in step S3, the temperature is 30-50° C., and the stirring speed is 30-120 rpm.

[0024] Preferably, in step S4, the ultrasonic treatment is performed at a frequency of 10-60 kHz and for a treatment time of 10-60 minutes.

[0025] In the present invention, ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt is introduced as stabilizer in the middle of catalyst, as a kind of efficient chelating agent, its unique molecular structure enables it to form stable and difficult to dissociate chelate particles with multiple metal ions in coal-burning process, especially active higher manganese ion, aluminum ion and magnesium ion. This process not only greatly enhances the stability of metal ions, effectively prevents their unfavorable aggregation or precipitation in catalytic reaction, but also significantly improves the antioxidant capacity of whole catalyst system. Through chelation, EDTA can protect these metal ions from the corrosion of oxidizing environment, extends the active life of catalyst, ensures that coal-burning process is efficient and stable. In addition, the addition of EDTA also promotes the uniform distribution of metal ions in catalyst, optimizes the kinetic conditions of catalytic reaction, thereby further improving the conversion efficiency and energy utilization rate of coal-burning.

[0026] In the present invention, copper, a transition metal, is used in the catalyst, exhibiting excellent redox and electron transfer properties. During coal combustion, copper effectively promotes the cracking and oxidation of organic matter in the coal, increasing the pyrolysis rate and combustion efficiency. Furthermore, copper reacts with the sulfur in the coal, inhibiting the production of harmful gases such as sulfur dioxide and reducing environmental pollution.

[0027] In this invention, the manganese element used in the catalyst readily forms multiple valence states during high-temperature reactions. This multivalent nature allows the manganese ion to flexibly transform during the catalytic process, participating in a variety of redox reactions. In coal-fired catalysts, manganese not only enhances the catalyst's catalytic activity but also broadens its operating temperature range, maintaining high catalytic efficiency under various combustion conditions.

[0028] In the present invention, aluminum is incorporated into the catalyst primarily to improve its structural stability and dispersibility. Potassium aluminum sulfate, as a source of aluminum, not only provides aluminum ions but also forms a stable network within the catalyst, preventing sintering or agglomeration at high temperatures. Furthermore, aluminum creates a synergistic effect with elements such as copper and manganese, further enhancing the catalyst's catalytic performance.

[0029] In this invention, the coal-fired catalyst utilizes organic salts as its primary component. Upon combustion, the anions in these salts produce only carbon dioxide and water, without emitting polluting gases such as nitrogen oxides. This significantly reduces environmental pollution and lowers emissions of these gases. Furthermore, compared to catalysts containing nitrates, this product poses no flammability or explosion risk, making it absolutely safe to transport and use.

[0030] In the present invention, the catalyst is homogenized, and through the effects of ultrasound and the like, the internal components of the catalyst are uniformly distributed at the nanoscale, which significantly improves the catalytic activity and stability, and brings a more efficient and stable catalytic effect to the coal combustion process.

[0031] The beneficial effects of the present invention include:

[0032] 1. Improved catalytic activity: While existing coal-saving catalysts for coal-fired boilers can improve combustion efficiency to a certain extent, their catalytic activity still needs to be improved. This invention aims to produce a coal-saving, combustion-supporting catalyst with higher catalytic activity by optimizing the catalyst formulation and preparation process, thereby further improving the combustion efficiency of coal-fired boilers and significantly reducing coal consumption.

[0033] 2. Cost reduction: Some high-efficiency catalysts require complex preparation processes and high raw material costs, making them difficult to commercialize and apply on a large scale. This invention aims to reduce the production cost of coal-saving combustion-supporting catalysts and improve their market competitiveness by simplifying the preparation process and selecting lower-cost raw materials.

[0034] 3. Reduce secondary pollution: Some catalysts may generate new pollutants during combustion, causing adverse environmental impacts. This invention focuses on the environmental performance of the catalyst to ensure that it improves combustion efficiency while not introducing new pollution sources, thereby reducing the generation of secondary pollution. DETAILED DESCRIPTION

[0035] The present invention is further described in conjunction with the following examples, but the scope of protection of the present invention is not limited thereto. Explanation for the examples: The raw materials used in the following examples are not limited to the raw materials required for this application and are only used for writing the examples.

[0036] Example 1

[0037] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises raw materials of water, magnesium acetate, potassium aluminum sulfate, ceric sulfate, manganese chloride, copper sulfate, sodium propionate and ethylenediaminetetraacetic acid in proportions by mass of 100, 11.5, 0.25, 0.625, 1.5, 3.375, 7.75 and 0.3 respectively.

[0038] Example 2

[0039] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises raw materials of water, magnesium acetate, potassium aluminum sulfate, ceric sulfate, manganese chloride, copper sulfate, sodium propionate and ethylenediaminetetraacetic acid in proportions by mass of 100, 8, 0.1, 0.1, 0.5, 1, 5 and 0.1 respectively.

[0040] Example 3

[0041] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises raw materials of water, magnesium acetate, potassium aluminum sulfate, ceric sulfate, manganese chloride, copper sulfate, sodium propionate and ethylenediaminetetraacetic acid in proportions by mass of 100, 10, 0.2, 0.3, 1, 2, 6.5 and 0.5 respectively.

[0042] Example 4

[0043] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises raw materials of water, magnesium acetate, potassium aluminum sulfate, ceric sulfate, manganese chloride, copper sulfate, sodium propionate and ethylenediaminetetraacetic acid in proportions by mass of 100, 12, 0.3, 0.8, 2.5, 4.5, 9 and 0.8 respectively.

[0044] Example 5

[0045] A coal-saving combustion-supporting catalyst for a coal-fired boiler comprises raw materials of water, magnesium acetate, potassium aluminum sulfate, ceric sulfate, manganese chloride, copper sulfate, sodium propionate and ethylenediaminetetraacetic acid in proportions by mass of 100, 15, 1, 1, 3, 5, 10 and 1 respectively.

[0046] Example 6

[0047] The rest is the same as Example 1, except that sodium propionate is replaced by sodium chloride.

[0048] Example 7

[0049] The rest is the same as Example 1, except that ethylenediaminetetraacetic acid is replaced by sodium ethylenediaminetetraacetate.

[0050] Example 8

[0051] The rest is the same as Example 1, except that ethylenediaminetetraacetic acid is replaced by potassium ethylenediaminetetraacetate.

[0052] Comparative Example 1

[0053] The rest are the same as in Example 1, except that magnesium acetate is replaced by magnesium nitrate.

[0054] Comparative Example 2

[0055] The rest is the same as Example 1, except that potassium aluminum sulfate is replaced by aluminum nitrate.

[0056] Comparative Example 3

[0057] The rest is the same as Example 1, except that potassium aluminum sulfate is replaced by potassium nitrate.

[0058] Comparative Example 4

[0059] The rest is the same as Example 1, except that ceric sulfate is replaced by ceric nitrate.

[0060] Comparative Example 5

[0061] The rest is the same as Example 1, except that manganese chloride is replaced by manganese nitrate.

[0062] Comparative Example 6

[0063] The rest is the same as Example 1, except that copper sulfate is replaced by copper nitrate.

[0064] Comparative Example 7

[0065] The rest is the same as Example 1, except that sodium propionate is replaced by sodium nitrate.

[0066] Comparative Example 8

[0067] The rest are the same as in Example 1, except that magnesium acetate is replaced by magnesium sulfate.

[0068] Comparative Example 9

[0069] The rest are the same as in Example 1, except that magnesium acetate is replaced by magnesium chloride.

[0070] Comparative Example 10

[0071] The rest is the same as Example 1, except that sodium propionate is replaced by sodium sulfate.

[0072] Comparative Example 11

[0073] The rest is the same as Example 1, except that ceric sulfate is replaced by praseodymium sulfate.

[0074] Comparative Example 12

[0075] The rest are the same as in Example 1, except that magnesium acetate is not added.

[0076] Comparative Example 13

[0077] The rest is the same as in Example 1, except that potassium aluminum sulfate is not added.

[0078] Comparative Example 14

[0079] The rest is the same as Example 1, except that ceric sulfate is not added.

[0080] Comparative Example 15

[0081] The rest is the same as Example 1, except that manganese chloride is not added.

[0082] Comparative Example 16

[0083] The rest is the same as in Example 1, except that copper sulfate is not added.

[0084] Comparative Example 17

[0085] The rest is the same as Example 1, except that sodium propionate is not added.

[0086] Comparative Example 18

[0087] The rest is the same as Example 1, except that EDTA is not added.

[0088] Implementation effect:

[0089] The experiments all used anthracite produced in Yulin, Shaanxi. After being ground into coal powder by a boiler pulverizer, the catalyst was evenly sprayed onto the coal powder using a spray device at an addition amount of 0.1%.

[0090]

[0091]

[0092] Testing revealed that Example 1 exhibited stable chemical properties, exhibiting no precipitation after prolonged periods of rest. However, Comparative Examples 1-7, which used the corresponding nitrates, exhibited highly reactive nitrate raw materials, posing a significant risk of operational errors during transportation or use. For safety reasons, these nitrates were not suitable for large-scale industrial production. Furthermore, compared to Comparative Examples 8-18, Examples 1-8 achieved significantly higher coal savings.

[0093] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention. Such changes and modifications are intended to fall within the scope of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A coal-saving combustion-supporting catalyst for a coal-fired boiler, characterized in that: The raw materials include, by mass, 100 parts of water, 8-15 parts of organic magnesium salt, 0.1-1 part of soluble aluminum salt, 0.1-1 part of compound containing cerium element, 0.5-3 parts of soluble divalent manganese salt, 1-5 parts of soluble divalent copper salt, 5-10 parts of soluble salt of alkali metal, and 0.1-1 part of ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt.

2. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: The organic magnesium salt includes one or more of magnesium propionate and magnesium acetate.

3. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: The soluble aluminum salt includes one or more of aluminum sulfate, aluminum chloride, and potassium aluminum sulfate.

4. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: The compound containing cerium element includes one or more of cerium sulfate, cerium acetate and cerium sulfate.

5. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: Soluble divalent manganese salts include one or more of manganese sulfate and manganese chloride; The soluble divalent copper salt includes one or more of copper chloride and copper sulfate; The soluble salt of the alkali metal includes one or more of sodium acetate, sodium chloride and sodium propionate.

6. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: The ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt includes one or more of ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, and potassium ethylenediaminetetraacetate.

7. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1, characterized in that: The coal-saving combustion-supporting catalyst for a coal-fired boiler comprises the following raw materials by mass: 100 parts of water, 10-13 parts of an organic magnesium salt, 0.1-0.5 parts of a soluble aluminum salt, 0.5-0.8 parts of a compound containing a rare earth element, 1-2 parts of a soluble divalent manganese salt, 3-4 parts of a soluble divalent copper salt, 7-8 parts of a soluble salt of an alkali metal, and 0.1-0.5 parts of ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt.

8. A coal-saving combustion-supporting catalyst for a coal-fired boiler as claimed in claim 1 or 7, characterized in that: The coal-saving combustion-supporting catalyst for a coal-fired boiler comprises the following raw materials by mass: 100 parts of water, 11-12 parts of an organic magnesium salt, 0.2-0.3 parts of a soluble aluminum salt, 0.6-0.7 parts of a compound containing a cerium element, 1-2 parts of a soluble divalent manganese salt, 3-3.5 parts of a soluble divalent copper salt, 7.5-8 parts of a soluble salt of an alkali metal, and 0.1-0.3 parts of ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt.

9. The method for preparing a coal-saving combustion-supporting catalyst for a coal-fired boiler according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Add 100 parts by weight of water into the reactor, start stirring and heat to a suitable temperature; S2. Add organic magnesium salt, soluble aluminum salt, compound containing cerium element, soluble divalent manganese salt, soluble divalent copper salt, soluble salt of alkali metal, ethylenediaminetetraacetic acid (EDTA) or its corresponding metal salt in sequence, and add the next raw material only after each raw material is fully dissolved: S3, keeping the uniformly mixed solution at a suitable temperature for a period of time; S4. Further homogenizing by ultrasonic treatment to obtain the coal-saving combustion-supporting catalyst for the coal-fired boiler.

10. The method for preparing a coal-saving combustion-supporting catalyst for a coal-fired boiler according to claim 9, characterized in that: In step S1, the temperature is 30-50°C and the stirring speed is 30-120 rpm; In step S3, the temperature is 30-50°C and the stirring speed is 30-120 rpm; In step S4, the conditions of the ultrasonic treatment are: frequency 10-60 kHz, and treatment time 10-60 minutes.

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