阅读说明：本技术 一种固态脱硫脱硝剂 (Solid desulfurization and denitrification agent ) 是由 郭若军 袁国洪 于 2020-10-29 设计创作，主要内容包括：本发明公开了一种固态脱硫脱硝剂,属于催化剂制备技术领域。包括原料：氧化铁,二氧化锰,尿素,醋酸钙镁,氧化钛,高岭土和碳酸钙。本发明通过进一步优化固态脱硝剂的配方组分,起到在脱硫同时进行脱硝的技术效果,具体通过对碳酸钙进行改性,增强其吸附脱除能力,脱硫脱硝效果好,脱硝率达80％以上,脱硫效果达97％以上。(The invention discloses a solid desulfurization and denitrification agent, and belongs to the technical field of catalyst preparation. Comprises the following raw materials: iron oxide, manganese dioxide, urea, calcium magnesium acetate, titanium oxide, kaolin and calcium carbonate. According to the invention, by further optimizing the formula components of the solid denitration agent, the technical effect of denitration during desulfurization is achieved, and specifically, by modifying calcium carbonate, the adsorption and removal capacity of the calcium carbonate is enhanced, the desulfurization and denitration effect is good, the denitration rate is up to more than 80%, and the desulfurization effect is up to more than 97%.)

1. The solid desulfurization and denitrification agent is characterized by comprising the following raw materials in parts by weight: 1-15 parts of ferric oxide, 2-6 parts of manganese dioxide, 40-60 parts of urea, 10-25 parts of calcium magnesium acetate, 1-10 parts of titanium oxide, 5-10 parts of kaolin and 120-150 parts of calcium carbonate.

2. The solid desulfurization and denitrification agent according to claim 1, wherein the solid desulfurization and denitrification agent comprises 10 parts of iron oxide, 4 parts of manganese dioxide, 50 parts of urea, 15 parts of calcium magnesium acetate, 5 parts of titanium oxide, 10 parts of kaolin and 130 parts of calcium carbonate.

3. The solid desulfurization and denitrification agent according to claim 1 or 2, wherein the calcium carbonate is composed of calcium carbonate and modified calcium carbonate in a mass ratio of 1: (2-3).

4. The solid desulfurization and denitrification agent according to claim 3, wherein the modified calcium carbonate is prepared by mixing heavy calcium carbonate, polyoxyethylene fatty alcohol ether and water at a mass ratio of 100: (3-4): (4-5) mixing and reacting for 2-3 h to obtain the catalyst.

5. The preparation method of the solid desulfurization and denitrification agent is characterized by comprising the following steps:

(1) mixing and crushing iron oxide, manganese dioxide, titanium oxide, kaolin and calcium carbonate to obtain a reducing base material;

(2) and (2) uniformly mixing the reducing base material prepared in the step (1) with urea and calcium magnesium acetate to obtain the solid desulfurization and denitrification agent.

6. The preparation method of the solid desulfurization and denitrification agent as claimed in claim 5, wherein the pulverized particle size in the step (1) is 30-70 nm.

Technical Field

The invention relates to the technical field of catalyst preparation, in particular to a solid desulfurization and denitrification agent.

Background

NO_XAnd acidic SO₂The emission of (a) causes serious pollution to the atmosphere,however, due to coal combustion, waste incineration, economic development and the like, pollutants discharged in the production process of working condition enterprises cannot be obviously reduced in a short time, and the problem of environmental pollution cannot be avoided, wherein nitric oxide and nitrogen dioxide are important reasons for forming photochemical smog and acid rain, nitrogen oxide is harmful to the human respiratory system, the lung structure can be changed due to the fact that the nitrogen oxide is inhaled for a long time, and acidic SO₂Mainly causing irritation symptoms of respiratory tract and eye mucosa to different degrees.

In order to reduce pollution, the prior art has a dry desulfurization absorption technology, which has the advantages of no discharge of sewage and waste acid, light equipment corrosion degree, less secondary pollution and the like, and the denitration technology also comprises a dry denitration technology.

However, the dry denitration/desulfurization technology has high requirements on the temperature range of flue gas, and in addition, the main problems are that the reaction efficiency is low, the denitration efficiency of the conventional denitration agent is lower than 70%, the desulfurization effect is lower than 80%, and the requirements on equipment are high.

Therefore, how to improve the removal efficiency by optimizing the raw materials and the process for desulfurization and denitrification has important value for dry-process denitrification, and is a problem to be solved by technical personnel in the field.

Disclosure of Invention

In view of the above, the present invention provides a solid desulfurization and denitrification agent.

In order to achieve the purpose, the invention adopts the following technical scheme:

a solid desulfurization and denitrification agent comprises the following raw materials in parts by weight: 1-15 parts of ferric oxide, 2-6 parts of manganese dioxide, 40-60 parts of urea, 10-25 parts of calcium magnesium acetate, 1-10 parts of titanium oxide, 5-10 parts of kaolin and 120-150 parts of calcium carbonate.

Has the advantages that: in order to enhance the desulfurization effect, the raw materials of the formula are optimized, and the calcium carbonate is added to play a role in enhancing the desulfurization and denitrification effects. Meanwhile, the ferric oxide is used as a raw material, so that the reaction temperature can be promoted to be reduced, and better catalytic activity is shown. The urea is used as a raw material and can react with NOx to generate nitrogen and water, so that the NOx can be removed better; the titanium oxide has better capability of removing NOx in the coal ash gas, and can promote the removal of NOx as part of the formula; the kaolin has excellent specific surface area and can promote the adsorption of NOx; the calcium magnesium acetate has excellent hollow and porous property and large specific surface area, and is beneficial to removing NOx. Meanwhile, calcium magnesium acetate is decomposed at high temperature to generate a plurality of strong reducing gases, and the strong reducing gases and NOx are subjected to reduction reaction, so that NOx can be removed.

Preferably: 10 parts of ferric oxide, 4 parts of manganese dioxide, 50 parts of urea, 15 parts of calcium magnesium acetate, 5 parts of titanium oxide, 10 parts of kaolin and 130 parts of calcium carbonate.

Preferably: the calcium carbonate is composed of calcium carbonate and modified calcium carbonate, and the mass ratio of the calcium carbonate to the modified calcium carbonate is 1: (2-3).

The calcium carbonate is modified and mixed with the common calcium carbonate, so that the effect of removing sulfur from the calcium carbonate can be improved, and the cost is considered.

Preferably: the preparation method of the modified calcium carbonate comprises the following steps of mixing heavy calcium carbonate, polyoxyethylene fatty alcohol ether and water at a mass ratio of 100: (3-4): (4-5) mixing and reacting for 2-3 h to obtain the catalyst.

Has the advantages that: provides a processing technology of modified calcium carbonate which is easy to be processed by industrial operation, and simultaneously applies the modified calcium carbonate to a desulfurizing agent.

The invention provides a preparation method of a solid desulfurization and denitrification agent, which is characterized by comprising the following steps:

(1) mixing and crushing iron oxide, manganese dioxide, titanium oxide, kaolin and calcium carbonate to obtain a reducing base material;

(2) and (2) uniformly mixing the reducing base material prepared in the step (1) with urea and calcium magnesium acetate to obtain the solid desulfurization and denitrification agent.

Preferably: the crushing particle size in the step (1) is 30-70 nm.

According to the technical scheme, compared with the prior art, the solid desulfurization and denitrification agent disclosed by the invention has the technical effects that various strong reducing gases are generated in the pyrolysis process by optimizing the component proportion, the dry-method denitrification reaction efficiency is improved, the temperature range requirement of dry-method denitrification and desulfurization is properly reduced, complex removal equipment is not needed, the denitrification rate reaches over 80 percent, and the desulfurization effect reaches over 97 percent, so that the temperature range of waste gas is 750-1200 ℃.

Detailed Description

The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The embodiment of the invention discloses a solid desulfurization and denitrification agent. The single chemicals required by the embodiment are purchased from commercial channels, and the brand of the chemicals is not limited; the (experimental) equipment and instruments involved in the embodiment are not limited in brand, and are conventional equipment, for example, a set of industrial denitration/sulfur equipment provided by Yixing Lu flood environmental protection science and technology limited (mainly comprising a storage unit, a quantitative feeding unit, a pneumatic conveying unit, a Venturi acceleration chamber and a spray gun, wherein the storage unit comprises a blanking system and a storage bin, the quantitative feeding unit comprises a hopper, a weighing module, a feeding screw and a valve, the pneumatic conveying unit comprises a Roots blower, a pneumatic conveying pipeline, a Venturi acceleration chamber and the spray gun, and the electronic control unit comprises an electrical system and a control system); sampling and analyzing the flue gas by adopting tail flue gas analysis equipment (FT-IR CX-4000 Fourier transform infrared spectrum analyzer of GASMET company in Finland); analyzing and identifying the raw materials and finished products of the desulfurization and denitrification agent by using a specific surface area and aperture analyzer produced by American Mac company; the smoke temperature measuring element adopts a K-type thermocouple (Anhui Tiankang instrument limited company, measuring range of 0-1300 ℃); the methods not mentioned are all conventional laboratory experimental methods, and are not described in detail herein.

Example 1

A solid desulfurization and denitrification agent comprises the following raw materials: 1g of ferric oxide, 6g of manganese dioxide, 40g of urea, 25g of calcium magnesium acetate, 10g of titanium oxide, 5g of kaolin and 120g of calcium carbonate.

Example 2

A solid desulfurization and denitrification agent comprises the following raw materials: 10g of ferric oxide, 4g of manganese dioxide, 50g of urea, 15g of calcium magnesium acetate, 5g of titanium oxide, 10g of kaolin and 130g of calcium carbonate.

Example 3

A solid desulfurization and denitrification agent comprises the following raw materials: 15g of ferric oxide, 2g of manganese dioxide, 60g of urea, 10g of calcium magnesium acetate, 1g of titanium oxide, 10g of kaolin and 150g of calcium carbonate.

Example 4

The preparation method of the solid desulfurization and denitrification agent of the embodiment 1-3 comprises the following steps:

(1) mixing and crushing iron oxide, manganese dioxide, titanium oxide, kaolin and calcium carbonate to obtain a reducing base material;

(2) and (2) uniformly mixing the reducing base material prepared in the step (1) with urea and calcium magnesium acetate to obtain the solid desulfurization and denitrification agent.

In order to further optimize the technical scheme: the crushing particle size in the step (1) is 30-70 nm.

The preparation method of the modified calcium carbonate comprises the following steps:

at the temperature of 70-80 ℃, mixing heavy calcium carbonate, polyoxyethylene fatty alcohol ether and water according to the mass ratio of 100: (3-4): (4-5) mixing and reacting for 2-3 h to obtain the catalyst.

Comparative example 1

The difference from the example 2 is only that the iron oxide and calcium magnesium acetate components are not included.

Comparative example 2

The only difference from example 2 is that manganese dioxide and titanium oxide were not contained.

Comparative example 3

The difference from example 2 is that the calcium carbonate is unmodified and is only ordinary calcium carbonate.

Comparative test

The denitration agents prepared in the embodiment 2 and the comparative examples 1-3 are implemented in a small coal powder power plant boiler.

The experimental conditions are as follows:

1. boiler parameters see table 1:

TABLE 1

2. Dry denitration/sulfur plant:

the method adopts Yixing salary flood environment-friendly technology limited company complete equipment, which mainly comprises the following steps:

storage unit (including blanking system and stock bin)

Quantitative feeding unit (comprising hopper, weighing module, feeding screw and valve)

Pneumatic conveying unit (Roots blower, pneumatic conveying pipeline, Venturi acceleration chamber, spray gun)

Electric control unit (including electric system and control system)

3. Flue gas analysis equipment:

the tail flue gas analysis equipment adopts FT-IR CX-4000 Fourier transform infrared spectrum analyzer of GANSMET corporation of Finland to sample and analyze the flue gas, and the heating temperature of the sample gas is 180 DEG C

4. A temperature measuring element:

the smoke temperature measuring element adopts a K-type thermocouple (Anhui Tiankang instrument Co., Ltd.), and the measuring range is 0-1300 DEG C

The method comprises the following steps:

the desorption equipment is arranged on a 0-meter layer, the spray gun is arranged on a 21.2-meter layer hearth position, the high-temperature region belongs to, and the spray guns are arranged on two sides of the hearth, so that the desulfurization and denitrification agent is sprayed into the hearth and then is mixed with the flue gas more fully. Manually feeding the materials to a complete equipment bin with high material level.

Keeping a boiler to stably operate, gradually increasing the injection amount of a dry desulfurization and denitrification agent by adjusting the quantitative feeding spiral rotating speed of a dry denitration complete equipment, adjusting the temperature of the flue gas of a hearth, keeping each temperature stage for 3 hours (580 ℃ and 1280 ℃ keep 1.5 hours due to influence on the safe operation of the boiler), adjusting the feeding amount of the dry desulfurization and denitrification agent in each stage to achieve the optimal removal effect of the temperature stage, and calculating the denitration efficiency through an NOx value; SO in the flue gas after 1-removal₂Concentration/raw flue gas SO₂Calculating the desulfurization rate for accurate calculationAnd (3) suspending removal 20 minutes before each temperature stage, and measuring NOx and SO by a flue gas analyzer₂The original concentration.

See table 2 for experimental data:

TABLE 2

	600℃	700℃	750℃	800℃	900℃	1000℃	1100	1200
									Example 1 Denitrification efficiency	69	77	81	85	87	89	88	85
Example 2 Denitrification efficiency	70	79	82	84	88	91	90	86
									Example 3 Denitrification efficiency	67	76	80	84	87	90	87	83
EXAMPLE 1 desulfurization efficiency	97	98	98	97	99	97	98	98
									EXAMPLE 2 desulfurization efficiency	97	96	97	97	98	97	97	98
Example 3 desulfurization efficiency	98	98	97	98	99	97	98	97
									Comparative example 1 denitration efficiency	64	63	69	72	84	87	84	79
Comparative example 2 denitration efficiency	61	66	71	74	85	89	80	72
									Comparative example 3 denitration efficiency	66	74	78	81	84	87	83	80
Comparative example 1 desulfurization efficiency	97	96	97	97	96	97	97	97
									Comparative example 2 desulfurization efficiency	96	97	98	97	96	96	97	97
Comparative example 3 desulfurization efficiency	74	76	75	76	74	76	75	74

The experimental result shows that the desulfurization and denitrification agent prepared in the embodiment has the following denitration effects:

the denitration effect reaches more than 80% at 750 ℃, the denitration effect is optimal at 750-1200 ℃, and compared with a pure denitration agent, the denitration agent has a slightly higher temperature requirement on waste gas, but is obviously superior to a comparative example, wherein the denitration effect of the embodiment 2 is optimal.

In terms of desulfurization effect:

experiments show that the desulfurization effect is relatively low, the influence of the adjustment of other components except the remover calcium carbonate on the whole is relatively low, but the desulfurization effect of the modified calcium carbonate is obviously better than that of the common calcium carbonate.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.