CN102643705B - Coal combustion-supporting hydrogel as well as preparation method and application thereof - Google Patents
Coal combustion-supporting hydrogel as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a coal combustion-supporting hydrogel as well as a preparation method and application thereof. The coal combustion-supporting hydrogel is prepared through the following steps of: (1) uniformly mixing 30-89% of metal nitrate, 5-60% of potassium chlorate, 1-3% of rare-earth elements, 5-30% of alkali metal hydroxide and 0-20% of sodium silicate, so as to obtain a mixture; (2) dissolving 3% of poly (N-isopropylacrylamide) and 30% of oxydol in water, and uniformly stirring, so as to obtain a solvent; and (3), dissolving the mixture in the solvent, so as to obtain the coal combustion-supporting hydrogel. The coal combustion-supporting hydrogel disclosed by the invention is non-corrosiveness, is stable in property, can be easily adsorbed to the surface of coal powder so as to form a loose porous combustion adjuvant layer, can be directly mixed with coal by virtue of a spraying device, and is convenient in use. By utilizing the coal combustion-supporting hydrogel disclosed by the invention, the desulfurization percent reaches 85%, the standard coal saving rate is 14.6%, the boiler thermal efficiency is improved by 10.6%, the carbon content of slags is reduced by 12.7%, and decoking, smoke abatement and corrosion inhibition reach more than 92%, so that the coal combustion-supporting hydrogel can achieve a combined action of saving coal and reducing the pollutant emission.
Description
Technical field
The present invention relates to a kind of coal combustion-promoting agents, be specifically related to a kind of coal combustion-supporting hydrogel and preparation method thereof and application, this coal combustion-supporting hydrogel also has smoke elimination, dedusting, energy-conservation effect in combustion-supporting, is applicable to Industrial Boiler, power station stove, cellar for storing things stove, steam oven and life-form coal stove.
Background technology
The coal resources of China are quite abundant, and explored reserves position is at the forefront in the world, but they will peter out after 100 years.Quality with regard to coal sees, the quality of coal is uneven, and medium-high sulfur coal and high sulphur coal that sulfur content in coal amount reaches more than 2% account for 1/3 of total reserves.Just because of this factor, coal in the middle of combustion processes, because its inferior quality makes burning abundant not, cause that fire box temperature is on the low side, burning-point is high, be difficult for catching fire, thermal capacitance greatly, do not readily conduct heat etc., add the SO discharging along with fire coal
x, NO
xdeng obnoxious flavour and flue dust, be on the increase, its result is not only energy dissipation, and the problem of environmental pollution is outstanding too.
Current, industrial coal is 70% left and right that China solves demand for energy, and nearly more than 40 ten thousand boilers are in running, because equipment and technology is outmoded, many boiler efficiencies are low, and energy-output ratio is large, exhaust gas emission exceeds standard, and topsoil is serious, becomes national problem urgently to be resolved hurrily.
In order to reduce the energy consumption of coal firing boiler and to reduce the pollution of coal firing boiler to environment, need to transform the structure of coal firing boiler, but do like this, need to drop into huge fund, and after transformation, also need the working cost of great number.In prior art, in order to improve coal-fired efficiency of combustion, adopting ignition dope is the way of relatively economical.
Both at home and abroad about the existing many achievements of research of coal combustion-promoting agents, composition mainly comprises raising agent, oxygenant, catalyzer, sweetening agent, smoke suppressor, water and organic additive etc. at present.In fire coal, add ignition dope, can significantly improve burning of coal characteristic, reduce kindling temperature, accelerate the combustionvelocity of coke, shorten combustion time, improve efficiency of combustion.
Ignition dope is in coal burning process, central metal ion, can participate in carbon necessary oxygen transmittance process in combustion processes such as ferric ion, tetravalence mn ion etc., contributes to transfer transport, can reduce the activation energy of coal burning, the effect of play combustion-supporting, energization, economizing on coal.By adjusting the proportionlity between different metal ion, can regulate and control the combustion-supporting effect under different temperature of combustion, be suitable for different types of boiler.Utilize the electrolytes such as sodium-chlor explosion characteristic at high temperature, also can improve the effect that contacts of coal and oxygen in combustion processes.In addition, there is chemical reaction in the crock on the compositions such as the basic oxide in ignition dope and heating surface and flue gas etc., makes the sulfide in crock and flue gas generate vitriol, with slag, discharges, reduce the discharge of the obnoxious flavoures such as sulfurous gas, nitrogen peroxide, be conducive to environmental protection.Therefore, adopt suitable coal combustion-promoting agents, easy to use, less investment, is relatively applicable to the existing economic condition of China and environmental requirement, has certain broad applicability.
Chinese patent application 200710050000.2,200610046154.X, 200510013262.2,200810028083.X etc. utilize some metal oxide, industrial residue, unslaked lime, mine tailing etc. as additive, utilize its combustion-supporting effect, add in coal, improve the calorific value of coal.Also can utilize the combustible waste of industrial or agricultural, add in raw coal, improve the calorific value of coal.
Patent application 03124816.0 discloses a kind of " coal additive ", unslaked lime, sodium-chlor, ferric oxide, SODIUMNITRATE etc. are pulverized, powder is dropped in coal, although play certain desulfating coal-saving effect, lack the coke cleaning of boiler itself, inhibition texts.Especially in the burning of coal process of inferior quality, limited by effective contact area and chamber structure, effective constituent in ignition dope can not most of contact with coal, contacts on the contrary with not supporting the impurity of burning with slag, and combustion-supporting effect is had a greatly reduced quality; Add that active substance release rate is too fast, for example oxygen G&W has just departed from coal and has been dissipated in air in the position that approaches burner hearth entrance, is unfavorable for playing a role at burner hearth center, loses best combustion-supporting effect.
Described in comprehensive, still there is following problem in most additive for fire coal on the market in the large-scale application of Industrial Boiler at present:
(1) material such as industrial residue, Wingdale effective constituent amount compared with low, need addition large;
(2) solid particulate additive is unfavorable for disperseing, and effectively contact area is too low;
(3) calcium sulfate that sulfur retention products is pure, at high temperature stable not, easily again decompose and emit the pollutents such as sulfurous gas;
(4) plurality of heavy metal in industrial residue and mine tailing and radioactive substance easily produce new pollution;
(5) oxygen and water vapour are shorter in the coal burning center residence time, are unfavorable for the lifting of combustion-supporting effect;
(6) coke cleaning, corrosion mitigating effect are not satisfactory.
Summary of the invention
In order to overcome the shortcoming and deficiency of existing coal combustion-promoting agents, primary and foremost purpose of the present invention is to provide a kind of preparation method of coal combustion-supporting hydrogel.
Another object of the present invention is to provide the coal combustion-supporting being prepared by aforesaid method hydrogel, this coal combustion-supporting hydrogel also has smoke elimination, dedusting, energy-conservation effect in combustion-supporting.
A further object of the present invention is to provide the purposes of above-mentioned coal combustion-supporting hydrogel.
Object of the present invention is achieved through the following technical solutions:
A preparation method for coal combustion-supporting hydrogel, comprises the following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Metal nitrate: 30 ~ 89%
Potcrate: 5 ~ 60%
Rare earth element: 1 ~ 3%
Alkali metal hydroxide: 5 ~ 30%
Water glass: 0 ~ 20%;
(2) get the hydrogen peroxide of 3% poly N-isopropyl acrylamide and 30% soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, obtains coal combustion-supporting hydrogel;
Preferably, the described mixture of step (1) obtains after being mixed by the composition of following mass percent:
Metal nitrate: 67 ~ 80%
Potcrate: 7 ~ 15%
Rare earth element: 1 ~ 3%
Alkali metal hydroxide: 5 ~ 10%
Water glass: 5 ~ 8%;
The described metal nitrate of step (1) is more than one in nitrocalcite, magnesium nitrate, strontium nitrate, saltpetre, SODIUMNITRATE, iron nitrate, manganous nitrate, nickelous nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
The described alkali metal hydroxide of step (1) is potassium hydroxide or sodium hydroxide;
The described rare earth element of step (1) is rare earth oxide or rare earth nitrate;
The number-average molecular weight of the described poly N-isopropyl acrylamide of step (2) is 5000-1000000;
The described hydrogen peroxide of step (2) can adopt technical grade hydrogen peroxide, wherein H
2o
2content be 50%;
Described its solid content of coal combustion-supporting hydrogel of step (3) preferably 30%.
The coal combustion-supporting hydrogel being prepared by aforesaid method can be used for coal combustion-supporting.Coal is before burning, first by coal combustion-supporting hydrogel of the present invention and coal in mass ratio 1: mix (50 ~ 300), then burn.
Mechanism of the present invention is: using technical grade iron nitrate, manganous nitrate, SODIUMNITRATE, nitrocalcite as ignition dope, nitrocalcite, as sulphur-fixing agent precursor, by add sodium hydroxide to regulate gel rheology energy at solution phase, obtains stable additive for fire coal hydrogel.In the middle of also add appropriate rare earth element as combustion supporting catalyst, in order to the lower coal of catalyticcombustion efficiency.
Activeconstituents is prepared into the gel of stable in properties according to suitable ratio, release of active agent progressively in combustion processes, thus improve combustion-supporting effect; Solved ignition dope low problem of active substance release efficiency in the process with coal Surface Contact.
Ironic hydroxide in gel, manganous hydroxide, calcium hydroxide etc. are sintered into vesicular composite oxides in coal burning process, are conducive to promote adsorption effect, reach fixedly slag, reach the object of coke cleaning, inhibition, solid sulphur.
Under this system, the decomposition course of hydrogen peroxide and steam ascension process become slowly, thereby reach in the position that approaches combustion centre, concentrate and discharge, and improve the efficiency of free radical reaction and improve to conduct heat.
The present invention has following advantage and effect with respect to prior art:
1, the present invention adopts the ignition dope of the form of hydrogel to contribute to the slowly-releasing of combustion-supporting composition, thereby the process of advancing in chain furnace along with coal, the combustion-supporting effect of ignition dope can be concentrated and more effectively bring into play in the position at burner hearth center, in addition, can utilize its structure fluffy and carry the more characteristic of positively charged ion, in the position that approaches stove tail, adsorb better the discharges such as coal smoke, reach the effect that reduces flue dust.
2, coal combustion-supporting hydrogel of the present invention adopts sol-gel method preparation, non-corrosiveness, stable in properties, be easy to be adsorbed on coal dust surface, form loose porous ignition dope layer, can with coal, directly mix by spray equipment, easy to use, be applicable to the fire coals such as Industrial Boiler, power station stove, steam oven and kiln.
3, through environmental administration and energy-saving monitoring Spot detection, use coal combustion-supporting hydrogel desulfurization degree of the present invention to reach 85%, feast-brand mark coal rate 14.6%, improve boiler thermal output 10.6%, boiler slag carbon content reduces by 12.7%, coke cleaning, smoke elimination, inhibition reach more than 92%, play the comprehensive action of economizing on coal and reducing pollutant emission.
4, coal combustion-supporting hydrogel of the present invention is used simply, raw material is sufficient, preparation technology is simple, cheap, stable in properties, and environmentally safe, is a kind of desirable coal combustion-promoting agents.
5, when using coal combustion-supporting hydrogel of the present invention, the water content of coal is remained on to 10% left and right, moisture content can be bonded together coal dust, by air-flow, is not blown afloat, so flying dust number and dust in flue gas greatly reduce, the flying dust in fly-ash separator reduces 9.2%.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A coal combustion-supporting hydrogel, is prepared by following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Nitrocalcite: 32%
SODIUMNITRATE: 20%
Manganous nitrate: 15%
Potcrate: 15%
Lanthanum nitrate: 3%
Sodium hydroxide: 10%
Water glass: 5%;
(2) get 3% poly N-isopropyl acrylamide and 30% hydrogen peroxide is soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, is made into solid content and is 30% coal combustion-supporting hydrogel.
The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with low grade coal at 1: 200, for a underproof class bituminous coal (2000 kilocalories/kilogram following), as the aphlogistic waste coal that is mixed with a large amount of coal gangues in coal or piles up throughout the year, burning cannot be used separately, but add after this hydrogel, through reasonable preparation, can realize sufficient burning, and can improve the production capacity effect of 1100 kilocalories/kilogram, realize utilization of waste material.In addition, find that the fuel value of low grade coal is brought up to 3700 ~ 4100 kilocalories/kilogram, improved 850 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 23%, saves raw coal approximately 29%, and sulphur content is reduced to below 0.7% by 1.0%.
For fat coal (fuel value is more than 5000 kilocalories), add this hydrogel and can greatly improve calorific value, reduce obnoxious flavour and smoke discharge amount simultaneously; The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with fat coal at 1: 200, find that the fuel value of fat coal is brought up to 5800 ~ 6400 kilocalories/kilogram, improved 1000 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 22%, saves raw coal approximately 28%, and sulphur content is reduced to below 0.7% by 1.0%.
Embodiment 2
A coal combustion-supporting hydrogel, is prepared by following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Nitrocalcite: 32%
SODIUMNITRATE: 17%
Manganous nitrate: 30%
Potcrate: 10%
Cerous nitrate: 1%
Sodium hydroxide: 5%
Water glass: 5%;
(2) get 3% poly N-isopropyl acrylamide and 30% hydrogen peroxide is soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, is made into solid content and is 30% coal combustion-supporting hydrogel.
The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with low grade coal at 1: 200, for a underproof class bituminous coal (2000 kilocalories/kilogram following), as the aphlogistic waste coal that is mixed with a large amount of coal gangues in coal or piles up throughout the year, burning cannot be used separately, but add after this hydrogel, through reasonable preparation, can realize sufficient burning, and can improve the production capacity effect of 1050 kilocalories/kilogram, realize utilization of waste material.In addition, find that the fuel value of low grade coal is brought up to 3700 ~ 4100 kilocalories/kilogram, improved 870 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 23%, saves raw coal approximately 29%, and sulphur content is reduced to below 0.6% by 1.0%.
For fat coal (fuel value is more than 5000 kilocalories), add this hydrogel and can greatly improve calorific value, reduce obnoxious flavour and smoke discharge amount simultaneously; By the coal combustion-supporting hydrogel of the present embodiment and fat coal 1:200 mixing afterfire in mass ratio, find that the fuel value of fat coal is brought up to 5700 ~ 6300 kilocalories/kilogram, improved 900 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 21%, saves raw coal approximately 27%, and sulphur content is reduced to below 0.7% by 1.0%.
Embodiment 3
A coal combustion-supporting hydrogel, is prepared by following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Nitrocalcite: 37%
SODIUMNITRATE: 38%
Potcrate: 10%
Cerous nitrate: 2%
Sodium hydroxide: 5%
Water glass: 8%;
(2) get 3% poly N-isopropyl acrylamide and 30% hydrogen peroxide is soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, is made into solid content and is 30% coal combustion-supporting hydrogel.
The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with low grade coal at 1: 200, for a underproof class bituminous coal (2000 kilocalories/kilogram following), as the aphlogistic waste coal that is mixed with a large amount of coal gangues in coal or piles up throughout the year, burning cannot be used separately, but add after this hydrogel, through reasonable preparation, can realize sufficient burning, and can improve the production capacity effect of 1150 kilocalories/kilogram, realize utilization of waste material.In addition, find that the fuel value of low grade coal is brought up to 3700 ~ 4100 kilocalories/kilogram, improved 880 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 24%, saves raw coal approximately 30%, and sulphur content is reduced to below 0.7% by 1.0%.
For fat coal (fuel value is more than 5000 kilocalories), add this hydrogel and can greatly improve calorific value, reduce obnoxious flavour and smoke discharge amount simultaneously; By the coal combustion-supporting hydrogel of the present embodiment and fat coal 1:200 mixing afterfire in mass ratio, find that the fuel value of fat coal is brought up to 5600 ~ 6200 kilocalories/kilogram, improved 800 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 20%, saves raw coal approximately 25%, and sulphur content is reduced to below 0.7% by 1.0%.
Embodiment 4
A coal combustion-supporting hydrogel, is prepared by following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Nitrocalcite: 40%
Manganous nitrate: 10%
SODIUMNITRATE: 30%
Potcrate: 7%
Cerous nitrate: 1%
Sodium hydroxide: 5%
Water glass: 7%;
(2) get 3% poly N-isopropyl acrylamide and 30% hydrogen peroxide is soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, is made into solid content and is 30% coal combustion-supporting hydrogel.
The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with low grade coal at 1: 200, for a underproof class bituminous coal (2000 kilocalories/kilogram following), as the aphlogistic waste coal that is mixed with a large amount of coal gangues in coal or piles up throughout the year, burning cannot be used separately, but add after this hydrogel, through reasonable preparation, can realize sufficient burning, and can improve the production capacity effect of 1000 kilocalories/kilogram, realize utilization of waste material.In addition, find that the fuel value of low grade coal is brought up to 3700 ~ 4100 kilocalories/kilogram, improved 820 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 19%, saves raw coal approximately 25%, and sulphur content is reduced to below 0.7% by 1.0%.
For fat coal (fuel value is more than 5000 kilocalories), add this hydrogel and can greatly improve calorific value, reduce obnoxious flavour and smoke discharge amount simultaneously; The coal combustion-supporting hydrogel of the present embodiment is mixed to afterfire in mass ratio with fat coal at 1: 200, find that the fuel value of fat coal is brought up to 5400 ~ 6000 kilocalories/kilogram, improved 600 kilocalories of/kilogram of left and right; Thermo-efficiency has improved more than 18%, saves raw coal approximately 23%, and sulphur content is reduced to below 0.7% by 1.0%.
As can be seen from the above embodiments, coal combustion-supporting hydrogel of the present invention can be used in conjunction with any coal, applied widely.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (6)
1. a preparation method for coal combustion-supporting hydrogel, is characterized in that comprising the following steps:
(1) composition of following mass percent is mixed, obtains mixture:
Metal nitrate: 30 ~ 89%
Potcrate: 5 ~ 60%
Rare earth element: 1 ~ 3%
Alkali metal hydroxide: 5 ~ 30%
Water glass: 0 ~ 20%;
(2) get the hydrogen peroxide of 3% poly N-isopropyl acrylamide and 30% soluble in water, stir, obtain solvent; Described per-cent is the per-cent that accounts for solvent cumulative volume;
(3) mixture is dissolved in solvent, obtains coal combustion-supporting hydrogel;
The described metal nitrate of step (1) is more than one in nitrocalcite, magnesium nitrate, strontium nitrate, saltpetre, SODIUMNITRATE, iron nitrate, manganous nitrate, nickelous nitrate or Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES;
The described rare earth element of step (1) is rare earth oxide or rare earth nitrate;
The described alkali metal hydroxide of step (1) is potassium hydroxide or sodium hydroxide;
The number-average molecular weight of the described poly N-isopropyl acrylamide of step (2) is 5000-1000000;
The hydrogen peroxide that step (2) is described, wherein H
2o
2content be 50%.
2. the preparation method of coal combustion-supporting hydrogel according to claim 1, is characterized in that: the described mixture of step (1) obtains after being mixed by the composition of following mass percent:
Metal nitrate: 67 ~ 80%
Potcrate: 7 ~ 15%
Rare earth element: 1 ~ 3%
Alkali metal hydroxide: 5 ~ 10%
Water glass: 5 ~ 8%.
3. the preparation method of coal combustion-supporting hydrogel according to claim 1 and 2, is characterized in that: described its solid content of coal combustion-supporting hydrogel of step (3) is 30%.
4. a coal combustion-supporting hydrogel, is characterized in that: be to be prepared by the method described in claim 1-3 any one.
5. the application of coal combustion-supporting hydrogel claimed in claim 4 in coal combustion-supporting.
6. the application of coal combustion-supporting hydrogel according to claim 5 in coal combustion-supporting, is characterized in that: coal is before burning, first by coal combustion-supporting hydrogel claimed in claim 4 and coal 1:(50 ~ 300 in mass ratio) mix, then burn.
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| CN104028306B (en) * | 2014-06-09 | 2016-06-29 | 中国海洋石油总公司 | A kind of coal burning composite catalyst |
| CN110684580B (en) * | 2019-11-14 | 2021-02-26 | 安徽省宗正农业科技开发有限公司 | Preparation method of composite high-energy biomass fuel rod |
| CN114437838B (en) * | 2022-02-08 | 2023-03-28 | 郑州市晟火冶金节能材料有限公司 | Liquid combustion improver for coal of iron-smelting blast furnace and its usage |
| CN118416937A (en) * | 2024-07-04 | 2024-08-02 | 中国科学技术大学先进技术研究院 | Coal-fired catalyst and preparation method thereof |
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| CN1335378A (en) * | 2000-07-21 | 2002-02-13 | 罗松涛 | Long-acting coal-saving comburant |
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Effective date of registration: 20190701 Address after: 510000 East Side of Longjiao Road Power Wire Material Factory, Jianggao Town, Baiyun District, Guangzhou City, Guangdong Province (Sangyuan Weitian) No. 38 Patentee after: Guangzhou Court Building Materials Co., Ltd. Address before: 511500 Dongcheng Street, Qingcheng District, Qingyuan City, Guangdong Province, No. 1 Jiazhou Road, No. 1 Jiazhou Garden District, No. 13 Building, No. 1 Ladder, No. 11 Floor, No. 04 Patentee before: Qingyuan Wei'erxin Chemical Building Materials Co., Ltd. |
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Address after: 510000 room 7-8, Room 201, No. 146, huangbian North Road, Helong street, Baiyun District, Guangzhou, Guangdong Patentee after: Gomes (Guangdong) building materials Co.,Ltd. Address before: 510000 East Side of Longjiao Road Power Wire Material Factory, Jianggao Town, Baiyun District, Guangzhou City, Guangdong Province (Sangyuan Weitian) No. 38 Patentee before: GUANGZHOU GOMIX BUILDING MATERIAL CO.,LTD. |
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