CN103725347A - Desulfurizing, denitrifying and decoking synergic additive for fire coal and preparation method of additive - Google Patents
Desulfurizing, denitrifying and decoking synergic additive for fire coal and preparation method of additive Download PDFInfo
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Abstract
The invention discloses a desulfurizing, denitrifying and decoking synergic additive for fire coal and a preparation method of the additive. The invention relates to the fields of desulfurizing and denitrifying, and particularly relates to a preparation method of an additive integrating desulfurization, denitrification, decoking and synergism in a process of combusting sulphur coal and coal. According to the additive and the preparation method disclosed by the invention, in an original coal combusting stage, a catalytic synergist which accounts for 0.1-0.8wt% of the total weight of the original coal is added into the fire coal, and meanwhile, a catalytic activating synergist which accounts for 0.02-0.2wt% of total weight of desulfuration slurry is further added into a slurry box of a desulfurization system. Under the premise of not changing an existing device, the catalytic activating synergist has the functions of saving coal, cleaning ash, decoking, desulfurizing and denitrifying to combustion of sulphur coal in a boiler. The catalytic activating synergist enhances the activity of lime stones in lime stone slurry and improves the desulfurizing efficiency as well as increases the denitrifying function, and meanwhile, the desulfurizing and denitrifying functions can reach or exceed national standards, so that the investment on selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) denitrifying equipment is lowered, and huge economical benefit and environment-friendly benefit are obtained.
Description
Technical field
The present invention relates to desulphurization denitration field, especially at burning high sulphur coal, in coal-fired process, there is the additives production process of desulphurization and denitration, decoking synergy one.
Background technology
Also for high sulphur coal, do not possess burning aid coal saving, SO both at home and abroad at present simultaneously
2,nO
xthe manufacture method of the several functions additives such as reduction of discharging, ash-cleaning and coke-removing, the desulfurization technology of simple function has several as follows:
(1) desulfurization before burning: raw coal is concentrated the methods such as washing, moulding carry out desulfurization.The subject matter existing is the structure sulphur in coal or claims that organosulfur cannot remove, and cost is high.Especially coal in power plant, cannot adopt especially.
(2) flue gas desulfurization: be mainly to adopt flue gas desulfurization (FGD) unit.Existing problems be costly, running cost is high, produces secondary pollution.
Adopt Wet Limestone-gypsum technology and equipment to carry out flue gas desulfurization, one ton of sulfurous gas of every processing, produce 2 tons of gypsum and 0.7 ton of carbonic acid gas, and denitration simultaneously.Current method of denitration comprises: SCR (SCR) and selective non-catalytic reduction (SNCR) denitration.The feature of these technology is: a technology, only for a kind of pollutent, realizes removing of pollutent by a set of special equipment.This pollutent classification administration way, exists that floor space is large, the problem such as facility investment and working cost and energy consumption is high, flue gas system poor stability, has a strong impact on economy and suitability that coal burning pollution is controlled.Therefore carry out the research that flue gas multiple pollutant removes simultaneously and have important practical significance, become the outer emerging research field of Present Domestic.Single solid desulfurization technology in burning, fails to solve in more than 900 ℃ high-temperature zones the solid sulphur problem of secondary release again, and desulfurization degree is lower, and sweetening effectiveness is not good.
It is a complicated technology that the NOx generating in raw coal combustion process is implemented to control, because the formation mechanism of NOx is different, the factor that affects its growing amount is also different, same controlling factor, to their influence degree, also each is variant, even a controlling factor can be implemented effective control to a certain type NOx, completely invalid to the control of another kind of NOx, therefore in business, reduces NOx, SO simultaneously
2, N
2o discharge is more difficult.Today advocating environmental protection and benefit, at some, relate in the field of coal burning, to possess burning aid coal saving, SO simultaneously
2, NOx, reduction of discharging, ash-cleaning and coke-removing technology be undoubtedly the demand of future development.
Summary of the invention
One of technical problem to be solved by this invention is to provide a kind of method of desulphurization denitration and coke cleaning in fire coal, in raw coal combustion process, adds catalytic synergist, can accelerate the coal-fired CO of generation and SO thermopositive reaction occurs, and the sulphur generating in reaction becomes SO through burning
2, part SO
2through katalysis, be oxidized to SO
3finally being had the extremely strong oxide compound of adsorptive power absorbs.Reduce coal-fired NOx, the ash-cleaning and coke-removing effect of economizing on coal producing; In the slurry tank of desulphurization system, add catalytic activity synergistic agent, at the SO in flue gas
2in active process, the Wingdale of slurries is carried out to catalytic activation simultaneously, improve desulfurization degree 10-15%, improve denitration rate and reach 50-80% and makes its increased activity, make itself and SO
2probability and the intensity of reaction increase substantially.
Two of technical problem to be solved by this invention is to provide a kind of technique of preparing catalytic synergist, by simple method, obtain catalytic synergist, in the situation that not changing original boiler plant, add this catalytic synergist, thereby reach the object of desulphurization and denitration, coke cleaning.
Three of technical problem to be solved by this invention is to provide a kind of technique of preparing catalytic activation synergistic agent, by simple method, obtain catalytic activation synergistic agent, in the situation that not changing original desulphurization denitration equipment, add this catalytic activation synergistic agent, further improve catalytic activation synergistic agent desulphurization and denitration, effect.
Technical scheme of the present invention is:
A kind of coal desulfurization denitration decoking Synergistic additives and manufacture method thereof, in the raw coal combustion stage, in fire coal, sneak into catalytic synergist, catalytic synergist accounts for raw coal total amount 1-8 ‰ (weight ratio), in the slurry tank of desulphurization system, add again catalytic activation synergistic agent, catalytic activation synergistic agent accounts for desulfurization slurry total amount 0.2-2 ‰ (weight ratio) simultaneously; Described catalytic synergist contains mass percent:
Cupric nitrate 8-20%
Potassium permanganate 5-15%
Manganse Dioxide 5-10%
Saltpetre 5-10%
Cerous nitrate 1-10%
Titanium dioxide 10-30%
Sodium perchlorate 5-20%
Hexamethylenetetramine 3-20%
Ammonium nitrate 10-50%.
Described catalytic activation synergistic agent contains mass percent:
Borax 10-30%
Sodium-acetate 20-30%
Textone 10-70%
Potassium permanganate 5-20%
Hexanodioic acid sodium 5-30%
Sodium dodecylbenzene sulfonate 2-10%
Cobalt oxide 0.2-5%
Do not changing present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to the physical and chemical index of user's fire coal, with 0.1-0.8%(weight ratio) catalytic synergist sneak into raw coal lunch, drop in boiler and burn.The different effects such as the low temperature according to raw coal in combustion processes, the required catalysis of middle gentle high temperature section, oxidation, loose, purification, reduce the point of ignition of coal, accelerate the burning progress of carbon, improve fire box temperature, strengthening heat transfer; Promote that coal fully burns at boiler furnace, obviously improve burning subenvironment, the oxygenizement of strengthening coal, in intensification and heat-processed, emit nascent state oxygen, promoter action has been played in making full use of of this chemical reaction burning situation in burner hearth, inflammable gas to raw coal, inflammable gas, oxygen level and ashes in flue gas are further reduced, thereby reduce consumption and the oke exhaust blackness of coal.
Some composition of catalytic synergist at high temperature decomposes.Gas and generation microexplosion, stir the gas in coal dust and coal dust, loosened in the coal seam of hardening, and air permeability is improved, and makes oxygen being evenly distributed in coal dust, and supply is abundant, is easy to make coal-fired dispersion, and surfactivity increases, and is beneficial to the abundant burning of raw coal.Also increase to a certain extent thermal conduction, reduce the hot melt degree of raw coal, and by the chemical reaction coal seam of loosen, impel wrapped coal grain fully to burn, the carbon content in minimizing slag, ash.
There is thermal response in the CO that catalytic synergist can be accelerated to produce in raw coal combustion and SO,, the sulphur generating in reaction becomes SO through burning
2, part SO
2through katalysis, be oxidized to SO
3finally there is the extremely strong oxide compound of adsorptive power and fixed and generate the slag ash that fusing point is higher.Oxide compound in catalytic synergist can also and be fixed in slag other nonferrous metal ion chemical combination that produce in coal burning process, thereby reaches the object of solid sulphur, desulphurization and denitration.
In the slurry tank of desulphurization system, add catalyst activator, at the SO in flue gas
2in reactivation process, the Wingdale of slurries is carried out to catalytic activation simultaneously, make its increased activity, make itself and SO
2probability and the intensity of reaction increase substantially, and this catalyst activator can change the pH value of slurries, comparatively speaking, the increased activity of Wingdale, utilization ratio has been enhanced; When the consumption of former Wingdale is constant, allow the SO of discharge
2concentration has increased, and in fire coal, sulphur content can increase, and desulfurization degree remains unchanged.
Technical scheme of the present invention is:
A kind of technique of preparing catalytic synergist, first by cupric nitrate, potassium permanganate, silicon oxide, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into, its mass percent is:
Cupric nitrate 8-20%
Potassium permanganate 5-15%
Manganse Dioxide 5-10%
Saltpetre 5-10%
Cerous nitrate 1-10%
Titanium dioxide 10-30%
Sodium perchlorate 5-20%
Hexamethylenetetramine 3-20%
Ammonium nitrate 10-50%.
Technical scheme of the present invention is:
A kind of technique of preparing catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, its mass percent is:
Borax 10-30%
Sodium-acetate 10-30%
Textone 10-70%
Potassium permanganate 5-20%
Hexanodioic acid sodium 5-30%
Sodium dodecylbenzene sulfonate 2-10%
Cobalt oxide 0.2-5%
The beneficial effect that the present invention compared with prior art brought is:
In former high sulfur coal combustion process, add catalytic synergist, can accelerate the coal-fired CO of generation and SO thermopositive reaction occurs, the sulphur generating in reaction becomes SO through burning
2, part SO
2through katalysis, be oxidized to S
o3finally being had the extremely strong oxide compound of adsorptive power absorbs; Reduce ammonia nitrogen discharge, the ash-cleaning and coke-removing effect of economizing on coal is conducive to environmental protection and energy saving, effectively utilizes and opened up an environmental protection passage to high sulphur coal, adds catalytic activation synergistic agent, at the SO in flue gas in the slurry tank of desulphurization system
2in reactivation process, the Wingdale of slurries is carried out to catalytic activation simultaneously, make its increased activity, make itself and SO
2probability and the intensity of reaction increase substantially, the increased activity of Wingdale, utilization ratio has been enhanced; When the consumption of former Wingdale is constant, increased desulfuration efficiency, increase again denitration function while desulphurization denitration and can meet or exceed national standard, reduced the investment of SCR (SCR) and selective non-catalytic reduction (SNCR) denitration device, economic benefit and environmental benefit are huge.
Embodiment:
Embodiment 1
A kind of preparation method of catalytic synergist, first by cupric nitrate, potassium permanganate, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into.Wherein catalytic synergist component contains mass percent: cupric nitrate 18%, potassium permanganate 12%, Manganse Dioxide 5%, saltpetre 10%, cerous nitrate 5% titanium dioxide 30% hexamethylenetetramine 15%, ammonium nitrate 10%, sodium perchlorate 8%.
Do not change present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to user, firing few high sulphur coal (sulphur content 2.5%), with the catalytic synergist of 3.0 ‰ (weight ratios), sneaking in raw coal, dropping into boiler combustion.Move 30 days desulfurization degree 42% after testing, denitration rate 28%, and improved boiler hearth temperature 50-100 ℃; Obviously reduce oke exhaust blackness; Ash-cleaning and coke-removing reaches more than 90%; Economize on coal 2.5%.
A kind of a kind of technique of preparing catalytic activation synergistic agent of preparation method of catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, the constituent mass per-cent of catalytic activation synergistic agent is: borax 15%, sodium-acetate 15%, hexanodioic acid sodium 10%, potassium permanganate 10% Sodium dodecylbenzene sulfonate 5% Textone 44.5%, cobalt oxide 0.5%.
In the slurry tank of desulphurization system, add 0.08 ‰ (weight ratio) catalytic activation synergistic agent, smoke inlet concentration SO
27500ppm,, NO entrance concentration is tetra-slurry circulating pumps of 800ppm, in absorption tower, ph value is 5.8 o'clock.An inactive slurry circulating pump, desulfuration efficiency increases to 98%, denitration 65%.
Embodiment 2
A kind of preparation method of catalytic synergist, first by cupric nitrate, potassium permanganate, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into.Wherein catalytic synergist component contains mass percent: cupric nitrate 15%, potassium permanganate 10%, Manganse Dioxide 8%, saltpetre 10%, cerous nitrate 5% titanium dioxide 25% hexamethylenetetramine 10%, ammonium nitrate 7%, sodium perchlorate 10%.
Do not change present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to user, firing few high sulphur coal (sulphur content 2.8%), with the catalytic synergist of 3.8 ‰ (weight ratios), sneaking in raw coal, dropping into boiler combustion.Move 30 days desulfurization degree 45% after testing, denitration rate 32%, and improved boiler hearth temperature 50-100 ℃; Obviously reduce oke exhaust blackness; Ash-cleaning and coke-removing reaches more than 95%; Economize on coal 2.8%.
A kind of a kind of technique of preparing catalytic activation synergistic agent of preparation method of catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, the constituent mass per-cent of catalytic activation synergistic agent is: borax 10%, sodium-acetate 10%, hexanodioic acid sodium 10%, potassium permanganate 10% Sodium dodecylbenzene sulfonate 5% Textone 54.5%, cobalt oxide 0.5%.
In the slurry tank of desulphurization system, add 0.9 ‰ (weight ratio) catalytic activation synergistic agent, smoke inlet concentration SO
28200ppm,, NO entrance concentration is tetra-slurry circulating pumps of 800ppm, in absorption tower, ph value is 5.6 o'clock.An inactive slurry circulating pump, desulfuration efficiency increases to 98%, denitration 68%.
Embodiment 3
A kind of preparation method of catalytic synergist, first by cupric nitrate, potassium permanganate, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into.Wherein catalytic synergist component contains mass percent: cupric nitrate 10%, potassium permanganate 10%, Manganse Dioxide 8%, saltpetre 10%, cerous nitrate 5% titanium dioxide 15% hexamethylenetetramine 10%, ammonium nitrate 22%, sodium perchlorate 10%.
Do not change present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to user, firing few high sulphur coal (sulphur content 2.0%), with the catalytic synergist of 3 ‰ (weight ratios), sneaking in raw coal, dropping into boiler combustion.Move 25 days desulfurization degree 48% after testing, denitration rate 29.5%, and improved boiler hearth temperature 50-100 ℃; Obviously reduce oke exhaust blackness; Ash-cleaning and coke-removing reaches more than 95%; Economize on coal 2.3%.
A kind of a kind of technique of preparing catalytic activation synergistic agent of preparation method of catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, the constituent mass per-cent of catalytic activation synergistic agent is: borax 20%, sodium-acetate 20%, hexanodioic acid sodium 20%, potassium permanganate 10% Sodium dodecylbenzene sulfonate 9% Textone 20%, cobalt oxide 1%.
In the slurry tank of desulphurization system, add 0.9 ‰ (weight ratio) catalytic activation synergistic agent, smoke inlet concentration SO
29500ppm,, NO entrance concentration is tetra-slurry circulating pumps of 860ppm, in absorption tower, ph value is 5.8 o'clock.An inactive slurry circulating pump, desulfuration efficiency increases to 97%, denitration 66.8%.
Embodiment 4
A kind of preparation method of catalytic synergist, first by cupric nitrate, potassium permanganate, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into.Wherein catalytic synergist component contains mass percent: cupric nitrate 10%, potassium permanganate 10%, Manganse Dioxide 8%, saltpetre 10%, cerous nitrate 8% titanium dioxide 20% hexamethylenetetramine 10%, ammonium nitrate 24%, sodium perchlorate 10%.
Do not change present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to user, firing few high sulphur coal (sulphur content 2.8%), with the catalytic synergist of 3.8 ‰ (weight ratios), sneaking in raw coal, dropping into boiler combustion.Move 28 days desulfurization degree 52% after testing, denitration rate 35.2%, and improved boiler hearth temperature 50-100 ℃; Obviously reduce oke exhaust blackness; Ash-cleaning and coke-removing reaches more than 95%; Economize on coal 3.42%.
A kind of a kind of technique of preparing catalytic activation synergistic agent of preparation method of catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, the constituent mass per-cent of catalytic activation synergistic agent is: borax 15%, sodium-acetate 25%, hexanodioic acid sodium 10%, potassium permanganate 15% Sodium dodecylbenzene sulfonate 8% Textone 26.5%, cobalt oxide 0.5%.
In the slurry tank of desulphurization system, add 1.1 ‰ (weight ratio) catalytic activation synergistic agent, smoke inlet concentration SO
27200ppm,, NO entrance concentration is tetra-slurry circulating pumps of 800ppm, in absorption tower, ph value is 5.5 o'clock.Inactive two slurry circulating pumps, desulfuration efficiency increases to 98%, denitration 74.2%.
Embodiment 5
A kind of preparation method of catalytic synergist, first by cupric nitrate, potassium permanganate, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively, then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into.Wherein catalytic synergist component contains mass percent: cupric nitrate 15%, potassium permanganate 10%, Manganse Dioxide 5%, saltpetre 10%, cerous nitrate 7% titanium dioxide 20% hexamethylenetetramine 15%, ammonium nitrate 8%, sodium perchlorate 10%.
Do not change present smoke evacuation Processes and apparatus, only from the burning link of raw coal, starting with, according to user, firing few high sulphur coal (sulphur content 3.1%), with the catalytic synergist of 4.8 ‰ (weight ratios), sneaking in raw coal, dropping into boiler combustion.Move 30 days desulfurization degree 43% after testing, denitration rate 31%, and improved boiler hearth temperature 50-100 ℃; Obviously reduce oke exhaust blackness; Ash-cleaning and coke-removing reaches more than 95%; Economize on coal 2.7%.
A kind of a kind of technique of preparing catalytic activation synergistic agent of preparation method of catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend were stirred Sodium dodecylbenzene sulfonate, Textone, cobalt oxide to mix for 10-30 minute and formed again after 20-30 minute, pack packing bag into, the constituent mass per-cent of catalytic activation synergistic agent is: borax 10%, sodium-acetate 20%, hexanodioic acid sodium 15%, potassium permanganate 12% Sodium dodecylbenzene sulfonate 5% Textone 37.2%, cobalt oxide 0.8%.
In the slurry tank of desulphurization system, add 0.08 ‰ (weight ratio) catalytic activation synergistic agent, smoke inlet concentration SO
28500ppm,, NO entrance concentration is tetra-slurry circulating pumps of 870ppm, in absorption tower, ph value is 5.4 o'clock.Inactive two slurry circulating pumps, desulfuration efficiency increases to 98%, denitration 72.2%.
Claims (2)
1. a coal desulfurization denitration decoking Synergistic additives and manufacture method thereof, it is characterized in that: at raw coal, burn the stage, in fire coal, add catalytic synergist, catalytic synergist accounts for raw coal and always measures 1 ~ 8 ‰ (weight ratio), in the slurry tank of desulphurization system, add catalyst activator again, catalytic activation synergistic agent accounts for the 0.2-2.0 ‰ (weight ratio) of desulfurization slurry total amount simultaneously.
2. a kind of coal desulfurization denitration decoking Synergistic additives manufacture method according to claim 1, is characterized in that:
(1) described catalytic synergist contains mass percent:
Cupric nitrate 8-20%
Potassium permanganate 5-15%
Manganse Dioxide 5-10%
Saltpetre 5-10%
Cerous nitrate 1-10%
Titanium dioxide 10-30%
Sodium perchlorate 5-20%
Hexamethylenetetramine 3-20%
Ammonium nitrate 10-50%.
(2) described catalytic activation synergistic agent contains mass percent:
Borax 10-30%
Sodium-acetate 20-30%
Textone 10-70%
Potassium permanganate 5-20%
Hexanodioic acid sodium 5-30%
Sodium dodecylbenzene sulfonate 2-10%
Cobalt oxide 0.2-5%
(3) manufacturing process of described catalytic synergist; first by cupric nitrate, potassium permanganate, silicon oxide, Manganse Dioxide, saltpetre, cerous nitrate, titanium dioxide, hexamethylenetetramine, add and stir 20-60 minute successively; then form adding ammonium nitrate, sodium perchlorate and stir to mix for 10-30 minute, pack packing bag into;
(4) manufacturing process of described catalytic activation synergistic agent, first borax, sodium-acetate, potassium permanganate, hexanodioic acid sodium mix and blend are stirred to even the forming that be mixed for 10-30 minute by Sodium dodecylbenzene sulfonate, Textone, cobalt oxide after 20-30 minute again, pack packing bag into.
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| CN106085547A (en) * | 2016-08-03 | 2016-11-09 | 安徽中缘新材料科技有限公司 | A kind of liquid clean coal additive |
| CN108905547A (en) * | 2018-06-29 | 2018-11-30 | 南通乐尔环保科技有限公司 | A kind of deep purifying Desulfurization synergist |
| CN110699150A (en) * | 2019-10-28 | 2020-01-17 | 山东亿维新材料有限责任公司 | Environment-friendly decoking agent and preparation method thereof |
| CN111992230A (en) * | 2020-08-31 | 2020-11-27 | 山东嘉禾新能源开发有限公司 | Coal-saving denitration catalyst, preparation method thereof and coal-saving denitration method |
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Application publication date: 20140416 |