CN1224684C - Biologically cleaning briquette as solid fuel - Google Patents
Biologically cleaning briquette as solid fuel Download PDFInfo
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- CN1224684C CN1224684C CN 01102652 CN01102652A CN1224684C CN 1224684 C CN1224684 C CN 1224684C CN 01102652 CN01102652 CN 01102652 CN 01102652 A CN01102652 A CN 01102652A CN 1224684 C CN1224684 C CN 1224684C
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Abstract
The present invention relates to a biological cleaning briquette as solid fuels, which is characterized in that a Ca desulfurizing agent and a Mg desulfurizing agent are mixed and added in coal powder, the molar ratio of Ca to S or Mg to S is from 1 to 2, and the extrusion forming is carried out for the mixture; the surface of the formed briquette as solid fuels is attached with Ca (OH) 2, CaO and CaCO3 to make compound solid fuels of the briquette with a white surface. The present invention reaches the purpose of cheap and efficient devulcanization. Simultaneously, waste black liquor from paper manufacture is used as a binding agent of the briquette, and a denitration effect can be obtained. The present invention provides an operable method for using high-S poor coal cheaply, efficiently and cleanly.
Description
The invention belongs to the coal solid fuel, particularly a kind of biologically cleaning briquette as solid fuel.
Mixing in coal dust in the past adds Ca or Mg matter sweetening agent and various binding agent, and the technology of coal briquette or honeycomb briquette etc. of making is known by common people already.And on this basis, developed the coal and the phyteral composite solid fuel of low grade coal (about 70-80 weight % degree) with phyteral (agricultural, forestry waste, about 20-30 weight % degree) mixing moulding.Catch fire and the incendivity of this fuel have all obtained effective improvement.Dust discharge in its combustion processes has also obtained certain inhibition.Again with Ca matter sweetening agent, as Wingdale (CaCO
3), unslaked lime (CaO) or slaked lime Ca (OH)
2Can obtain sweetening effectiveness preferably Deng being mixed in this solid fuel.To this, we also have quite detailed relevant report on the professional technique Za Chi of the U.S. and Japan.
At present, owing to the greenhouse effects of the earth that the burning of fossil oil causes, topsoil phenomenon such as acid rain and human beings'health have become global key subjects because of pollution is undermined.Especially in developing country, low grade coal (high-sulfur, high nitrogen, ash-rich and lower calorific value) becomes medium and small boiler as 1 energy, and family's fuel such as heating and cooking are used widely.The SO that these low grade coals are discharged without the direct burning of any processing treatment
2, NOx and dust polluting environment, the disease of also having aggravated the human breathing organ.Because technology and difficulty economically, dedusting and desulfurization, denitration (removing NOx) device also do not obtain popularizing widely in these countries.
As mentioned above, mixed C a matter sweetening agent in low grade coal can be with a part of SO that generates in the burning
2Be fixed in the ash, reduce SO
2Discharging.But its desulfuration efficiency generally is lower than 75%.The coal-fired sulphur content of using in the home-use stove in some place (as the certain areas in southwest) of China can reach more than 4% (the weight % d.a.f.).Sulphur content is also more in the volatile matter of these coals.With the moulded coal of these high sulphur coal manufacturings, both made to mix and added Ca matter sweetening agent, its desulfuration efficiency is also below 75%.Thereby SO in the smoke evacuation of home-use stove
2Concentration still more than 1000ppm, is also still threatening user's health and is polluting environment.
Therefore for making high sulphur coal be able to cheapness, efficient, the clean burning utilization, desulfurizer therefor must be cheap, addition will be less and desulfuration efficiency want height.
The purpose of this invention is to provide a kind of biologically cleaning briquette as solid fuel, overcome the shortcoming and defect of prior art.Exploitation has high burning efficiency, and is high from desulfurization, denitration usefulness power, and synthesis pressure is low but destruction is resisted the high moulded coal composite solid fuel of intensity.
The object of the present invention is achieved like this:
A kind of biologically cleaning briquette as solid fuel is characterized by: in coal dust, mix to add Ca, Mg matter sweetening agent, the mol ratio of Ca/S or Mg/S between 1-2, extrusion forming; And the solid-fuelled surface attachment Ca of the moulded coal after moulding (OH)
2, CaO, CaCO
3, make the moulded coal composite solid fuel that the surface is white in color.
Moulded coal surface attachment Ca (OH)
2, CaO, CaCO
3Amount be the Ca/S mol ratio between 0.1-2, and make the moulded coal composite solid fuel that the surface is white in color.
Described coal is the sulphur content weight ratio greater than 0.5% coal, makes the moulded coal composite solid fuel that the surface is white in color with it.
Described Ca matter sweetening agent such as the Ca (OH) of containing
2, CaO, CaCO
3Trade waste, as the solid-fuelled surface attachments of moulded coal, make the moulded coal composite solid fuel that the surface is white in color with it.
Adopt the phyteral composition to mix, make the moulded coal composite solid fuel that the surface is white in color with coal dust.
Mix with coal dust with binding agent, make the moulded coal composite solid fuel that the surface is white in color.
Adopt black liquid as binding agent, make the moulded coal composite solid fuel that the surface is white in color.
The present invention mixes to add Ca or Mg matter sweetening agent in the mixing of coal dust (70-80 weight %) and phyteral (20-30 weight %), and moulding.With its surface attachment sweetening agent, can remove the SO that in burning, generates again
2And NOx.Make the be white in color moulded coal composite solid fuel of cleaner appearance of surface.
Advantage of the present invention is: the present invention is mixed into moulded coal inside with Ca or Mg matter sweetening agent, and the Ca (OH) of trace
2Be attached to the moulded coal composite solid fuel that the surface of making on solid-fuelled surface is white in color.Make total Ca/S mol ratio between 1-2, and desulfuration efficiency increase to 90% significantly.Reached the purpose of Cheap highly effective desulfurization.Simultaneously, the black liquor that uses waste paper-making both can improve the intensity of moulded coal as the binding agent of moulded coal, can obtain certain denitration effect again.The present invention provides practicable method for the low grade coal (especially sulphur content is higher than 4 weight % d.a.f.) of developing country's high sulfur content is able to the Cheap highly effective clean utilization.
Below in conjunction with description of drawings embodiment:
Fig. 1 is the influence figure of chamber temperature to desulfuration efficiency
Fig. 2 is the figure that influences of Ca/S comparison desulfuration efficiency
Fig. 3 be the smoke evacuation in SO through the time change curve
Fig. 4 be in desulfuration efficiency and the fixed carbon sulphur content get in touch figure
Fig. 5 is a comparison diagram of planting the sweetening agent sweetening effectiveness
Fig. 6 be in the combustion processes smoke evacuation SO through the time comparison diagram that changes
Fig. 7 is the different desulfurization test of a sweetening agent not of the same race and addition manner comparison diagram as a result
Fig. 8 is the comparison diagram of sweetening effectiveness
Fig. 9 is the graph of a relation of sulphur content in desulfuration efficiency and the fixed carbon
Figure 10 is the comparison diagram of sweetening effectiveness
Figure 11 destroys the variation diagram of opposing intensity with condition of molding
Figure 12 be the smoke evacuation in NO concentration through hourly variation
Figure 13 is the influence figure of black liquor content to denitration effect
The present invention mixes to add Ca or Mg matter sweetening agent in the mixing of coal dust (70-80 weight %) and phyteral (20-30 weight %), and moulding.With its surface attachment sweetening agent, can remove the SO that in burning, generates again
2And NOx.Make the be white in color moulded coal composite solid fuel of cleaner appearance of surface.
Inventor of the present invention has improved sweetening agent mixing addition manner in the past, when the internal mix of coal dust and phyteral mixture adds Ca or Mg matter sweetening agent, moulded coal solid fuel surface after synthesizing forms the Ca matter sweetening agent thin layer of trace more again, has developed brand-new white moulded coal composite solid fuel.The cost of this fuel is low, and desulfuration efficiency is higher than dry type desulfurizing efficient (about 75%) in the past, can reach equal sweetening effectiveness (about 90%) with wet desulfurization method.That is, the present invention adds Ca or Mg matter sweetening agent in the mixture of coal dust or coal dust and phyteral, Ca/S or Mg/S mol ratio between 1-2, mixing moulding.Solid-fuelled surface attachment Ca (OH) after moulding again
2, (CaO) or CaCO
3, make the moulded coal composite solid fuel that the surface is white in color.Its adhesion amount is that the mol ratio of Ca/S or Mg/S is between 0.1-2.The present invention can be higher than sulphur content the coal of 0.5% (weight %) and make the moulded coal composite solid fuel that the surface is white in color.The present invention also can will contain Ca matter such as Ca (OH)
2, (CaO) or CaCO
3Trade waste make the moulded coal composite solid fuel that the surface is white in color as sweetening agent.The present invention also can make the moulded coal composite solid fuel that the surface is white in color with black liquid as binding agent.
Make moulded coal composite solid fuel that the surface is white in color in combustion processes with aforesaid method, can be with most SO
2Be fixed in the ash.Especially the Ca matter sweetening agent of surface attachment can remove the SO that is generated by volatile combustion effectively
2Make the Ca/S of internal mix sweetening agent or Mg/S mol ratio between 1-2 and desulfuration efficiency rises significantly up to 90%.In addition, especially the sweetening effectiveness of the Ca matter sweetening agent of surface attachment is very big, therefore, also can suitably reduce the amount of internal mix sweetening agent.And the moulded coal composite solid fuel of white also gives the user with clean feel, and its commodity value is risen.
As raw material of the present invention, each coal all is suitable for.Its product is applicable to the various moulded coal burners that coal is fit to.Can be with coal dust and agricultural wastes (straw, corn tangerine, the Chinese sorghum tangerine of pulverizing at certain particle size, grass etc.) or forestry waste (culled wood, waste wood is cut, bark etc.) mix, add certain binding agent, low pressure molding (20-100MPa) is to reduce the manufacturing cost of moulded coal.
Blended Ca matter sweetening agent can be Wingdale (CaCO in moulded coal
3), slaked lime (Ca (OH)
2), or as the shell of industrial waste and carbide slag etc.The Ca of moulded coal surface attachment (OH)
2Or the amount of CaO, its Ca/S mol ratio is between 0.1-2.The Ca/S ratio is lower than 0.1, and desulfuration efficiency is also low.The Ca/S ratio is higher than 2, and desulfuration efficiency does not increase, and production cost is increased.
At moulded coal surface attachment sweetening agent Ca (OH)
2Method be: with Ca (OH)
2Ratio in 100-900g/L (water) is mixed with water, mixed solution is attached to moulded coal surface (as be coated with and touch, spraying etc.), dry getting final product again.
And have desulfurization, denitration function binding agent adds in the moulded coal, can pounce on oxygen sulfur compound and nitrogen compound that when burning collection produces, forms sulfuric acid and sulfurous acid Ca and nitric acid Na etc. in ash.Reaction mechanism is:
The denitration of volatile component combustion processes:
The denitration of coke combustion:
Trade wastes such as available black liquid are made binding agent, obtain high strength under low forming pressure, the moulded coal of high burning efficiency.Particularly when making binding agent with black liquid, itself is desulfidation but also denitrification is arranged not only not only.For another example, when coal dust and phyteral (as agricultural wastes) are mixed and made into the moulded coal composite solid fuel,, make intensity reduce breakage easily because the easy water-swelling of phyteral produces be full of cracks after the moulded coal composite solid fuel of making is made moist.To this, under the situation of high humidity, can adopt and add a small amount of depleted oil, heavy oil or depleted lubricating oil make the surface of moulded coal composite solid fuel produce water-repellancy.
Now produce high sulphur coal, hereinafter to be referred as BJ coal (sulphur content with the man village of Chinese Shanxi White; 2.2 weight % d.a.f.) and phyteral (sulphur content is almost nil) be raw material, Ca matter sweetening agent mix is added, make pure moulded coal and moulded coal composite solid fuel (BJ coal: 80 weight %; Phyteral: 20 weight %), surperficial non-cohesive sweetening agent.Experimental result is as follows:
Test of the influence of 1 chamber temperature to the desulphurizing ability of ' pure moulded coal ' and ' moulded coal composite solid fuel '.
Sweetening agent is common Wingdale.The Ca/S mol ratio of internal mix sweetening agent is 3.Chamber temperature 873-1173K.Fig. 1 has shown the influence of chamber temperature to the desulphurizing ability of ' pure moulded coal ' and ' moulded coal composite solid fuel '.The longitudinal axis is a desulfurization degree among the figure, and transverse axis is a chamber temperature.As seen from Figure 1, ' pure moulded coal ' is almost completely consistent with the desulfuration efficiency of ' moulded coal composite solid fuel '.This explanation: both desulfurization characteristic are consistent, promptly do not change its desulfurization characteristic because of having mixed phyteral.
Test of the influence of 2 Ca/S mol ratios to desulfuration efficiency.The addition of Ca matter sweetening agent is few more, and the price of Ca matter sweetening agent is low more, and the cost of moulded coal composite solid fuel is also low more.Therefore, this experiment is with common, and cheap Wingdale is that sweetening agent and coal dust and phyteral are mixed and made into the moulded coal composite solid fuel, carries out desulfurization test.Fig. 2 has shown that the Ca/S mol ratio changes (addition of sweetening agent changes) influence to sweetening effectiveness.As shown in the figure, increase with the Ca/S mol ratio, desulfuration efficiency raises.When Ca/S=3, desulfuration efficiency can reach about 68%.But after this Ca/S continues to increase, and desulfuration efficiency increases become quite slow.As if it is saturated that the Ca/S=5 desulfuration efficiency has reached.
Fig. 3 has provided SO in the smoke evacuation of above-mentioned experiment
2Through the time change curve.By this figure as seen, increase (addition of sweetening agent increases), SO in the smoke evacuation with Ca/S
2Concentration obviously descend.But, when Ca/S greater than 3 the time, the influence that the continuation of Ca/S increases desulfuration efficiency becomes very not remarkable.It can also be seen that from this figure desulphurization reaction mainly occurs in the combustion zone (the burning beginning back 5-75 divide Bell) of fixed carbon.Regardless of Ca/S, as if in the combustion zone (burning beginning back 0-5 minute) of volatile matter, desulphurization reaction does not take place.This explanation during with lime masonry sweetening agent, is difficult to pounce on the SO that grasps by fugitive constituent burning generation
2
Fig. 4 has represented that the desulphurization during combustion experiment and the thermolysis of the moulded coal composite solid fuel made by different charcoal kinds test.Its temperature of combustion and heat decomposition temperature are 1073K.Sweetening agent remains above-mentioned Wingdale, and the Ca/S mol ratio is 3.Left side axle is a desulfurization degree, and right axle is the partition ratio of sulphur content in the solid fuel, and transverse axis is fuel ratio (in the fuel in fixed carbon/fuel fugitive constituent).Fig. 4 shows, the coal difference, and the partition ratio of the sulphur content in the coal is also different, and desulfuration efficiency is also different.But desulfuration efficiency always is lower than the content of the sulphur in the fixed carbon of coal.Fig. 4 has confirmed again, when mixing interpolation with lime masonry sweetening agent, by the SO of volatile combustion generation
2Do not removed effectively.
Test the comparison of 3 various sweetening agent sweetening effectivenesss.All the other conditions are identical, only change the kind of sweetening agent, and the result of desulfurization is illustrated among Fig. 5 in the combustion processes.Desulfurizer therefor be Wingdale and industrial waste shell (particle diameter: 297-420 μ m), Ca (OH)
2(experiment reagent; Particle diameter: 25 μ m are following) and carbide slag (particle diameter: below the 1mm; Major ingredient is: CaO, also contain the BaO of several %, SrO) in addition.The Ca/S mol ratio is 1.5.As shown in Figure 5, carbide slag and Ca (OH)
2Have sweetening effectiveness much at one, desulfuration efficiency can reach about 75%.Its desulfuration efficiency is 2 times of Wingdale, than the desulfuration efficiency high about 10% of shell.As if by above experiment as can be known, Ca matter sweetening agent is when mixing interpolation, and desulfuration efficiency is the upper limit with 75%.
With internal mix sweetening agent (CaCO
3Ca/S=1) and surface attachment sweetening agent (Ca (OH)
20.2g) the results of combustion tests of moulded coal composite solid fuel in aforesaid just internal mix sweetening agent (CaCO
3) the results of combustion tests of moulded coal composite solid fuel compare.SO in its combustion processes smoke evacuation
2Through the time change curve be illustrated among Fig. 6.By the comparative result among Fig. 6 as can be known, although the Ca/S=1 of internal mix sweetening agent, the just Ca (OH) of trace of surface attachment
2(0.2g), still, the SO in the smoke evacuation
2Amount is reduced significantly.Desulphurization reaction is not the combustion phases that only limits to fixed carbon (burning beginning back 5-75 minute), and, the SO that is emitted by volatile combustion (burning beginning back 0-5 minute)
2Also pounced on effectively and caught.This is because the Ca (OH) of surface attachment
2The CaO[that decomposes rapidly and produce
] with volatile matter in H
2The SO that S and burning produce
2The result of reaction [
With
]。The desulfurization degree of surface attachment and SO
2And H
2The contact rate of S is big than internal mix also.
Showed the desulfurization result that sweetening agent not of the same race and addition manner are different among Fig. 7.The longitudinal axis is a desulfurization degree among the figure, and transverse axis is also listed sweetening agent kind and different addition manners.The desulfurization dosage of internal mix identical (when being Ca/S=1.5) among the figure.But, surface trace adhere to Ca (OH)
2, make desulfuration efficiency rise about 58% than the desulfuration efficiency (about 35%) that is internal mix.Than inner simple mixing Ca (OH)
2Risen about 18% with the desulfuration efficiency (about 75%) of carbide slag.Ca (OH)
2Higher nearly 2 times with the desulfuration efficiency of carbide slag than Wingdale, than shell high about 10%.
Showed sweetening agent not of the same race among Fig. 8, the desulfurization result that addition and addition manner are different.The longitudinal axis is a desulfurization degree among the figure, and transverse axis is the Ca/S ratio.As known in the figure, although the Ca/S of internal mix sweetening agent is 1,, surface attachment Ca (OH)
2Desulfuration efficiency can reach 93%.This is because the Ca (OH) of surface attachment
2Can effectively catch the H in the fugitive constituent
2S and from the SO of volatile combustion
2And the internal mix of sweetening agent can only be deviate from the SO that the fixed carbon burning produces
2[
；
]。And, surface attachment Ca (OH)
2Desulfuration efficiency not with the Ca/S of internal mix sweetening agent than increasing.
Figure 10 represented with BJ, and the NT coal is the sweetening effectiveness of the moulded coal composite solid fuel made of raw material.At the Ca of the about 0.2g of they surface attachment (OH)
2, change the Ca/S ratio that internal mix is added Wingdale.The longitudinal axis is a desulfurization degree among the figure, and transverse axis is the Ca/S ratio.As shown in this experiment, even Ca/S=1, its desulfuration efficiency also can be up to about 90%.Increase the Wingdale amount (increasing the Ca/S ratio) of internal mix again, its desulfuration efficiency also no longer increases.This experiment also proves once more, the coal different to sulphur content, and the method for this surface attachment sweetening agent is effective, all can make desulfuration efficiency up to about 90%.
Test the cohesiveness and the denitration effect of 6 black liquids.The moulded coal composite solid fuel is by synthetic, and its destruction opposing intensity (destroying under this intensity) is one of important techniques index.Forming pressure, the bonding characteristic of binding agent and addition are all destroyed opposing intensity to this and are produced great influence.This experiment is to be binding agent with the black liquid, changes its addition and forming pressure, measures the destruction opposing intensity of moulded coal.Figure 11 has provided result of experiment.The longitudinal axis has represented to destroy opposing intensity among the figure, and transverse axis is a forming pressure.Mei Strip curve representation certain black liquor containing ratio.As can be seen from Figure, forming pressure is lower than 25MPa (about 250kg/cm
2) time, resisting intensity with the increase destruction of forming pressure obviously increases.But when forming pressure surpassed 25MPa, it was almost certain to destroy opposing intensity.When the containing ratio of black liquor increases, destroy opposing intensity and rise.Yet, after the containing ratio of black liquor surpasses 20% (weight %), destroy opposing intensity and descend on the contrary.As shown in this experiment, being lower than under the forming pressure of 25MPa,, still can reach sufficiently high destruction opposing intensity by the interpolation of binding agent.
Experiment 7 is with nitrogen content 1.1%, sulphur content 2.9% (weight % d.a.f), Chinese Shanxi Province Dongshan mineral products of fuel ratio 4.3 (in the coal in fixed carbon/coal volatile matter) high sulphur coal inferior is mixed and made into the moulded coal composite solid fuel hereinafter to be referred as DS coal (80 weight %) and corn tangerine (20 weight %: sulphur content is similar to 0 in the corn tangerine).Be allowed to condition under the chambers temp of 1073K and burn, when having added black liquid and not added black liquid in the smoke evacuation NO concentration through the time change list be shown among Figure 12.As can be seen from the figure, though added the nitrogen content (because black liquor contains certain nitrogen) when not adding black liquid of nitrogenous (N) amount in the moulded coal composite solid fuel of black liquid,, the NO amount that the former produces in combustion processes is much larger than the latter.The interpolation of black liquid has presented the obvious denitration effect (NO reduces effect) that gets.Figure 13 has showed that the containing ratio with black liquid increases, and denitration rate (NO removes rate) rises in the burning of moulded coal composite solid fuel.When the containing ratio of black liquor was higher than 10%, it is slow that the rising of denitration rate becomes.Finally, denitration rate can reach 40%.
Claims (1)
1, a kind of biologically cleaning briquette as solid fuel is characterized by: in coal dust, mix to add Ca matter sweetening agent, the mol ratio of Ca/S between 1-2, extrusion forming; And the solid-fuelled surface attachment Ca of the moulded coal after moulding (OH)
2Make the moulded coal composite solid fuel that the surface is white in color; Moulded coal surface attachment Ca (OH)
2Amount be the Ca/S mol ratio between 0.1-2, described coal is the sulphur content weight ratio greater than 0.5% coal, makes the moulded coal composite solid fuel that the surface is white in color with it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01102652 CN1224684C (en) | 2001-02-08 | 2001-02-08 | Biologically cleaning briquette as solid fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01102652 CN1224684C (en) | 2001-02-08 | 2001-02-08 | Biologically cleaning briquette as solid fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1368542A CN1368542A (en) | 2002-09-11 |
| CN1224684C true CN1224684C (en) | 2005-10-26 |
Family
ID=4652899
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|---|---|---|---|
| CN 01102652 Expired - Fee Related CN1224684C (en) | 2001-02-08 | 2001-02-08 | Biologically cleaning briquette as solid fuel |
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| CN (1) | CN1224684C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2561102C2 (en) * | 2006-03-31 | 2015-08-20 | ДжейУай Кэпитал Инвестмент ЭлЭлСи | Methods and devices for improvement of solid fuel quality |
| CN100404654C (en) * | 2006-04-18 | 2008-07-23 | 苗冠强 | Industrial honey comb briquette |
| CN102703153A (en) * | 2012-07-02 | 2012-10-03 | 昆明理工大学 | Preparation method of biomass moulding fuel |
| CN105674317B (en) * | 2015-12-21 | 2019-03-22 | 宁波高新区世代能源科技有限公司 | The energy-saving and emission-reduction complete set of equipments of the desulphurization denitration dedusting of high-efficient energy-saving environment friendly |
| CN105505500A (en) * | 2015-12-21 | 2016-04-20 | 宁波高新区世代能源科技有限公司 | Desulfurization, denitration and dust-removal type energy-saving and emission-reduction briquette with effects of high efficiency, energy saving and environment protection |
| CN113061476B (en) * | 2021-03-20 | 2021-10-29 | 河北烈焰机械工程有限公司 | Novel PMC solid fuel |
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