CN101033430A - Fire coal sulfur-fixing agent and sulfur-fixing type fire coal for the same - Google Patents
Fire coal sulfur-fixing agent and sulfur-fixing type fire coal for the same Download PDFInfo
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- CN101033430A CN101033430A CN 200710078216 CN200710078216A CN101033430A CN 101033430 A CN101033430 A CN 101033430A CN 200710078216 CN200710078216 CN 200710078216 CN 200710078216 A CN200710078216 A CN 200710078216A CN 101033430 A CN101033430 A CN 101033430A
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Abstract
This invention relates to a sulfur-fixing agent of coal and its coal with fixed sulfur, in which, the sulfur-fixing agent is composed of crushed master and assistant materials, and the master one is lime or calcium oxide, the assistant material is a biology material of farming and forest or plant ash generated by burning them, the percentage of the master material is 40-70% and that of the assistant material is 60-30%, in which, the coal with fixed sulfur is formed by mxing and processing the crushed raw coal with the sulfur-fixing agent in the rate of 2-20%.
Description
Technical field
The present invention relates to administer coal-fired SO
2The additive for sulfur capture of discharging and mixed the fire coal of this additive.
Background technology
Along with the minimizing day by day of petroleum resources, coal will be China's main Energy resources for a comparatively long period of time.China is coal-fired big country, and coal accounts for 75% of primary energy source total quantity consumed.In China, in the coal production, sulphur content accounts for 70% at the low sulphur coal below 1%, and wherein sulphur content is lower less than 0.5% ratio, and high sulphur coal output is near 1/5 of national coal ultimate production.The coal usage quantity of China is 1,300,000,000 tons/year, uses the environment-friendly type fire coal only less than 100 tons/year.Along with the continuous growth of consumption of coal, coal fire discharged sulfurous gas also constantly increases, and surpasses 2,000 ten thousand tons for years, occupies first place in the world, causes China's acid rain and sulfur dioxide pollution to be on the rise.Therefore, the exploitation of coal combustion and sulfur fixation technology is very important with research.
In clean coal technology, main purpose is to administer SO
2Quantity discharged, at present main method has 3 kinds: the solid sulphur of solid sulphur, combustion desulfurization and flue gas before the burning.Wherein, combustion desulfurization is to add absorption agent in coal combustion process, makes it and sulfur dioxide gas precursor reactant, reaches the effect of solid sulphur.Relative other sulfur solidifying techniques, combustion desulfurization have simple, the solid sulphur low cost and other advantages of technology, are well suited for China's national situation, and therefore the value of research and extension arranged.
The sulphur-fixing agent that generally adopts is Wingdale or unslaked lime at present.Main component in the unslaked lime is the main component CaCO of CaO, Wingdale
3The CaO that is generated by " sintering " back (so being also referred to as calcium based sulphur-fixation reagent).Its solid sulphur principle is CaO and SO in burning situation
2Chemical combination generates CaSO
4, SO
2Just to be converted to CaSO
4Existence form be cured and kept.Like this, just reduce SO
2Discharging, reached improvement SO
2The purpose of discharging.Yet, because the CaSO that generates behind the solid sulphur
4Molecular volume is big, makes the CaSO that very thin and intensive pore is generated in the CaO particle
4Stop up, thereby stoped SO
2Diffusion to its inside has limited solid sulphur efficiency and sulphur-fixing agent utilization ratio.Therefore, be major ingredient (or claiming host) with Wingdale or unslaked lime, a class coal-fired sulfur fixing agent that adds an amount of auxiliary material (or claiming auxiliary agent) has more just arisen at the historic moment.In the patent documentation of having reported, all adopt the chemical reagent of interpolation alkali metal containing oxide compound and the solid sulphur efficiency that industrial waste improves sulphur-fixing agent.Mainly be in burning, to produce porous mass (itself also has porosity characteristic the auxiliary material that has), the sulphur-fixing agent particle that contains CaO is blended in the porous mass, improving its specific surface area, and then improve and allow SO by auxiliary material
2Probability to CaO particle internal diffusion.Include in this class coal-fired sulfur fixing agent, the patent No. is the coal-fired sulfur fixing agent in " a kind of efficient composite sulphur-fixing agent for coal burning fume " of ZL98114090.4: the patent No. is the coal-fired sulfur fixing agent in " a kind of efficient fuel coal sulfur stabilizing agent and its production and use " of ZL01114874.8.The former is a major ingredient with the Wingdale, has added MgO, MnO
2, Fe
3O
4, BaO, NaNO
2, V
2O
5, B
2O
3With multiple auxiliary materials such as tertiary butyl diamyl iron; The latter is a major ingredient with the Wingdale also, has added multiple auxiliary materials such as rhombohedral iron ore, magnesite, solid alkaline thing, scrap iron powder commercial catalysts and/or industrial soda.Though they have all improved solid sulphur efficiency and sulphur-fixing agent utilization ratio to a certain extent.But they all have the following disadvantages again: (1) described auxiliary material all is industrial reagent or industrial chemicals, and cost is higher relatively; (2) used auxiliary material component complexity is of a great variety, and proportioning is regulated difficulty relatively, makes troubles to practice, more is unfavorable for promoting; (3) actual solid sulphur efficiency is still on the low side.
Summary of the invention
First purpose of the present invention provides a kind of cheapness, coal-fired sulfur fixing agent efficiently, to overcome cost height of the prior art, component complexity, poor operability and solid sulphur efficiency problem on the low side.
Second purpose of the present invention provides a kind of sulfur-fixing type fire coal that has added above-mentioned coal-fired sulfur fixing agent, to simplify solid sulphur operation and relevant device, the solid sulphur cost of reduction.
For realizing first goal of the invention, provide a kind of like this coal-fired sulfur fixing agent.Aspect same as the prior art is, this coal-fired sulfur fixing agent also is made up of chippy major ingredient and auxiliary material, and its major ingredient is Wingdale or unslaked lime.Its improvements are, the auxiliary material among the present invention is agriculture and forestry biomass materials or the plant ash that produced by these agriculture and forestry biomass materials afterburnts.As everyone knows, in the described agriculture and forestry biomass materials, include straw, wood chip, stalk etc., especially the depleted agriculture and forestry biomass materials can be used especially.
For realizing second goal of the invention, provide a kind of like this sulfur-fixing type fire coal.This sulfur-fixing type coal-fired for chippy raw coal and coal-fired sulfur fixing agent by mixing, forming after the forming process.The weight percent that coal-fired sulfur fixing agent is mixed in the raw coal is 2%～20%.
From the scheme that realizes first goal of the invention, following as can be seen advantage:
(1) auxiliary material that is comprised in the coal-fired sulfur fixing agent of the present invention has not had industrial reagent of the prior art or industrial chemicals, but at very easy obtain and the agriculture and forestry biomass materials that normally gone out of use (straw, wood chip, stalk etc.) in vast rural area and forest zone.Replace industrial soda metal oxide reagent with an alkali metal salts such as the soluble potassium in these agroforestry wastes, sodium, reached waste recycling, reduced the purpose of sulphur-fixing agent cost greatly;
(2) agriculture and forestry biomass materials (plant ash) of burning after the ashing has porous, fluffy, characteristics that specific surface area is big, is that auxiliary material mixes with major ingredient with it, can improve the dispersity and the effective ratio area of major ingredient Wingdale or unslaked lime, improves SO
2Transmission path in the major ingredient hole increases SO
2With the reactive behavior point of CaO, thereby further improved the utilization ratio of solid sulphur efficiency and sulphur-fixing agent;
(3) because the auxiliary material among the present invention is actually this one-component of the plant ash that utilizes agriculture and forestry biomass materials to produce after burning, therefore, the proportion relation that does not just have the sort of complexity that existence brought because of multiple auxiliary material of the prior art with regard to auxiliary material itself, when reality is made, only need characteristics, do limited routine test several times and just can determine corresponding blending ratio exactly according to different biological materials; Especially in the vast rural area and the forest zone of advocating " with coal for wood " at present energetically, for friend peasant and Lin worker, grasp also not difficult, promote nature and also be very easy to.
In conjunction with the introduction of background technology, can also be clear that, be major ingredient with Wingdale or unslaked lime, be auxiliary material is produced coal-fired sulfur fixing agent with the alkalimetal oxide, become those skilled in the art's common recognition already; Regulate in the coal-fired sulfur fixing agent proportioning between the major ingredient and auxiliary material and when reality is used, in raw coal, add the coal-fired sulfur fixing agent ratio according to the sulphur content in the different raw coal, only all become and just can draw the conventional means of its correct value by limited simple experiment several times.Therefore, distinguishing characteristics of the present invention is the component of auxiliary material in the coal-fired sulfur fixing agent and is not proportioning and specific implementation process thereof.
From the scheme that realizes second goal of the invention, can clearly be seen that the present invention has added the so-called sulfur-fixing type fire coal made in the raw coal into to above-mentioned coal-fired sulfur fixing agent.Its great advantage is, people can go burning as using existing fire coal put them into various coal furnaces fully, and it not only can not influence coal-fired other performances (as thermal value), and existing coal furnace all needn't be transformed.Like this, not only further reduce the input of environmental protection fund, but also improved available scope widely.This uses the relative area that falls behind any with forest zone or economy, coal-fired rural area to remaining single household so far, and its value of environmental protection is just more great.
The present invention is further illustrated with embodiment below.
Embodiment
A kind of coal-fired sulfur fixing agent, aspect same as the prior art be, this coal-fired sulfur fixing agent also is made up of chippy major ingredient and auxiliary material, and its major ingredient is Wingdale or unslaked lime.Auxiliary material among the present invention is agriculture and forestry biomass materials or the plant ash that produced by these agriculture and forestry biomass materials afterburnts.Agriculture and forestry biomass materials comprises straw, wood chip, stalk etc.Major ingredient among the present invention can adopt the unslaked lime of natural limestone or industrial waste.
Usually, according to sulphur content in the different raw coal and concrete agriculture and forestry biomass materials (straw, wood chip or stalk) or the determined proportional range of selecting of its corresponding plant ash be, the weight percent content of major ingredient is 40%～70%, and the weight percent content of auxiliary material is 60%～30%.Obviously, when auxiliary material during for unburned agriculture and forestry biomass materials still, should be to the upper limit side of this ratio value; When auxiliary material is the plant ash in afterburnt, should be to the lower limit side of this ratio value.
Further, this coal-fired sulfur fixing agent can use as using method of the prior art fully.But best using method is, itself and chippy raw coal mixed make the sulfur-fixing type fire coal.This sulfur-fixing type coal-fired for chippy raw coal and coal-fired sulfur fixing agent by mixing, forming after the forming process.Obviously, blending ratio also needs to determine according to the sulphur content in the different raw coal.Usually, to be mixed into the weight percent in the raw coal be 2%～20% to coal-fired sulfur fixing agent.
Above-mentioned coal-fired sulfur fixing agent and sulfur-fixing type fire coal thereof can more need not to add other main equipments with existing relevant device or device direct production fully.
With in vitro part test and checking, the advantage of the present invention improving solid sulphur efficiency illustrates below.
Checking example one:
With after the straw burning, pulverize rice-straw ash, get granularity and mix with unslaked lime 6g less than 40 purpose rice-straw ash 4g, add the less water ageing afterwards 1 day that stirs, promptly get sulphur-fixing agent; Raw coal is got granularity and is pulverized raw coal 200g less than 40 purposes at first through pulverizing, and mixes with above-mentioned sulphur-fixing agent and an amount of clay and water, is the sulfur-fixing type fire coal after adopting traditional technology machine-shaping, drying.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged is 20～35mg/g (raw coal); The SO of sulfur-fixing type fire coal
2Quantity discharged is 3～5mg/g (a sulfur-fixing type fire coal).Calculating sulfur-fixing rate is 78.3%.
Checking example two:
After the straw pulverizing, to get granularity and mix less than 40 purpose straw 5g and unslaked lime 5g, ashing under the condition of normal temperature, normal pressure, natural ventilation promptly gets sulphur-fixing agent; Raw coal (granularity is less than 40 orders) after getting 200g and pulverizing mixes with above-mentioned sulphur-fixing agent and an amount of clay and water, is the sulfur-fixing type fire coal after adopting traditional technology machine-shaping, drying.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged is 20～35mg/g (raw coal); The quantity discharged of sulfur-fixing type fire coal is 0.8～3.0mg/g (a sulfur-fixing type fire coal), and calculating sulfur-fixing rate is that sulfur-fixing rate is 81.7%.
Checking example three:
Wood-processing industry depleted wood chip is burnt under the condition of normal temperature, normal pressure, natural ventilation fully, pulverize wood ash, get granularity and mix with unslaked lime 7g, add the less water ageing afterwards 1 day that stirs, promptly get sulphur-fixing agent less than 40 purpose wood ash 3g; Raw coal is got granularity and is pulverized raw coal 200g less than 40 purposes at first through pulverizing, and mixes with above-mentioned sulphur-fixing agent, and the clay and the water of ginseng amalgamation certainty ratio stir, and adopt traditional technology machine-shaping, be drying to obtain the sulfur-fixing type fire coal.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged is 20～35mg/g (raw coal); The SO of sulfur-fixing type fire coal
2Quantity discharged is 6～9mg/g (a sulfur-fixing type fire coal), and calculating sulfur-fixing rate is 68.4%.
Checking example four:
After wood-processing industry depleted wood chip pulverized, get granularity and mix with unslaked lime 7g, add the less water ageing afterwards 1 day that stirs, promptly get sulphur-fixing agent less than 40 purpose wood chip 3g; Raw coal is got granularity and is pulverized raw coal 200g less than 40 purposes at first through pulverizing, and mixes with above-mentioned sulphur-fixing agent, and the clay and the water of ginseng amalgamation certainty ratio stir, and adopt traditional technology machine-shaping, be drying to obtain the sulfur-fixing type fire coal.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged is 20～35mg/g (raw coal); The SO of sulfur-fixing type fire coal
2Quantity discharged is 8～13mg/g (a sulfur-fixing type fire coal), calculation result, and sulfur-fixing rate is 60.8%.
Checking example five:
After the stalk perfect combustion ashing with agriculture waste, pulverize, get granularity, mixes, add the less water ageing afterwards 1 day that stirs, promptly get sulphur-fixing agent with 5g unslaked lime less than 40 purpose ash 5g; Raw coal is got granularity and is pulverized raw coal 200g less than 40 purposes at first through pulverizing, mixes with above-mentioned sulphur-fixing agent, and the clay and the water of ginseng amalgamation certainty ratio, the back that stirs is adopted traditional technology machine-shaping, is drying to obtain the sulfur-fixing type fire coal.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged is 20～35mg/g (raw coal); The quantity discharged of sulfur-fixing type fire coal is 4～6mg/g (a sulfur-fixing type fire coal), and calculating sulfur-fixing rate is 76.8%.
Checking example six:
With the crushed stalk of agriculture waste, get granularity and mix less than 40 purpose stalk 5g and unslaked lime 5g, after burning ashing under the condition of normal temperature, normal pressure, natural ventilation, add the less water back ageing 1 day that stirs, be sulphur-fixing agent; With the raw coal grinding and sieving, get the 200g granularity less than 40 purpose raw coal, mix with above-mentioned sulphur-fixing agent and an amount of clay, stir, adopt traditional technology machine-shaping, be the sulfur-fixing type fire coal after the seasoning.Raw coal burns under identical condition respectively with the sulfur-fixing type fire coal, promptly all at 800 ℃ of burning 1h, all adopt formaldehyde solution to absorb respectively to the tail gas that is produced after, with the SO of its release of spectrophotometry
2Amount.The SO of raw coal
2Quantity discharged 20～35mg/g (raw coal); The SO of sulfur-fixing type fire coal
2Quantity discharged is 2～5mg/g (a sulfur-fixing type fire coal), and calculating sulfur-fixing rate is 78.6%.
Claims (3)
1, a kind of coal-fired sulfur fixing agent, this coal-fired sulfur fixing agent is made up of chippy major ingredient and auxiliary material, its major ingredient is Wingdale or unslaked lime, it is characterized in that, described auxiliary material is agriculture and forestry biomass materials or the plant ash that produced by these agriculture and forestry biomass materials afterburnts.
2, coal-fired sulfur fixing agent according to claim 1 is characterized in that, the weight percent content of major ingredient is 40%～70%, and the weight percent content of auxiliary material is 60%～30%.
3, a kind of sulfur-fixing type fire coal that has mixed claim 1 or 2 described coal-fired sulfur fixing agents is characterized in that, this sulfur-fixing type coal-fired for chippy raw coal and described coal-fired sulfur fixing agent by mixing, forming after the forming process; The weight percent that described coal-fired sulfur fixing agent is mixed in the raw coal is 2%～20%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710078216 CN101033430A (en) | 2007-02-13 | 2007-02-13 | Fire coal sulfur-fixing agent and sulfur-fixing type fire coal for the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710078216 CN101033430A (en) | 2007-02-13 | 2007-02-13 | Fire coal sulfur-fixing agent and sulfur-fixing type fire coal for the same |
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|---|---|
| CN101033430A true CN101033430A (en) | 2007-09-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014179904A1 (en) * | 2013-05-07 | 2014-11-13 | Lei Xuejun | Method for planting, shaping for carbon sequestration and storage, and comprehensive utilization of fast-growing plant |
| CN115029170A (en) * | 2022-06-08 | 2022-09-09 | 华东理工大学 | Sulfur-fixing additive for sulfur emission treatment of fire coal and preparation method thereof |
-
2007
- 2007-02-13 CN CN 200710078216 patent/CN101033430A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014179904A1 (en) * | 2013-05-07 | 2014-11-13 | Lei Xuejun | Method for planting, shaping for carbon sequestration and storage, and comprehensive utilization of fast-growing plant |
| CN115029170A (en) * | 2022-06-08 | 2022-09-09 | 华东理工大学 | Sulfur-fixing additive for sulfur emission treatment of fire coal and preparation method thereof |
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Open date: 20070912 |