CN1079772A - A kind of coal combustion and sulfur fixation additive and with the method for solid sulphur cinder calcining cement clinker - Google Patents

A kind of coal combustion and sulfur fixation additive and with the method for solid sulphur cinder calcining cement clinker Download PDF

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CN1079772A
CN1079772A CN 93107373 CN93107373A CN1079772A CN 1079772 A CN1079772 A CN 1079772A CN 93107373 CN93107373 CN 93107373 CN 93107373 A CN93107373 A CN 93107373A CN 1079772 A CN1079772 A CN 1079772A
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coal
sulfur
sulphur
cinder
additive
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CN 93107373
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Chinese (zh)
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肖佩林
沈迪新
林国珍
何占源
王玉蓉
李书年
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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Priority to CN 93107373 priority Critical patent/CN1079772A/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • C04B7/44—Burning; Melting
    • C04B7/4407—Treatment or selection of the fuel therefor, e.g. use of hazardous waste as secondary fuel ; Use of particular energy sources, e.g. waste hot gases from other processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A kind of coal combustion and sulfur fixation additive relates to environment protection, the energy and cement manufacture technology field, is used for improving the sulfur-fixing rate of high sulphur content coal in combustion processes, to reduce sulfurous gas to atmospheric pollution.The invention provides the prescription of this additive for sulfur capture, the solid sulphur cinder after the burning can directly be made cement clinker.

Description

A kind of coal combustion and sulfur fixation additive and with the method for solid sulphur cinder calcining cement clinker
One, affiliated technical field
Present technique relates to cement making field in environment protection, the energy and the material of construction.
Two, background technology
China's main energy at present is coal.Power source mainly relies on thermal power plant, and incendiary is a coal.The industrial steam boiler incendiary also mainly is a coal.The coal of China is a lot, most regional pit ash height, and the sulphur content of some regional coal is also quite high.Industrial coal, particularly arcola and Civil energy-saving cooking stove spread all over the place below 4 tons, spread all over town and country, give off a large amount of sulfurous gas (SO in its combustion processes 2), cause the big area topsoil.Because SO 2Under the atmospheric chemistry physical action, can form large-area acid deposition Deng sour gas, and can carry, lake waters, soil, hydrobiont, forest, farm crop etc. are worked the mischief at the atmosphere middle and long distance.Acid rain harm has become one of significant problem of current global environment.Coal is discharged a large amount of boiler ash sediments in industrial furnace and Civil energy-saving cooking stove burning back, is used for the farmland, will change Soil structure, reduces soil fertility, is used to pave the way fill out the hole more in the past.Cinder is stacked not only land occupation in a large number, and causes environmental pollution.The outlet that addresses these problems from science and technology is that coal-fired process reduces SO 2Discharge, and cinder is used as production cement or its auxiliary material, make it resource utilization.China is big coal country, also is to consume the maximum country of coal in the world.Indented material had been done many researchs, obtained many achievements.For example: (1) Chinese patent 85102767 moulded coal heating and producing cement chamotte simultaneouslies; (2) a kind of method of making solidification of sulfur dregs cement of coal-fired sulfur fixing agent or the like Chinese patent 89108564.5(CN1051717A).Shaped coal technology and circular fluid bed have improved thermo-efficiency, have reduced slag, adopt sulphur-fixing agent to make SO in the stack gas simultaneously 2Discharging greatly reduces, and has reduced pollution.But at a large amount of boilers more than 1200 ℃, the sulfur-fixing rate of sulphur-fixing agent is not high at present for furnace temperature, and problem is still serious.
Circulating fluidized bed technique is to adopt fine coal inferior and the part slag is circulated burning to improve thermo-efficiency, temperature of combustion reaches 800-900 ℃, in combustion processes, dose calcium based sulphur-fixation reagent, captured sulfur result can reach 80%, then with slag in order to make cement, shaped coal technology can improve combustion conditions, though add calcium based sulphur-fixation reagent certain captured sulfur result is arranged, but can be because of the grate firing boiler furnace temperature up to 1200 ℃, sulfur-fixing rate is not as good as 50% usually, and slag fails to utilize.
Three, purpose of the present invention
The task of the technology of the present invention is the deficiency that overcomes prior art, prepares a kind of novel additive for sulfur capture to improve sulfur-fixing rate in the coal-fired process, and the slag that will consolidate sulphur then is used for making cement clinker.Purpose of the present invention just provides this novel additive for sulfur capture prescription of preparation and utilizes solid sulphur slag to make the method for cement clinker.
Four, technical scheme of the present invention
1, theoretical explanation
When in the coal during sulfur-bearing, issue in the strong atmosphere of incendiary and to give birth to the row reaction:
R is an organic group
The pyrite thermolysis
When sulphur content in the coal surpasses 1%, contain SO 2Flue gas just can cause remarkable atmospheric pollution.Surpass 3% fire coal district in some sulphur content and usually SO in the atmosphere can occur 2Heavily contaminated.
When removing SO with calcium based sulphur-fixation reagent 2The time, its reaction is:
The suitable temperature range of this reaction is below 900 ℃, when furnace temperature surpasses 900 ℃, and formed CaSO 4, resolve into SO again 2, i.e. the reversed reaction of above-mentioned reaction.To grate firing boiler, furnace temperature usually reaches 1200 ℃ or higher, thereby is difficult to obtain satisfied captured sulfur result.
Applied catalysis theory of the present invention as catalyzer, makes SO with iron silicon based compound 2Generate 3CaO.3Al 2O 3.CaSO 4Complex inorganic salt catalyst, delayed CaSO 4Decomposition, add Si oxide simultaneously and form and to comprise CaSO 4, CaO, Fe 2O 3, SiO 2At an interior stable Solid solution, thereby be that fixedly sulphur is created a good condition, to have improved sulfur-fixing rate.The slag that the past boiler is discharged is regarded as solid waste, and being mainly used in paves the way fills out the hole.Yet the solid sulphur cinder through aforesaid method is handled contains Fe because of it is added with in combustion processes, the additive of Si, and its content can be regulated, and the chemical ingredients of burning back slag can become cement clinker through aftertreatment within the scope of cement composition.
2, the technology of the present invention content
The laboratory study of present technique is to have in the electric tube furnace that carries temperature control unit at one to carry out, and uses the platinum platinum-rhodium thermocouple thermometric, and the temperature of electric furnace evenly rises to 1300 ℃ by room temperature, and its heat-up rate can be controlled by temperature control unit.During test the coal for preparing is stretched in the stove by electric furnace one end, air feeds the other end by an end, with SO 2Survey meter links.
Test is a raw coal with the self-sufficient and strategically located region, Sichuan coal, and its coal analysis is as follows:
Table 1 coal analysis data
Coal C f% A f% V f% S f% Q f DTMJ H f% N f%
Self-sufficient and strategically located region bituminous coal 54.94 34.00 15.85 3.58 22.45 3.29 0.93
Table is annotated: C ' in the table: the as analysed basis carbon content (%, weight percent, down together): A ': ash content; V ': fugitive constituent; S ': sulfur; Q ' MJ: calorific value; H ': hydrogen part; N ': nitrogen part.
Sulphur-fixing agent is a unslaked lime, and its total calcium is 96%, if then should analyze effective calcium and full calcium contents with building lime, and is converted into the content of above-mentioned unslaked lime.
The additive for sulfur capture prescription is as follows: 1 part of (weight ratio, down together)+α Fe of unslaked lime 2O 31 part+α SiO 21 part, in ball mill, grind and 200 orders that sieve, standby.
During experiment, adopt following prescription:
Coal (80-95) %+ unslaked lime (4-15) %+ additive for sulfur capture (1-5) %
Contrast contains additive and the captured sulfur result that does not contain the additive coal blending.
As can be seen from the above table, under similarity condition, the sulfur-fixing rate of coal blending that contains additive for sulfur capture is more than the height that does not contain additive.
Two kinds of methods have been adopted in coal blending, and one is the laggard stove of powder material uniform mixing, and another uses 200kg/cm for after adding a little binder (polyvinyl alcohol) 2Moulded coal is made in the small-sized oil press moulding of pressure, and relatively its captured sulfur result comes to the same thing.Therefore present technique both had been applicable to the moulded coal combustion processes, also was applicable to the combustion processes of coal-powder boiler.
The slag that contains additive for sulfur capture is carried out X-ray powder crystalline diffraction method and the X-fluorescent spectrometry is analyzed, can obviously find out CaSO from the powder crystal diffractogram 4Crystalline exists and and FeSO 3And SiO 2Symbiosis has formed a stable Solid solution, has played captured sulfur result.
X-fluorescent spectroscopy result such as following table.
The solid sulphur slag X-fluorescent spectroscopy result of table 3
Content (%) Fe Ca Si Al Ti S
Metal 5.71 22.28 11.54 10.22 0.79 10.25
Metal oxide 8.16 31.2 24.6 19.3 1.34 20.6
Five, useful effect
The present invention compares with background technology, has the following advantages:
1, grate firing Industrial Boiler furnace temperature generally can reach 1200 ℃, even higher, and existing sulphur-fixing agent captured sulfur result adds that not as good as 50% additive for sulfur capture of the present invention then can reach about 80%, pollutes more useful to controling environment;
2, the technology of the present invention technology is simple, and raw material is cheap and easy to get, promotes the use of easily;
3, the technology of the present invention has solved the environmental problem that the Industrial Boiler slag is caused, and makes it resource utilization, makes cement clinker, and economic benefit is considerable.
Therefore, we can say the economic benefit of the technology of the present invention, environmental benefit, social benefit are all relatively good.
Six, embodiment
In the simulation port that a device is hundreds of gram coals, carried out the experiment that the solid sulphur formed coal examination is burnt.
In order to make furnace temperature keep constant, stove inwall and nichrome wire have twined insulation effect, and nichrome wire is the naked light heating, has also played ignition action, when actual examination is burnt, moulded coal consumption 300g, use following prescription:
I raw coal moulded coal: Guizhou bituminous coal 95%(content sulfur content 5.5%)+polyvinyl alcohol 5%.
The II raw coal adds the unslaked lime moulded coal: Guizhou bituminous coal 80%+ unslaked lime 15%+ polyvinyl alcohol 5%.
The III solid sulphur formed coal, Guizhou bituminous coal 80%+ unslaked lime 15%+ polyvinyl alcohol 5% adds 1% iron silicon additive for sulfur capture.
Above-mentioned three kinds of prescriptions are respectively in above-mentioned port internal combustion, and measure SO in the exhaust with the sulphur dioxide measuring instrument 2Content (ppm) calculates the sulfur-fixing rate of three kinds of prescriptions
Adopt following formula during calculating
R＝[1- (CV)/(2AS) ]×100
R is a sulfur-fixing rate in the formula; C is SO in the flue gas 2Concentration (measured value; Mg/Nm 3); V is flue gas flow rate (Nm 3/ h); A is coal consumption speed (kg/h); S be sulphur content in the coal (wt, %).
After the burning, its result is as calculated: prescription I sulfur-fixing rate is 40%, and prescription II sulfur-fixing rate is 55%, and prescription III sulfur-fixing rate is 80%.
The slag of prescription III has carried out observing on scanning electron microscope and with 425 #Cement compares, and the two is apparent very similar, sees the Calucium Silicate powder phase of the solid sulphur cinder of Fig. 1, and Figure 24 25 #The Calucium Silicate powder phase (being photo) of cement.Through chemical analysis, the results are shown in Table 4.
Figure 931073731_IMG3
III prescription cinder and 425 #The cement composition is variant, but within the cement composition variation range, after processing, can become cement clinker.

Claims (4)

1, the method for a kind of coal combustion and sulfur fixation additive and solid sulphur cinder making cement clinker thereof, in the coal of high sulphur content, add calcium based sulphur-fixation reagent (CaO) reduces sulfur dioxide of flue gases in combustion processes discharging, make cement with solid sulphur cinder then, it is characterized in that the applied catalysis theory, add iron silicon based compound and be catalyzer to improve sulfur-fixing rate, make it to form one and comprise CaSO 4, CaO, Fe 2O 3, SiO 2Stable Solid solution interior can be used for directly making cement clinker.
2, coal combustion and sulfur fixation additive according to claim 1 is characterized in that including 1 part of unslaked lime (CaO), α Fe 2O 31 part and α SiO 21 part (by weight).
3, according to claim 1,2 described coal combustion and sulfur fixation additives is characterized in that it can mix to make the moulded coal afterfire in the coal, also can mix coal dust and directly burn.
4, the solid sulphur cinder according to claim 1 method of making cement clinker is characterized in that because coal, and the difference of ature of coal can be regulated the catalyst component of additive for sulfur capture.
CN 93107373 1993-06-25 1993-06-25 A kind of coal combustion and sulfur fixation additive and with the method for solid sulphur cinder calcining cement clinker Pending CN1079772A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007071A1 (en) * 1995-08-14 1997-02-27 Bureau Of Administrative Service, The Chinese Academy Of Sciences Process for producing heat and cement clinkers in one boiler, its products, the equipment used and its uses
CN1047373C (en) * 1995-08-14 1999-12-15 中国科学院 One furnace two purpose simultaneously concurrent heat and cement clinker producing method, equipment and product
CN113213858A (en) * 2021-05-14 2021-08-06 中国科学院生态环境研究中心 Method for preparing aluminate-based 3D printing material by gasifying slag

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007071A1 (en) * 1995-08-14 1997-02-27 Bureau Of Administrative Service, The Chinese Academy Of Sciences Process for producing heat and cement clinkers in one boiler, its products, the equipment used and its uses
AU713233B2 (en) * 1995-08-14 1999-11-25 Bureau Of Administrative Service, The Chinese Academy Of Sciences Process for producing both steam power and cement clinker simultaneously in one apparatus its products, apparatus and use
CN1047373C (en) * 1995-08-14 1999-12-15 中国科学院 One furnace two purpose simultaneously concurrent heat and cement clinker producing method, equipment and product
US6468345B1 (en) 1995-08-14 2002-10-22 The Chinese Academy Of Sciences Process for producing both steam power and cement clinker simultaneously in one apparatus its products, apparatus and use
CN113213858A (en) * 2021-05-14 2021-08-06 中国科学院生态环境研究中心 Method for preparing aluminate-based 3D printing material by gasifying slag
CN113213858B (en) * 2021-05-14 2022-08-23 中国科学院生态环境研究中心 Method for preparing aluminate-based 3D printing material by gasifying slag

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