CN107573980A - A kind of coal supply chain combustion adjuvant and preparation method thereof - Google Patents
A kind of coal supply chain combustion adjuvant and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of coal supply chain combustion adjuvant and preparation method thereof, by 2 10 parts of 20 30 parts of pickling iron and steel waste residue, 20 25 parts of flyash, 5 10 parts of white lime, 10 25 parts of coke blacking and lanthanum-cerium chloride dispensings, Ca-Ti ore type catalysis material La is generated by high temperature thermal chemical reaction0.51Ce0.49FeO3And inorganic salt mixt, further it is crushed to 100 200 mesh and obtains.By its using in the incorporation coal of mass percent 0.2% 5.0% as solid sulphur denitration combustion adjuvant, the sulfur-fixing rate of environment friendly combustion-supporting agent is 60% 85% during coal burning, and denitration rate is 50% 75%.Coal supply chain combustion adjuvant of the present invention not only reduces sulfur dioxide and the nitrogen oxide contaminants discharge of coal burning, and can solve pickling iron and steel waste residue and flyash is difficult to pollution problem caused by handling, and realizes the treatment of wastes with processes of wastes against one another and comprehensive utilization.
Description
Technical field
The present invention relates to a kind of coal supply chain combustion adjuvant and preparation method thereof, in particular with waste residue caused by pickling iron and steel
The method that comprehensive utilization prepares coal supply chain combustion adjuvant, belong to environmental protection and field of new materials.
Background technology
In recent years, both there is Trans-Provincial/Municipal, gray haze a wide range of, seasonality is strong, the duration is short in China, also occurred
Local, small range, normalization, duration very long gray haze.According to Beijing PM2.5Origin analysis newest research results, north
Capital city whole year PM2.5In source, area transmissions " contribution " account for 28%~36%, and local disposal of pollutants " contribution " accounts for 64%~72%.
In this ground contamination " contribution ", vehicular emission (31.1%), coal-fired (22.4%), the proportion of industrial production (18.1%) occupy first three
Position.It is that current China is big according to national environmental monitoring work on-the-spot meeting in 2015, motor vehicle, industrial production, fire coal, airborne dust etc.
The main pollution source of particulate matter, accounts for 85%-90% in the surrounding air of urban.
China is currently in the high speed development stage for moving towards modernization, is undisputed world's factory, consumes every year
The coal in the whole world about 1/2, coal account for primary energy consumption in more than 70%.If motor vehicle is the PM in city2.5Member
It is fierce, then coal burning is clearly small and medium-sized cities PM2.5Arch-criminal.Limiting emission measure is presently mainly taken, with greater need for research
Exploitation know-how is administered from source, reduces the total emission volumn of atmosphere pollution.Try hard at present with natural gas and fuel oil replacement
Coal, to reduce the measure of pollution, but there is a problem as industrial production energy supply in financial cost, it is difficult to large area
Popularization and application, in the period of modern the latter is longer in, coal will be the most important energy in China.In coal containing a large amount of sulphur and
Nitrogen, it is difficult to efficiently separate before combustion；And desulfurization and denitrogenation need to invest huge Special Equipment and flower from flue gas after burning
Taking high operating cost, small and medium-sized manufacturing enterprises are often difficult to bear, so, coal combustion-promoting agents are researched and developed again by wide
General attention.
Coal combustion-promoting agents can improve the precipitation rate of volatile matter in coal, reduce the ignition temperature of coal, shorten igniting and prolong
The slow time, accelerate coal burnout rates, reduce ash content carbon residue, improve efficiency of combustion, relative increase combustion heating amount, and have companion
There is the advantages that desulfurization removing nitric.Coal combustion-promoting agents are further divided into combustion adjuvant, sulfur-fixating combustion promoter, denitration combustion adjuvant and solid sulphur
Denitration combustion adjuvant etc..Combustion adjuvant can be divided into alkali or alkaline-earth metal class combustion adjuvant, transition metal-type combustion adjuvant, rare earth by chemical composition
Metal oxide-type combustion adjuvant, composite oxides combustion adjuvant etc..Common combustion adjuvant includes Na2CO3、K2CO3、Ca(NO3)2、Ca
(OH)2、CaO、KCl、NaCl、Al2O3、KMnO4、MnO2、Fe2O3、FeCl2、FeCl3、CuO、CuSO4、 ZnO、ZnCl2、CeO2With
La2O3Deng.
Absorption conversion of the nitrogen oxide to sulfur dioxide with catalysis and acts synergistically in air, strengthens denitration technology research and development,
It is the current important measures for administering haze nitrogen oxide contaminants is translated into nitrogen before air is not discharged into.It is intended that
Increase solid sulphur denitration function on the basis of the original function of coal combustion-promoting agents, add, make in coal in the combustion process of coal
Convert sulfur compounds enter clinker for stable sulfate, the nitrogen compound in coal is converted into nitrogen discharge.Patent is public
The solid sulphur denitration combustion adjuvant of coal opened is mainly Ca, Mg, Ba, K, Na, Al, Fe, Cu, Mn, Zn, Si compound；Rare earth miberal powder, mistake
Cross metal mining powder, flyash, carbide slag, diatomite and biomass etc..For example, KeYu Genie et Environnement of Ma'an Mountain exists
Chinese patent CN106350147A（ 2017-01-25）In disclose a kind of high performance coal saving and combustion aid denitrfying agent and preparation method thereof,
Including following raw material：Chlor-alkali salt sludge slag, flyash, dialkyl titanocenes, calcium metatitanate, tin indium oxide, improve the combustion of fire coal
Efficiency is burnt, coal conservation reaches more than 6%, and nitrogen oxides reduces 28% or so, and chlor-alkali salt sludge slag is effectively utilized；Chenzhou Hui Kang
Science and technology limited Company is in Chinese patent CN106190430A（2016-12-07）In to disclose a kind of desulphurization denitration combustion-supporting
Agent and its application in fire coal, desulphurization denitration combustion adjuvant are made up of component as follows by mass percentage：Rape cake 40%-
70%, carbon ammonium 10%-15%, gangue 2%-6%, sodium nitrate 0.3%-1%, potassium permanganate 0.1%-0.5%, aluminum sulfate 3%-6% are acidified,
Sodium chloride 1%-10%, potassium chlorate 2%-8%, manganese dioxide 0.3%-0.7%, sodium phosphate 3%-5%, soda ash 5%-10%, SO in flue gas2And
NOxRemoval efficiency reach more than 80%, flue dust can reduce by more than 70%, and coke cleaning, the effect of inhibition can reach more than 90%；It is interior
Mongolian University of Science and Technology is in Chinese patent CN105289267A（2016-02-03）In disclose a kind of coal desulfurization denitrfying agent and its
Preparation method, rare-earth tailing is milled to 200 mesh with ball mill, is then placed in Muffle furnace and sinters, be fabricated to porous material,
By crusher in crushing into millimetre-sized particle, then will it is broken after particle add in agstone, wherein the particle after broken
Quality accounts for the 1%-8% of agstone quality；Eternal prosperous Science and Technology Development Co., Ltd. of Harbin City is in Chinese patent
CN104974813A （2015-10-14）In disclose a kind of coal-fired combustion-supporting additive for saving energy, mainly by nitrification rare earth, chlorination
Sodium, magnesium nitrate, potassium permanganate, nitric acid are by composition, the percentage by weight of each component：Nitrify rare earth 5-15%, sodium chloride 5-20%,
Magnesium nitrate 10-20%, potassium permanganate 5-10%, nitric acid press 5-10%, and its surplus forms for water；The limited public affairs of Gansu Black horse petrochemical industry project
Department is in Chinese patent CN103194295A（2013-07-10）In disclose the combustion-supporting denitrfying agent composition of boiler fired coal and its preparation
Method, composition are made up of the raw material of following portions by weight：Sodium carbonate 2-8 parts, aluminium hydroxide 3-7 parts, ferric trichloride 2-5, urine
Plain 6-15 parts, ammonium carbonate 4-10 parts, ammonium chloride 4-10 parts, di-iron trioxide 3-9 parts, potassium permanganate 7-22 parts, potassium chlorate 7-22
Part, active attapulgite carclazyte 15-40 parts, chrome green 4-8 parts, manganese oxide 2-6 parts, zinc oxide 4-8 parts, copper chloride 4-8 parts,
Cupric oxide 2-6 parts, copper carbonate 2-6 parts, zinc sulfate 3-7 parts, zinc nitrate 2-5 parts, barium molybdate 0.5-1.5 parts, titanium oxide 1-2 parts,
Vanadic anhydride 0.5-1.5 parts, copper sulphate 0.2-0.5 parts, cerium oxide 0.2-0.5 parts, penetrating agent JFC 1-3 parts and sulfomethylated lignin
Hydrochlorate 0.1-0.2 parts；Hunan Shengtong Technology Group Co., Ltd is in Chinese patent CN103160356A（2013-06-19）Middle public affairs
Open combustion-supporting solid sulfide denitration and devoke integrated additive for fire coal and its preparation method and application, the composition of additive for fire coal and each
The percentage by weight of composition is respectively：MnO2：13%-27%；Fe2O3：8%-22%；CaO：8%-22%；CuO：2%-9%；KNO3：6%-
18%；KMnO4：2%-12%；Al2O3：3%-14%；SiO2：2%-7%；Cu(NO3)2：2%-11%；Al(NO3)3：4%-12%；TiO2：
0.5%-4%；Middle material international environment engineering（Beijing）Co., Ltd is in Chinese patent CN102618348A（2012-08-01）Middle public affairs
Cement industry denitration combustion adjuvant of economizing on coal is opened, by sodium perchlorate as oxygenation agent；By sodium chloride as leavening agent；It is inclined by six
Sodium phosphate is as dispersant；Catalyst is formed by barium carbonate, boron mud, ferrocene, zinc oxide, calcium oxide, manganese oxide, aluminum oxide,
Can be economized on coal consumption reduction, and and can effectively reduces the nitrogen oxides discharged in cement production process, and the performance of clinker is not appointed
What is negatively affected；Yunnan Ze Neng Science and Technology Ltd.s are in Chinese patent CN102304408A（2012-01-04）In disclose one
Kind carbon nanometer combustion improver, preparation method and device, the mass percent of combustion adjuvant are：Emulsifying agent：Emulsifier EL-60,
Sorbitan tristearate, account for 15%-23%；Bleeding agent：Sodium butylnaphthalenesulfonate, aerosol-OT, account for 18%-
27%；Oxidant：Castor oil, account for 12%-20%；Activator：Polyvinyl alcohol, Beta-methyl acrylic acid, accounts for 20%-47%；Nano material：
TiO2, ZnO, MgO, Fe2O3, account for 8%-10%, it is possible to increase coal combustion efficiency, improve burning situation, realize solid sulphur denitration.It is existing
Having combustion adjuvant product and technology to subtract dirt to environmental protection has certain effect, but is also deposited in denitration rate, stability and economy etc.
In many problems, it is necessary to consider comprehensive function of the coal combustion-promoting agents at energy-conservation and the aspect of emission reduction two, from the treatment of wastes with processes of wastes against one another and comprehensive profit
Started with two aspects, the production cost and lifting environmental benefit of coal combustion-promoting agents is greatly reduced.
The content of the invention
It is an object of the invention to provide a kind of coal supply chain combustion adjuvant, by pickling iron and steel waste residue 20-30 parts, flyash 20-25 parts,
White lime 5-10 parts, coke blacking 10-25 parts and lanthanum-cerium chloride 2-10 part dispensings, it is anti-that high temperature heat chemistry is carried out at 500-600 DEG C
Ca-Ti ore type catalysis material La should be generated0.51Ce0.49FeO3And inorganic salt mixt, then be crushed to 100-200 mesh and obtain, by it
Mixed using mass percent 0.2%-5.0% in coal as consolidating sulphur denitration combustion adjuvant, sulfur-fixing rate during coal burning is 60%-
85%, denitration rate is 50%-75%.
Pickling iron and steel waste residue is steel surface waste residue caused by watery hydrochloric acid cleans in coal supply chain combustion adjuvant of the present invention, main
Want in composition Fe to account for 10%-15%, Zn and account for 0.5%-1%, Ca and account for 5%-10%, HCl and account for 2%-5%, SiO2Account for 1%-2%, Al2O3Account for 0.5%-
1%, remaining is mainly water；It is as the raw material for forming Perovskite Catalytic material, second, transition metal conduct therein that it, which acts on one,
Coal middle or low price sulphur is converted into the catalyst of calcium sulfate, third, the effect such as exchange by being catalyzed, aoxidizing, between metal ion,
The activation energy of coal oxidation reaction is reduced as combustion adjuvant.
Flyash is lime-ash caused by coal burning in coal supply chain combustion adjuvant of the present invention, SiO in main component2Account for
40%-50%, Al2O3Account for 25%-30%, Fe2O33%-5% is accounted for, CaO accounts for 5%-15%, and MgO accounts for 1%-4%, Na2O accounts for 1%-4%.It is acted on
First, the carrier as coal supply chain combustion adjuvant, improves combustion adjuvant dispersive property；Second, as the alkali for neutralizing pickling iron and steel waste residue
Property raw material；Third, using the characteristics of wherein sial content is high, the calcium sulfate formed during desulfurization reaction is coated, prevents it at high temperature
Twice decomposition；Fourth, as desulfurizing agent and combustion adjuvant.
Coke blacking is metallurgical coke powdered carbon in coal supply chain combustion adjuvant of the present invention, apparent density 0.88-1.08g/cm3, stomata
Rate is 35%-55%, specific surface area 0.6-0.8m2/g；It is the reaction carriers as generation environment friendly combustion-supporting agent that it, which acts on one,；Second,
The local temperature of reaction zone is improved by combustion-supporting effect, cerium lanthanum oxide and iron oxide is carried out thermalization under relatively low stoving temperature
Learn reaction and form Ca-Ti ore type catalysis material；Third, as the reducing agent being catalyzed nitrogen oxide gas when being reduced to nitrogen.
Ca (OH) in white lime main component in coal supply chain combustion adjuvant of the present invention2Account for 90%-95%, CaCO33%-5% is accounted for,
CaSiO3Account for 1%-2%；It is that lanthanum-cerium chloride and iron chloride are formed into active hydroxide co-precipitation that it, which acts on one,；Second, ensure material
It is middle excessive basic materials to be present, prevent that equipment is corroded during roasting；Third, generate sulphur with the sulphur compound reaction in coal
Sour calcium is as sulphur-fixing agent；Fourth, playing oxygen transmission is used as combustion adjuvant.
The Total rare earth oxide TREO of lanthanum-cerium chloride is more than 45%, La in coal supply chain combustion adjuvant of the present invention2O3/ TREO is
25%-35%, CeO2/ TREO is 45%-70%, Fe 0.05%；Its main function one is and the iron in raw material and other transition metal
Compound carries out thermal chemical reaction and forms Ca-Ti ore type catalysis material, is nitrogen for nitrogen oxide to be catalyzed into reduction or thermal decomposition；
Second, effect, the activation energy for reducing coal oxidation reaction such as exchange by being catalyzed, aoxidizing, between metal ion play combustion-supporting work
With.The chemical composition that Perovskite Catalytic material is formed according to raw material proportioning lanthanum-cerium chloride and pickling iron and steel waste residue is
La0.51Ce0.49FeO3, when the temperature and inadequate reaction time for carrying out thermal chemical reaction, Ca-Ti ore type catalysis material is difficult to shape
Into although continuing reaction in follow-up coal burning forms La0.51Ce0.49FeO3, the effect of catalytic denitration will be influenceed.
For the combustion-supporting mechanism of coal combustion-promoting agents, current main aerobic transfer theory and electron transfer theory.Oxygen transmission is managed
By thinking gaseous reactant effect can be promoted to burn by combustion adjuvant, i.e., combustion adjuvant is reduced into first in a heated condition
Metal, then by metal adsorption oxygen, metal is set to aoxidize to obtain metal oxide, and then reducing metal aoxidizes carbon again
Thing, such metal are constantly in oxidation-reduction circulation, changed back and forth in metal and oxide two states.From macroscopic view
On, oxygen atom accelerates oxygen diffusion velocity constantly from metal to carbon atom transmission, makes coal combustion reaction be easy to carry out.Electronics turns
Move theory to think that by effect of the perfect combustion catalizer to solid-state reactants burning of coal process can be improved, that is, think in combustion adjuvant
Metal ion can be activated in heating process, shift so as to the electronics of its own, turn into electronq donor.Metal
Ion will form hole, and the electronic structure of carbon surface will also change, and the migration of electric charge will accelerate some reactions, so as to carry
The speed that height entirely reacts, obtains carbon burning more complete.In a word, the exchange of combustion adjuvant by being catalyzed, aoxidizing, between metal ion etc.
Effect, the activation energy of coal oxidation reaction is reduced, the ignition temperature of coal is reduced, improves the oxidation rate of coal, shorten coal
Tail-off time.
The action principle of coal supply chain combustion adjuvant of the present invention is that Ca-Ti ore type catalysis material has storage to nitrogen oxide and urged
Change reducing power, coal denitration combustion adjuvant, the Fe contained in mixture can be used as2O3、CaO、CaCl2、SiO2、Al2O3It can inhale
Attached, catalytic reaction, chemical bond and cladding sulphur compound turn into coal sulfur-fixating combustion promoter.
Raw material pickling iron and steel waste residue, coke blacking, flyash, white lime and lanthanum-cerium chloride that the present invention uses etc. is industry
Raw material.
It is a further object to provide a kind of preparation method of coal supply chain combustion adjuvant, including metal salt is negative
Load, the co-precipitation of active hydroxide, composite oxides are formed, Ca-Ti ore type catalysis material forms four parts, the technology taken
Scheme and step are：
（1）Pickling iron and steel waste residue 20-30 parts, flyash 20-25 parts, coke blacking 10-25 parts and lanthanum-cerium chloride 2-10 parts are mixed
Uniformly, metal iron ion and lanthanum cerium ion absorption carriage are made on coke blacking；
（2）Under agitation to drenching into white lime breast 5-10 parts on the mixed material of coke blacking, the pH to material is 8-10, continues to stir
1-2h is mixed, the iron ion and lanthanum cerium ion for making absorption generate Fe (OH) in coke blacking surface hydrolysis2、Fe(OH)3、La(OH)3And Ce
(OH)3Co-precipitation；
（3）The coke blacking mixed material for having loaded active hydroxide precipitation is transferred in convection oven, done at 110-150 DEG C
Dry 2-4h, it is that air oxidation is ferric iron compound to make ferro-compound, at the same make active hydroxide be dehydrated to be formed it is compound
Oxide；
（4）The composite oxides that coke powder mixture loads are bakeed into 2-4h at 500-600 DEG C, it is combustion-supporting on the surface of coke blacking
Under effect, it is La that composite oxides, which carry out thermal chemical reaction and are converted into chemical composition,0.51Ce0.49FeO3Ca-Ti ore type catalysis material
Material；
（5）Inorganic salt mixt containing perovskite composite oxide is further crushed to 100-200 mesh, coal supply chain is made
Combustion adjuvant；It is mixed in coal as solid sulphur denitration combustion adjuvant using mass percent 0.2%-5.0%, coal burning effect can be improved
Rate and the effective utilization for realizing pickling iron and steel waste residue, sulfur-fixing rate is 60%-85% during coal burning, and denitration rate is 50%-75%.
Environment friendly combustion-supporting agent of the present invention can be applied to SO in coal-burning boiler, cement kiln, miberal powder roasting process2And NOxWaste gas disappears
Subtract and save coal；The solid sulphur denitrogenation that can also be applied to during slag oil crack, volatile solvent burning, incineration treatment of garbage.
Sulphur in coal exists generally in the form of elemental sulfur, troilite and organic sulfur, is divided into height according to sulfur content size
Sulphur, middle sulphur and low-sulfur coal, combustion adjuvant addition need to be adjusted according to sulfur content, it is desirable to which wherein calcium and magnesium molal quantity is total sulfur mole
Several more than 2 times, it is general to require to be 4 times, to reach optimal sulfur-fixing rate.
Organonitrogen compound burning and the nitrogen high temperature in air that nitric oxide source in coal burning contains in coal
Two approach are aoxidized, to improve denitration rate, it is desirable to which ignition temperature is controlled below 1000 DEG C, oxygen in perovskite-type material and flue gas
Change nitrogen mol ratio more than 0.01.
The evaluation procedure of combustion adjuvant is：It is put into after combustion adjuvant is mixed with coal sample in high temperature process furnances, being passed through flow is
1.2L/min air, furnace temperature is risen to 1000 DEG C by room temperature under 15 DEG C/min heating rate, stopped at 1000 DEG C
Stop heating after 30 min, after being naturally cooling to room temperature, collect lime-ash, weigh, and determine wherein sulfur content；Carry the sky of flue gas secretly
Gas is discharged by being absorbed after cooling tube and buffer with aqueous slkali, measure wherein content of nitrogen oxide.
It is combustion-supporting to determine to compare the burn tinctuer for having the coal sample of no added combustion adjuvant before and after imperfect combustion in the present invention
The combustion-supporting effect of agent.Burn tinctuer is the weight percent that the coal sample raw material that will be dried at 105-110 DEG C loses after 1000 DEG C of calcinations
Than.
The sulfur content of residue determines sulfur-fixing rate after coal sample burning when having no added combustion adjuvant in the present invention with measure, counts
Calculate formula：
Sulfur-fixing rate=（After being burnt during no added combustion adjuvant during quality-the have addition combustion adjuvant of residual sulfur after burning residual sulfur matter
Amount）The quality of residual sulfur after being burnt during/no added combustion adjuvant.
Content of nitrogen oxide determines denitration in the smoke absorption liquid of coal sample when having no added combustion adjuvant in the present invention with measure
Rate, calculation formula：
Denitration rate=（Nitrogen oxide quality during nitrogen oxide quality during no added combustion adjuvant-have addition combustion adjuvant）/ no added combustion adjuvant
When nitrogen oxide quality.
The beneficial effects of the invention are as follows：
（1）Environment friendly combustion-supporting agent of the present invention has the combustion-supporting multiple functions of solid sulphur denitration, the safe and non-toxic non-volatility of contained component, combustion
Residue can be recycled or as cement and steel and iron industry raw material, not produce secondary pollution after burning；
（2）Environment friendly combustion-supporting agent of the present invention not only alleviates the pollutant emission of coal burning, and can solve pickling iron and steel waste residue
It is difficult to pollution problem caused by handling with flyash, realizes the treatment of wastes with processes of wastes against one another and comprehensive utilization.
Embodiment
Embodiment 1
Pickling iron and steel waste residue 30g, flyash 20g, coke blacking 25g and lanthanum-cerium chloride 10g are well mixed, under agitation to coke
Drenched on powder mixture material into white lime breast 10g, the pH to material is 8-10, continues to stir 2h, makes the iron ion and lanthanum cerium of absorption
Ion is in coke blacking surface hydrolysis and co-precipitation；The coke blacking mixed material for having loaded active hydroxide precipitation is transferred to air blast
In baking oven, 3h is dried at 110-150 DEG C, forms composite oxides.The composite oxides that coke powder mixture loads are transferred to
In high temperature Muffle furnace, 2h is bakeed at 500-600 DEG C, composite oxides progress thermal chemical reaction is converted into chemical composition and is
La0.51Ce0.49FeO3Perovskite-type material, be further crushed to 100-200 mesh, coal supply chain combustion adjuvant 80g be made.By coal
Carbon ring protects combustion adjuvant 0.2g and 10g sulfur content 1.5%, nitrogen content 0.7%, and granularity is well mixed for the coal powder of 50 mesh, is put into height
In warm tube furnace, the air that flow is 1.2L/min is passed through, rises to furnace temperature by room temperature under 15 DEG C/min heating rate
1000 DEG C are tested, and when not adding coal supply chain combustion adjuvant compared with test, the sulfur-fixing rate of environment friendly combustion-supporting agent is
71%, denitration rate is 73%, and coal burn tinctuer improves 18%.
Embodiment 2
Coal supply chain combustion adjuvant is prepared according to the charge ratio of embodiment 1, is a difference in that the combined oxidation of coke powder mixture load
Thing, which is not transferred in high temperature Muffle furnace, carries out baking processing, and coal supply chain combustion adjuvant 90g is made.By coal supply chain combustion adjuvant 0.2g with
10g sulfur content 1.5%, nitrogen content 0.7%, granularity are well mixed for the coal powder of 50 mesh, are put into high temperature process furnances, are passed through flow
For 1.2L/min air, under 15 DEG C/min heating rate furnace temperature is risen into 1000 DEG C by room temperature is tested, and with
Test is compared when not adding coal supply chain combustion adjuvant, the sulfur-fixing rate of environment friendly combustion-supporting agent is 64%, and denitration rate is 43%, and coal burns
Mistake rate improves 12%.
Embodiment 3
Pickling iron and steel waste residue 20g, flyash 20g, coke blacking 10g and lanthanum-cerium chloride 2g are well mixed, under agitation to coke
Drenched on powder mixture material into white lime breast 5g, the pH to material is 8-10, continue stir 2h, make absorption iron ion and lanthanum cerium from
Son is in coke blacking surface hydrolysis and co-precipitation；The coke blacking mixed material for having loaded active hydroxide precipitation is transferred into air blast to dry
In case, 2h is dried at 110-150 DEG C, forms composite oxides.The composite oxides that coke powder mixture loads are transferred to height
In warm Muffle furnace, 2h is bakeed at 500-600 DEG C, composite oxides progress thermal chemical reaction is converted into chemical composition and is
La0.51Ce0.49FeO3Perovskite-type material, be further crushed to 100-200 mesh, coal supply chain combustion adjuvant 50g be made.By coal
Carbon ring protects combustion adjuvant 0.2g and 10g sulfur content 2.3%, nitrogen content 0.9%, and granularity is well mixed for the coal powder of 50 mesh, is put into height
In warm tube furnace, the air that flow is 1.2L/min is passed through, rises to furnace temperature by room temperature under 15 DEG C/min heating rate
1000 DEG C are tested, and when not adding coal supply chain combustion adjuvant compared with test, the sulfur-fixing rate of environment friendly combustion-supporting agent is
65%, denitration rate is 67%, and coal burn tinctuer improves 15%.
Claims (6)
1. a kind of coal supply chain combustion adjuvant, it is characterised in that by pickling iron and steel waste residue 20-30 parts, flyash 20-25 parts, white lime
5-10 parts, coke blacking 10-25 parts and lanthanum-cerium chloride 2-10 part dispensings, high temperature thermal chemical reaction generation is carried out at 500-600 DEG C
Ca-Ti ore type catalysis material La0.51Ce0.49FeO3And inorganic salt mixt, then be crushed to 100-200 mesh and obtain.
2. the coal supply chain combustion adjuvant as described in claim 1, it is characterised in that pickling iron and steel waste residue is the dilute salt of steel surface
Waste residue caused by acid cleaning, Fe, which accounts for 10%-15%, Zn and accounts for 0.5%-1%, Ca and account for 5%-10%, HCl, in main component accounts for 2%-5%, SiO2
Account for 1%-2%, Al2O3Account for 0.5%-1%.
3. the coal supply chain combustion adjuvant as described in claim 1, it is characterised in that flyash is lime-ash caused by coal burning, main
Want SiO in composition2Account for 40%-50%, Al2O3Account for 25%-30%, Fe2O33%-5% is accounted for, CaO accounts for 5%-15%, and MgO accounts for 1%-4%,
Na2O accounts for 1%-4%.
4. the coal supply chain combustion adjuvant as described in claim 1, it is characterised in that coke blacking is metallurgical coke powdered carbon, and apparent density is
0.88-1.08g/cm3, porosity 35%-55%, specific surface area 0.6-0.8m2/g。
5. the coal supply chain combustion adjuvant as described in claim 1, it is characterised in that the Total rare earth oxide TREO of lanthanum-cerium chloride is big
In 45%, La2O3/ TREO is 25%-35%, CeO2/ TREO is 45-70%, Fe 0.05%.
6. a kind of preparation method of coal supply chain combustion adjuvant, including the load of metal salt, active hydroxide are co-precipitated, are compound
Oxide is formed, Ca-Ti ore type catalysis material forms four parts, and the technical scheme and step taken are：
（1）Pickling iron and steel waste residue 20-30 parts, flyash 20-25 parts, coke blacking 10-25 parts and lanthanum-cerium chloride 2-10 parts are mixed
Uniformly, metal iron ion and lanthanum cerium ion absorption carriage are made on coke powder mixture；
（2）Under agitation to drenching into white lime breast 5-10 parts on the mixed material of coke blacking, the pH to material is 8-10, continues to stir
1-2h is mixed, the iron ion and lanthanum cerium ion for making absorption generate Fe (OH) in coke blacking surface hydrolysis2、Fe(OH)3、La(OH)3And Ce
(OH)3Co-precipitation；
（3）The coke blacking mixed material for having loaded active hydroxide precipitation is transferred in convection oven, done at 110-150 DEG C
Dry 2-4h, it is that air oxidation is ferric iron compound to make ferro-compound, at the same make active hydroxide be dehydrated to be formed it is compound
Oxide；
（4）The composite oxides that coke powder mixture loads are bakeed into 2-4h at 500-600 DEG C, it is combustion-supporting on the surface of coke blacking
Under effect, it is La that composite oxides, which carry out thermal chemical reaction and are converted into chemical composition,0.51Ce0.49FeO3Ca-Ti ore type catalysis material
Material；
（5）Inorganic salt mixt containing perovskite composite oxide is further crushed to 100-200 mesh, coal supply chain is made
Combustion adjuvant；It is mixed in coal as solid sulphur denitration combustion adjuvant using mass percent 0.2%-5.0%, coal burning effect can be improved
Rate and the effective utilization for realizing pickling iron and steel waste residue, sulfur-fixing rate is 60%-85% during coal burning, and denitration rate is 50%-75%.
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| CN110387280A (en) * | 2019-08-15 | 2019-10-29 | 南宁方力电气有限公司 | A kind of coal combustion clean catalysis agent |
| CN113717768A (en) * | 2021-09-23 | 2021-11-30 | 内蒙古大学 | Coal sulfur-fixing additive and preparation method thereof |
| CN114574262A (en) * | 2022-03-04 | 2022-06-03 | 安徽工业大学 | Coal-fired catalyst produced by using titanium white waste acid and preparation method thereof |
| CN114700088A (en) * | 2022-03-23 | 2022-07-05 | 天津水泥工业设计研究院有限公司 | Medium-low temperature denitration catalyst prepared by recycling fly ash as resource and preparation method and application thereof |
| CN115418258A (en) * | 2022-09-14 | 2022-12-02 | 滁州智慧城市环保科技有限责任公司 | Boiler coking inhibitor and preparation method thereof |
| CN115772587A (en) * | 2023-02-10 | 2023-03-10 | 山西潞安环保能源开发股份有限公司 | Environment-friendly blast furnace injection coal multi-effect additive, preparation method and adding device thereof |
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| CN115418258B (en) * | 2022-09-14 | 2024-03-22 | 滁州智慧城市环保科技有限责任公司 | Boiler coking inhibitor and preparation method thereof |
| CN115772587A (en) * | 2023-02-10 | 2023-03-10 | 山西潞安环保能源开发股份有限公司 | Environment-friendly blast furnace injection coal multi-effect additive, preparation method and adding device thereof |
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