CN105219477A - A kind of fluidized bed preparation method for material of area load rare earth oxide catalyst - Google Patents

A kind of fluidized bed preparation method for material of area load rare earth oxide catalyst Download PDF

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CN105219477A
CN105219477A CN201510759979.5A CN201510759979A CN105219477A CN 105219477 A CN105219477 A CN 105219477A CN 201510759979 A CN201510759979 A CN 201510759979A CN 105219477 A CN105219477 A CN 105219477A
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rare earth
earth oxide
fluidized bed
area load
oxide catalyst
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CN105219477B (en
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武文斐
张凯
李保卫
龚志军
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Inner Mongolia University of Science and Technology
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Inner Mongolia University of Science and Technology
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Abstract

The present invention relates to a kind of fluidized bed preparation method for material, particularly relate to a kind of fluidized bed preparation method for material of area load rare earth oxide catalyst.SiO will be rich in 2, Al 2o 3, be mixed in proportion after MgO, CaO and alkalimetal oxide powder process form modified auxiliary material and with hot steel slag at high temperature consolute and homogenizing, the liquid low viscosity silicate melt obtained, through high temperature wire drawing, granulation process, obtains the high temperature bead that particle diameter is 5-7mm; The micro/nano level RE oxide powder with catalysis is sprayed into dirt system, forms rare earth oxide cloud; High temperature bead is carried out dirt process in rare earth oxide cloud, obtains area load spherolite; Area load spherolite cooling process is obtained fluidized bed material.The present invention is raw material with hot steel slag, prepares the fluidized bed material of surperficial supported rare earth oxide catalyst, at the coal-fired fluidized bed middle burning-point realizing reduction coal, accelerates combustionvelocity, suppresses the generation of fuel type NOx.

Description

A kind of fluidized bed preparation method for material of area load rare earth oxide catalyst
Technical field
The present invention relates to a kind of fluidized bed preparation method for material, particularly relate to a kind of fluidized bed preparation method for material of area load rare earth oxide catalyst.
Background technology
Development along with China's economic technology and the raising to environmental requirement, the effective and reasonable utilization of the energy and the emission control of burning pollutant are subject to extensive concern.Combustion technology of circulating fluidized is the high-efficiency low-pollution clean burning branch art developed rapidly in recent years, have coal adaptability wide, can effectively control in combustion and generation, the plurality of advantages such as intensity of combustion is large, heat and mass is strong, be used widely in fields such as station boiler, Industrial Boiler and offal treatment utilizations.The in-furnace temperature of fluidized-bed combustion boiler is lower, is generally 800-950 DEG C, make thermal NO x and fuel type NOx generation less, its starting point concentration is generally 100-500mg/m 3.
Fluidized-bed combustion boiler denitration is carried out at afterbody usually, main employing tail flue gas Selective catalytic reduction (SCR) technology and selective non-catalytic reduction (SNCR) technology.Wherein SNCR gas denitrifying technology is a kind of commercial gas denitrifying technology of main flow, has reduced investment, and take up an area few, the duration is short, is convenient to the advantages such as maintenance.But for the pulverized coal firing boiler of large power plant, the denitration efficiency of SNCR technique is lower, is generally 30%-60%, major cause is the impact by boiler structure size, and NOx mixes uneven with reductive agent.It is 100mg/m that independent employing SNCR gas denitrifying technology to be difficult to meet in emission standard coal-powder boiler NOx emission limit value 3requirement, multiplexly supplement process means.Develop efficient, oligosaprobic coal clean combustion technology, the discharge reducing NOx is current problem anxious to be resolved.
By still rare for the example that the link of fluidized-bed combustion boiler denitration denitrating flue gas advances to the coal combustion stage.The bed material of current fluidized bed combustion coal burning boiler adopts quartz sand or slag usually, in coal combustion process, all do not have obvious catalytic effect.Bed material area load prepared by the present invention has rare-earth oxidation, has catalysis, can realize carrying out denitration in combustion, and can reduce the burning-point of coal, accelerates combustionvelocity.Sustainable development for China's energy industry and national economy has great importance.
Summary of the invention
The object of the present invention is to provide a kind of method preparing the fluidized bed material of surperficial supported rare earth oxide catalyst, realize the burning-point of coal-fired fluidized bed middle reduction coal, accelerate combustionvelocity, suppress the generation of fuel type NOx.
Technical scheme of the present invention comprises following processing step:
The fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst of the present invention, comprises following methods step:
1) SiO will be rich in 2, Al 2o 3, MgO, CaO and alkalimetal oxide powder process mix by a certain percentage, obtain modified auxiliary material;
2) hot steel slag at high temperature with modified auxiliary material consolute and homogenizing, obtain liquid low viscosity silicate melt;
3) low viscosity silicate melt is by high temperature granulation, obtains the high temperature bead that particle diameter is 5-7mm;
4) the micro/nano level RE oxide powder with catalysis is sprayed into dirt system, form rare earth oxide cloud;
5) carry out dirt process in the rare earth oxide cloud formed in step 4) by the high temperature bead in step 3), obtain area load spherolite;
6) area load spherolite is cooled, obtain fluidized bed material.
Further, the raw materials used high temperature hot steel slag being steel-making and producing.
Further, the component of modified auxiliary material is dynamic conditioning according to the change of slag composition, to meet the element requirement of principal crystalline phase in high temperature bead.
Further, at high temperature consolute obtains mode is liquid-liquid consolute or liquid-solid consolute for hot steel slag and modified auxiliary material.Hot consolute temperature: 1250 DEG C-1350 DEG C.
Further, the micro/nano level RE oxide powder with catalysis is the rare earth oxide of the metal nano level powder such as CeO2 or doping Au, Pt, Pb.
Further, the temperature that high temperature bead enters dirt system is 1050-1150 DEG C, is in semi-melting state.
Further, the temperature of rare earth oxide dirt system is 1000-1050 DEG C.
Further, the particle diameter of area load spherolite is 5-8mm, has the burning-point reducing coal, the function accelerated combustionvelocity, suppress fuel type NOx to generate.
Further, the principal crystalline phase of area load spherolite is diopside or spinel.
Rare earth element is important in irreplaceable effect because its distinctive performance makes it play in multiple catalytic material.Research shows, the existence of rare earth element can improve the dispersity storing oxygen ability and active metal of catalyzer, improves the catalytic activity at active metal particles interface and reduces noble metal dosage; Improve the thermostability of catalytic material and the mobility etc. of lattice oxygen.RE treatment steel is broadly divided into complex rare-earth oxidate containing valuable metal, rare earth-(expensive) metal and rare earth-molecular sieve etc. by its composition.Be divided into metal carrier catalyst and ceramic-substrate catalyst by solid support material catalyzer, ceramic-substrate catalyst weather resistance is strong, and density is light, is adopt maximum catalyst support materials.
Started to the research of catalysis of rare-earth compound performance both at home and abroad middle 1960s.Catalyst application containing rare earth is used widely in purifying vehicle exhaust by Libby in 1971, and that research is more at present is CeO 2-ZrO 2(CZO) sosoloid.In coal combustion field, have and rare earth oxide to be mixed in coal dust multifuel combustion to play the research reducing burning of coal temperature and speed.But there is rare earth oxide to be difficult to reclaim, the deficiency such as cannot to reuse.
The present invention is based on the technical characterstic of fluidized bed combustion coal burning boiler, exploitation has high catalytic performance, low cost, resistant to elevated temperatures fluidized bed material, and to promotion burning of coal, the generation controlling oxynitride is significant.The catalysis that the bed material utilizing hot steel slag directly to prepare surperficial supported rare earth oxide compound burns for Coal in Fluidized Bed does not have bibliographical information at present.
Invention feature: feature of the present invention is that the matrix of fluidized bed material is mainly derived from hot steel slag, takes full advantage of the slag in slag and heat.The process of bed material area load rare earth oxide is at high temperature carried out.Prepared bed material is used to fire coal circulating fluid bed boiler, in the process of coal combustion, fluidized bed material fully contacts with coal dust, has promotion burning of coal, suppress nitrogen content of coal Element generation oxynitride, the link of fluidized-bed combustion boiler denitration denitrating flue gas can be advanceed to the coal combustion stage.
Accompanying drawing explanation
Accompanying drawing is process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.Providing of embodiment limits the present invention anything but.
Embodiment 1
the determination of hot steel slag and modified adjunct ingredient
The complicated components of hot steel slag is changeable, need design corresponding auxiliary material and carry out modified, to meet the component requirements of supported porous bead.The moiety of auxiliary material and the design calculation of consumption are the moietys based on slag, dynamically carry out under the constraint of target sample component, the supported porous bead sample of different components, and the consumption of slag is also different with the design of auxiliary material, specifically as shown in table 1.
hot consolute and homogenizing
1) according to the component of slag and target sample, prepare corresponding auxiliary material, the auxiliary material mixed is put into the inherent 1350 DEG C of heating and meltings of platinum crucible and become liquid, then hot steel slag is poured in auxiliary material liquid carry out mixing homogenizing, obtain slag silicate melt.
high temperature granulation and load
1) be incorporated in High Temperature Rotating equipment by low viscosity slag silicate melt and carry out granulation, (temperature is 1100 DEG C, and particle diameter is 6-7mm, and density is 2.8g/cm to obtain spherical granules 3), spherical granules completes the area load of rare earth oxide catalyst again through dirt system.
thermal treatment
The spherical granules of area load rare earth oxide catalyst enters heat treatment system again and completes core Crystallizing treatment: nucleation temperature: 720 DEG C-780 DEG C, nucleation time 30-60min, crystallization temperature: 880 DEG C-920 DEG C, crystallization time 40-70min.Obtain the spherical granules with fixing crystalline phase.
cool and be separated
After ball, powder mixture are cooled to room temperature, utilize the difference of RE oxide powder and spherical granules character to be separated by spherical granules, obtain the fluidized bed material of area load rare earth oxide catalyst, particle diameter is 6-8mm, and density is 2.75g/cm 3, heat resisting temperature is 980 DEG C.

Claims (10)

1. a fluidized bed preparation method for material for area load rare earth oxide catalyst, is characterized in that, supported rare earth oxide catalyst on bed material, has the burning-point reducing coal, the function accelerated combustionvelocity, suppress fuel type NOx to generate.
2. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, comprise following methods step:
(1) SiO will be rich in 2, Al 2o 3, MgO and alkalimetal oxide powder process mix by a certain percentage, obtain modified auxiliary material;
(2) hot steel slag under 1250-1400 DEG C of high temperature with modified auxiliary material consolute and homogenizing, obtain liquid low viscosity silicate melt;
(3) low viscosity silicate melt is by high temperature granulation, obtains the high temperature bead that particle diameter is 5-7mm;
(4) the micro/nano level RE oxide powder with catalysis is sprayed into dirt system, form rare earth oxide cloud;
(5) carry out dirt process in the rare earth oxide cloud formed in step 4) by the high temperature bead in step 3), obtain area load spherolite;
(6) area load spherolite is cooled to room temperature, obtains fluidized bed material.
3. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, it is characterized in that, raw materials used be steel-making produce high temperature hot steel slag, temperature 1400-1500 DEG C, the main chemical in slag by weight percentage: comprising: SiO 210-20%, CaO30-45%, Al 2o 35-10%, TiO 20.5-1, MgO30-45%, Fe 2o 325-35%, K 2o1-5%, Na 2o2-6%, all the other are impurity.
4. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, the compositions in weight percentage of modified auxiliary material: SiO 230-40%, CaO20-30%, Al 2o 315-25%, MgO10-15% and alkalimetal oxide 5-8% powder process, mix change according to slag composition and dynamic conditioning, to meet the element requirement of principal crystalline phase in high temperature bead.
5. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, alkalimetal oxide is K 2o or Na 2o.
6. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 2, is characterized in that, the micro/nano level RE oxide powder with catalysis is CeO 2or the rare earth oxide of doping Au, Pt, Pb metal nano level powder.
7. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, the temperature that high temperature bead enters dirt system is 1050-1150 DEG C, is in semi-melting state.
8. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, the temperature of rare earth oxide dirt system is 1000-1050 DEG C.
9. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, is characterized in that, the particle diameter of area load spherolite is 5-8mm, makes material temperature degree 950 DEG C-1050 DEG C.
10. the fluidized bed preparation method for material of a kind of area load rare earth oxide catalyst according to claim 1, it is characterized in that, the principal crystalline phase of area load spherolite is diopside or spinel, area load spherolite heat treatment process: temperature: 720 DEG C-780 DEG C, nucleation time 30-60min, crystallization temperature: 880 DEG C-920 DEG C, crystallization time 40-70min.
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CN108949287A (en) * 2018-08-08 2018-12-07 桂林桂特板业有限公司 A method of biomass molding fuel ash softening point is improved using porous ceramics
CN110595217A (en) * 2019-08-30 2019-12-20 中国科学院广州能源研究所 Degradation of NO in high-temperature combustion of industrial furnaceXMethod and system
CN111495383A (en) * 2020-04-22 2020-08-07 陕西延长石油（集团）有限责任公司 Method and catalyst for preparing hexamethylene diamine from hexanediol and ammonia gas
CN117646896A (en) * 2024-01-29 2024-03-05 东北大学 Self-heat-exchanging device for catalytic reduction of pollutants, heat-exchanging ceramic balls and combustor

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CN111495383A (en) * 2020-04-22 2020-08-07 陕西延长石油（集团）有限责任公司 Method and catalyst for preparing hexamethylene diamine from hexanediol and ammonia gas
CN111495383B (en) * 2020-04-22 2023-03-10 陕西延长石油（集团）有限责任公司 Method and catalyst for preparing hexamethylene diamine from hexanediol and ammonia gas
CN117646896A (en) * 2024-01-29 2024-03-05 东北大学 Self-heat-exchanging device for catalytic reduction of pollutants, heat-exchanging ceramic balls and combustor
CN117646896B (en) * 2024-01-29 2024-04-12 东北大学 Self-heat-exchanging device for catalytic reduction of pollutants, heat-exchanging ceramic balls and combustor

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