CN108264279A - A kind of method that porous and granular composite material is prepared using red mud, flyash as raw material - Google Patents

A kind of method that porous and granular composite material is prepared using red mud, flyash as raw material Download PDF

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Publication number
CN108264279A
CN108264279A CN201810006908.1A CN201810006908A CN108264279A CN 108264279 A CN108264279 A CN 108264279A CN 201810006908 A CN201810006908 A CN 201810006908A CN 108264279 A CN108264279 A CN 108264279A
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China
Prior art keywords
flyash
red mud
raw
porous
granular composite
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CN201810006908.1A
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CN108264279B (en
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王丽萍
赵雅琴
张家明
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016Particle form
    • B01J20/28021Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02Selection of the hardening environment
    • C04B40/0204Selection of the hardening environment making use of electric or wave energy or particle radiation
    • C04B40/0213Electromagnetic waves
    • C04B40/0218Microwaves
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/02Selection of the hardening environment
    • C04B40/024Steam hardening, e.g. in an autoclave
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The present invention provides a kind of method that porous and granular composite material is prepared using red mud, flyash as raw material; cement waste material is chosen as binding agent; it is uniformly mixed by flyash for the 10 30% of red mud mass ratio with matching the binding agent in 5%, a diameter of 5 8mm raw meal particulates of uniform size is made by comminutor;In the microwave activated reactor for being 5 20w/g in power per unit mass by raw material, 15 30min of steam activation is passed through, porous and granular composite material is obtained after room temperature cools down.The present invention promotes the excitation of flyash activity using CaO in red mud, pass through microwave heating, part of the metal oxide in red mud and flyash reacts the intensity that can increase granular materials with ingredients such as silica, simultaneously, the uncompleted burned carbon contained in flyash can increase specific grain surface product and generation pore structure after microwave activates.The porous and granular composite material large specific surface area produced, strong adsorption, resistance to temperature stability is good, while preparation process is simple, and low energy consumption, environmentally friendly.

Description

A kind of method that porous and granular composite material is prepared using red mud, flyash as raw material
Technical field
The present invention relates to aluminum oxide industry highly basic waste and coal base technical field of comprehensive utilization of solid waste, specifically relate to A kind of and method that porous and granular composite material is prepared using red mud, flyash as raw material.
Background technology
Red mud is the strong basicity solid waste generated in aluminum oxide industry production process, due to technique and bauxite grade Difference, production 1t aluminium oxide about generate 1.0~2.0t red muds.The occurrence status stabilization of red mud chemical bonding alkali, salt content High, chemical composition and mineral phase composition are complicated, therefore comprehensively utilize hardly possible.Mainly based on stockpiling, global red mud storage in 2015 Up to 4,000,000,000 tons, and with 1.2 hundred million ta- 1Speed increase the Chinese aluminium oxide yield about 6100 × 10 in 2016 of4T, red mud are arranged outside It measures up to 7000 × 104T, accumulation volume of cargo in storage surpass 5 × 108t.The Environment Ecological Safe problem of red mud pilling restricts aluminum oxide industry Sustainable development.
Red mud is during stockpiling, and because its skin granulate object is overbased salts, grain size is easily led to tight mostly at 2~20 μm The air pollution of weight, alkali grain settlement action also can generate potential hazard to periphery ecological environment and health.Red mud It is slow there are soil-forming process, the problems such as plant is difficult to grow, and stockyard ecological reconstruction is difficult.
Using coal as main energy sources, 70% or so coal is used for thermal power generation for China, and the flyash that fire coal generates always is stored up Amount is more than 1,000,000,000 t.Flyash storage does not only take up a large amount of soils, can also cause serious environmental pollution.The coal measures such as flyash Solid waste comprehensively utilizes, and can support the sustainable development of China's economic and coal electricity industry.
Bayer process is to produce the main technique of aluminium oxide, and the red mud for comprehensively utilizing the discharge of its production process is one worldwide Problem, using red mud, flyash for raw material porous and granular composite material microwave activating technology, can effectively handle red Mud waste reduces red mud pollution on the environment, the treatment of wastes with processes of wastes against one another, while has that preparation process is simple, low energy consumption, environment friend Well, the advantages that the treatment of wastes with processes of wastes against one another.
Invention content
It is an object of the present invention to provide one kind using red mud, flyash as raw material, porous and granular is prepared by microwave activation and is answered It the problem of method of condensation material, this method can not be utilized effectively for current red mud waste, flyash, realizes to red The comprehensive utilization of mud and flyash, while have many advantages, such as that preparation process is simple, low energy consumption, the environmental-friendly, treatment of wastes with processes of wastes against one another.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of method that porous and granular composite material is prepared using red mud, flyash as raw material, includes the following steps:
Step 1:Red mud, flyash, binding agent are uniformly mixed;
Step 2:Raw meal particulate is made in step 1 gained mixture;
Step 3:Step 2 gained raw meal particulate is passed through steam activation in microwave activated reactor;
Step 4:Porous and granular composite material is obtained after the cooling of step 3 treated raw meal particulate.
Preferably, the red mud is Bayer process red mud, and the flyash is circulating fluidized bed boiler flyash.
Preferably, in step 1 gained mixture, the 10-30% of the mass ratio of flyash for the mass ratio of red mud, binding agent Mass ratio be not more than 5%.
Preferably, described adhesive is cement.
Preferably, the time of the activation of microwave described in step 3 is 15-30min.The too short inadequate pore-creating of microwave soak time, It is long to be sintered.
Preferably, the power per unit mass of the microwave activated reactor is 5-20w/g.
Preferably, the granularity of the granular adsorption material is 5-8mm.
Advantageous effect:(1) this method can improve the work of composite material due to the presence of flyash-red mud (lime) system Property and intensity.Contained vitreum is more in flyash under 900 DEG C of circulating fluidized bed boiler of raw material selection, wherein soluble SiO2、Al2O3, activity SiO2、Al2O3The water with higher-strength and the hydraulicity can be generated after being mixed with the lime in red mud and water Change calcium silicates (C-S-H) and drated calcium aluminate (C-A-H).
(2) chemical composition of flyash is in faintly acid, its activity is more easy to be swashed in the preparation process with Bayer process red mud Hair.Under the action of OH-, Si-O the and Al-O keys fracture on fly ash grain surface can reduce the poly- of Si-O-Al network polymerization bodies It is right.
(3) material makes electromagnetic energy under the action of microwave electromagnetic field by way of dipole rotation and ionic conduction For thermal energy, it can realize inside and outside quick heating simultaneously, achieve the effect that catalysis reaction.In preparation process, microwave activation material Material sample can obtain higher specific surface area, sample be made to have the characteristics that layering and porosity and looseness, and can greatly shorten work Change the time, reduce energy consumption.Therefore, in the preparation of porous material, microwave activation has compared with the mode that common heating activates Apparent advantage.
(4) by microwave heating, part of the metal oxide (such as CaO, Al in red mud and flyash2O3And Fe2O3) and oxygen The ingredients such as SiClx can react to form the metastable silicate of structure, and intensity increases after making material granule, improve material and resist Hydraulic blow load-bearing capacity.Meanwhile raw meal particulate is in activation process, hydrated mineral and carbonate mine in red mud and flyash Object etc. easily decomposes and releases moisture or gas, helps to form pore structure inside particle;Contain certain proportion in flyash Uncompleted burned carbon, through microwave activation can reach increase specific grain surface product and generation pore structure purpose.
(5) the porous and granular composite material epigranular prepared by the present invention, large specific surface area, strong adsorption, heatproof are steady It is qualitative good, while preparation process is simple, low energy consumption, environmentally friendly, has very big advantage in terms of adsorption treatment waste water.
Specific embodiment
Further explanation is done to the present invention with reference to embodiment.
The present invention provides one kind using red mud, flyash as raw material, porous and granular composite wood is prepared by microwave activation The method of material, this method include following steps:
1) present invention sampling selects Bayer process iron red mud and circulating fluidized bed boiler flyash as preparing composite material Primary raw material;To increase the quick plasticity of granular materials, choosing cement waste material, (consumption proportion control exists as binding agent Within 5%).
2) by raw material drying, it is broken after, sieve with 100 mesh sieve screening, make raw material powder grain size is relatively uniform to be convenient for being sufficiently mixed; It is uniformly mixed by 10-30% of the flyash for red mud mass ratio with matching the binding agent in 5%, diameter is made by comminutor For 5-8mm raw meal particulates of uniform size;In the microwave activated reactor for being 5-20w/g in power per unit mass by raw material, lead to Enter steam activation 15-30min, the granular adsorption material with some strength is obtained after room temperature cools down.
Chalco Shandong branch company (Shandong Zibo) Bayer process red mud is selected, main component see the table below:
Select magnificent near coal-mine environmentally friendly Thermal Power Co., Ltd (Xuzhou) circulating fluidized bed boiler flyash:
Embodiment 1:
By aluminium manufacturer's red mud drying, it is broken after, sieve with 100 mesh sieve screening, make raw material powder grain size relatively uniform convenient for fully mixing It closes;It is 85 according to red mud from sintering process, flyash, cement quality ratio:10:5 take the raw material of certain mass to be uniformly mixed, and pass through granulation A diameter of 5-8mm raw meal particulates of uniform size are made in machine;Raw material are passed through vapor maintenance in microwave activated reactor to live Change 15min, power per unit mass 7.3667w/g.Obtain that there is the granular porous of some strength after room temperature cools down Sorbing material, specific surface area 17.8372m2/g。
Embodiment 2:
By aluminium manufacturer's red mud drying, it is broken after, sieve with 100 mesh sieve screening, make raw material powder grain size relatively uniform convenient for fully mixing It closes;It is 80 according to red mud from sintering process, flyash, cement quality ratio:15:5 take the raw material of certain mass to be uniformly mixed, and pass through granulation A diameter of 5-8mm raw meal particulates of uniform size are made in machine;Raw material are passed through to air care activation in microwave activated reactor 20min, power per unit mass 13.8667w/g.The granular porous suction with some strength is obtained after room temperature cools down Enclosure material, specific surface area 19.4283m2/g。
Embodiment 3:
By aluminium manufacturer's red mud drying, it is broken after, sieve with 100 mesh sieve screening, make raw material powder grain size relatively uniform convenient for fully mixing It closes;It is 75 according to red mud from sintering process, flyash, cement quality ratio:20:5 take the raw material of certain mass to be uniformly mixed, and pass through granulation A diameter of 5-8mm raw meal particulates of uniform size are made in machine;Raw material are passed through to air care activation in microwave activated reactor 30min, power per unit mass 19.5w/g.The granular porous absorption with some strength is obtained after room temperature cools down Material, specific surface area 23.2719m2/g。
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (6)

  1. A kind of 1. method that porous and granular composite material is prepared using red mud, flyash as raw material, which is characterized in that including as follows Step:
    Step 1:Red mud, flyash, binding agent are uniformly mixed;
    Step 2:Raw meal particulate is made in step 1 gained mixture;
    Step 3:Step 2 gained raw meal particulate is passed through steam activation in microwave activated reactor;
    Step 4:Porous and granular composite material is obtained after the cooling of step 3 treated raw meal particulate.
  2. 2. a kind of method that porous and granular composite material is prepared using red mud, flyash as raw material according to claim 1, It is characterized in that, the red mud is Bayer process red mud, the flyash is circulating fluidized bed boiler flyash.
  3. 3. a kind of method that porous and granular composite material is prepared using red mud, flyash as raw material according to claim 1, It is characterized in that, in step 1 gained mixture, the 10-30% of the mass ratio of flyash for the mass ratio of red mud, the matter of binding agent Amount is than no more than 5%.
  4. 4. a kind of method that porous and granular composite material is prepared using red mud, flyash as raw material according to claim 1, It is characterized in that, in step 3, the time of the microwave activation is 15-30min.
  5. 5. a kind of method that porous and granular composite material is prepared using red mud, flyash as raw material according to claim 1, It is characterized in that, in step 3, the power per unit mass of the microwave activated reactor is 5-20w/g.
  6. 6. porous and granular composite material is prepared as raw material using red mud, flyash according to any described one kind of Claims 1 to 5 Method, which is characterized in that described adhesive is cement.
CN201810006908.1A 2018-01-04 2018-01-04 Method for preparing porous granular composite material by using red mud and fly ash as raw materials Active CN108264279B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109485454A (en) * 2018-12-12 2019-03-19 雅安远创陶瓷有限责任公司 It is a kind of to have effects that the ceramic of water purification and preparation method
CN109731544A (en) * 2019-01-30 2019-05-10 中国矿业大学 A kind of red mud-clinker-cementitious composite dephosphorization agent preparation method
CN110653247A (en) * 2019-09-30 2020-01-07 中国矿业大学 Soil phosphorus condition improvement method based on red mud-based composite solid waste material recycling
CN111256944A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Porous material for hydromechanics visual measurement and preparation method and application thereof
CN111517702A (en) * 2020-04-28 2020-08-11 宁夏大学 Porous material for desert water retention and preparation method thereof, desert water retention material and desert water retention covering method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101143312A (en) * 2006-09-12 2008-03-19 中国科学院生态环境研究中心 Method for manufacturing and regenerating granular red mud absorber used for water process
CN102908983A (en) * 2012-10-31 2013-02-06 昆明理工大学 Method for preparing porous adsorption material by using microwave low-temperature pore-forming activated granular red mud

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101143312A (en) * 2006-09-12 2008-03-19 中国科学院生态环境研究中心 Method for manufacturing and regenerating granular red mud absorber used for water process
CN102908983A (en) * 2012-10-31 2013-02-06 昆明理工大学 Method for preparing porous adsorption material by using microwave low-temperature pore-forming activated granular red mud

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111256944A (en) * 2018-11-30 2020-06-09 中国科学院大连化学物理研究所 Porous material for hydromechanics visual measurement and preparation method and application thereof
CN111256944B (en) * 2018-11-30 2021-05-25 中国科学院大连化学物理研究所 Porous material for hydromechanics visual measurement and preparation method and application thereof
CN109485454A (en) * 2018-12-12 2019-03-19 雅安远创陶瓷有限责任公司 It is a kind of to have effects that the ceramic of water purification and preparation method
CN109731544A (en) * 2019-01-30 2019-05-10 中国矿业大学 A kind of red mud-clinker-cementitious composite dephosphorization agent preparation method
CN110653247A (en) * 2019-09-30 2020-01-07 中国矿业大学 Soil phosphorus condition improvement method based on red mud-based composite solid waste material recycling
CN111517702A (en) * 2020-04-28 2020-08-11 宁夏大学 Porous material for desert water retention and preparation method thereof, desert water retention material and desert water retention covering method

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