CN103145442A - Method for preparing non-sintered ceramisites by using chemical sludge - Google Patents

Method for preparing non-sintered ceramisites by using chemical sludge Download PDF

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Publication number
CN103145442A
CN103145442A CN2013101057074A CN201310105707A CN103145442A CN 103145442 A CN103145442 A CN 103145442A CN 2013101057074 A CN2013101057074 A CN 2013101057074A CN 201310105707 A CN201310105707 A CN 201310105707A CN 103145442 A CN103145442 A CN 103145442A
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sludge
sintered
dry blend
ash
roasting
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CN2013101057074A
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Chinese (zh)
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CN103145442B (en
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徐炎华
潘丽娟
胡俊
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南京工业大学
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    • 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 invention relates to a method for preparing non-sintered ceramisites by using chemical sludge, belonging to the technical field of hazardous solid waste treatment, disposal and resource recovery in the chemical industry. The method comprises the following steps of: drying the sludge to obtain dry sludge firstly; then roasting the dry sludge, and crushing obtained sludge ashes by a crusher; and uniformly mixing a sludge ash powder, coal ashes, cement, a plaster powder, light materials and a foaming agent in proportion, adding water into a mixture, stirring to prepare spherical particles, and carrying out natural curing finally to prepare a non-sintered filler. According to the method disclosed by the invention, hazardous solid waste chemical sludge and industrial solid waste coal ash are used as main raw materials, a non-sintered technology is adopted, and the natural curing is carried out at the later stage, so that the equipment investment is little, a technological route is simple, and the energy consumption is low; and the prepared ceramisite has high strength, large specific surface area, rough surface and more holes, leached toxicity of heavy metals accord with GB5085.3-2007, and the prepared ceramisite can be used for water treatment engineering.

Description

A kind of method of utilizing chemical engineering sludge to prepare non-sintered haydite
Technical field
The present invention relates to a kind of method of utilizing chemical engineering sludge to prepare non-sintered haydite, belong to that the chemical industry hazardous solid waste process to be disposed and the resource technology field.
Background technology
Chemical industry is polluted many and serious, and especially in the chemical wastewater treatment process, every annual meeting produces a large amount of excess sludges, and their complicated components contain poisonous and hazardous organism and heavy metal etc.For a long time, domestic ubiquity the tendency of the light mud of heavy water, and the safe disposal ability of mud is in lower level always.
The disposal options of existing chemical engineering sludge is mainly to burn, but the incineration disposal expense is high, and there are the problem of disposing capacity deficiency in many units, therefore, then mud is illegally shifted, topples over, and causes serious environmental pollution.The lime-ash that sludge incineration produces is also dangerous solid waste, generally needs first pre-treatment, then carries out security landfill.Therefore the processing costs of incineration residue is also very high, and a lot of enterprises are difficult to bear, then process as general solid waste, make sludge burning ash residue not obtain rational ultimate disposal, become important environment risk source, also reasonably do not fully utilized, caused the waste of resource.Sludge burning ash residue is carried out innoxious and resource utilization, turn waste into wealth, meet the requirement of recycling economy and Sustainable development, be extremely important.
Haydite take lytag as representative generally has the characteristics such as specific surface area is large, and porosity is large, and physical strength is high, and chemistry and biologically stable are good, has obtained using more and more widely in engineering of water treatment.The main chemical compositions of chemical engineering sludge lime-ash and flyash are very approaching, all belong to CaO-SiO 2-Al 2O 3-Fe 2O 3System, thereby have the utilization of resources.
The preparation method of present China haydite is take sintering process as main, but the agglomerating plant investment is large, and energy consumption is high, and production cost is improved, and has limited to a certain extent the development of haydite manufacturer.
Summary of the invention
The object of the invention is to provide in order to improve the deficiencies in the prior art that a kind of physical strength is high, specific surface area is large, chemistry and a kind of good method of utilizing chemical engineering sludge to prepare non-sintered haydite of biologically stable, this haydite utilizes chemical engineering sludge and industrial waste flyash, adopt non-sintered method, thereby investment reduces, energy efficient, reduce costs, for the recycling treatment of chemical engineering sludge has been opened up new approach.
Technical scheme of the present invention is: a kind of method of utilizing chemical engineering sludge to prepare non-sintered haydite, it is characterized in that, and concrete steps are as follows:
(1) dry chemical engineering sludge, obtain dewatered sludge;
(2) roasting dewatered sludge, gained mud lime-ash is pulverized with pulverizer;
(3) various raw materials are mixed by proportioning, the dry blend that stirs to get, the mass percent that wherein in dry blend, each component and each component account for the dry blend total amount is respectively: mud lime-ash 20%-50%, flyash 25%-40%, cement 10%-25%, gypsum 5%-15%, light material 1%-5%, whipping agent 0.2%-0.6%;
(4) add water also stirring, mixing in above-mentioned dry blend, its amount of water is the 30%-40% of dry blend weight;
(5) make spheroidal particle, its particle diameter is 5-10mm;
(6) natural curing 7-15 days.
Preferred described light material is pearlstone, rice husk or wood chip.Preferred selected whipping agent is aluminium powder or zinc powder.In preferred steps (1), the temperature of sludge-drying is 105-120 ℃, and be 8-24h time of drying.In preferred steps (2), the temperature of roasting dewatered sludge is 550 ℃-700 ℃, and roasting time is 20-40min.
In the present invention, the mud lime-ash is similar to the main chemical compositions of flyash, possesses potential pozzolanic activity.Cement provides an effective alkaline environment as exciting agent, with SiO 2And Al 2O 3Effect generates the compound with hydraulic gelling property, simultaneously the heavy metal in the mud lime-ash is had solidification.Adding of gypsum can be accelerated active SiO 2, A1 2O 3Reaction, simultaneously gypsum again can with A1 2O 3Reaction, the calcium sulphoaluminate gum material of the generation hydraulicity.Light material can reduce the density of haydite, makes it lightization, and has certain bioaffinity.Whipping agent can be given birth to the reaction releasing hydrogen gas with steeping in water for reconstitution in alkaline environment, make filler produce pore, forms light porous structure.
Beneficial effect:
Compare with traditional sludge treatment and haydite preparation method, have following advantage:
1, in the present invention, the mass percent of mud lime-ash reaches 20%~50%, and utilization ratio is high, has greatly solved the problem of outlet of chemical engineering sludge.
2, the flyash in the present invention is also industrial solid castoff, further embodies efficient recycling rate, and obviously good environmental benefit and economic benefit arranged, and has dissemination.
3, the present invention in the mud ash comprehensive utilization, has realized the curing to heavy metal, therefore has innoxious and double effects resource utilization.
4, the present invention adopts non-sintered technique, and the later stage is carried out natural curing, and facility investment is few, operational path is simple, and energy consumption is low.
5, the haydite intensity of the present invention's preparation is high, and specific surface area is large, surface irregularity, and hole is many; All more than 60%, Leaching Heavy Metals meets " Hazardous wastes judging standard leaching characteristic identification " and (GB5085.3-2007), can be used for engineering of water treatment to the fixed rate of each heavy metal.
Description of drawings
Fig. 1 is the SEM Electronic Speculum figure on the prepared pottery material surface of embodiment 1;
Fig. 2 is the SEN Electronic Speculum figure of the prepared haydite section of embodiment 1;
Fig. 3 is process flow diagram of the present invention.
Embodiment
Process flow diagram of the present invention is as shown in Figure 3:
Embodiment 1:
Get water ratio and be certain chemical plant excess sludge of 84%, 110 ℃ of dry 12h are placed in retort furnace in 700 ℃ of roasting 20min with dewatered sludge, cooling pulverize with pulverizer afterwards.Get respectively mud lime-ash 35g, flyash 20g, 32.5R composite Portland cement 10g, gypsum 5g, wood chip 1g, aluminium powder 0.4g, fully stirring and evenly mixing gets dry blend, adds water and accounts for dry blend quality 36%, stirring and evenly mixing, then make spherical haydite again, and its diameter is at 5-10mm.Haydite at normal temperature, protected under damp condition maintenance 10 days.Test, its tap density is 723kg/m 3, the 1h water-intake rate is that 28.5%, BET specific surface area is 30.801m 2/ g, ultimate compression strength is 3.2MPa.Prepared pottery material surface and the SEM Electronic Speculum figure of section can find out on scheming as depicted in figs. 1 and 2: non-sintered haydite is surperficial and inside is coarse, numerous micro channels are arranged, and this structure is highly beneficial to adhering to, growing of microorganism.
Embodiment 2:
Get water ratio and be certain chemical plant excess sludge of 89%, 105 ℃ of dry 24h are placed in retort furnace in 600 ℃ of roasting 30min with dewatered sludge, cooling pulverize with pulverizer afterwards.Get respectively mud lime-ash 35g, flyash 40g, 32.5R composite Portland cement 15g, gypsum 10g, pearlstone 3g, zinc powder 0.4g, fully stirring and evenly mixing gets dry blend, adds water and accounts for 32% of dry blend quality, stirring and evenly mixing, then make spherical haydite again, and its diameter is in the 5-10mm left and right.Haydite at normal temperature, protected under damp condition maintenance 7 days.Test, its tap density is that tap density is 785kg/m 3, the 1h water-intake rate is that 25.7%, BET specific surface area is 21.175m 2/ g, resistance to compression Compressive Strength are 3.5Mpa.
Embodiment 3:
Get water ratio and be certain chemical plant excess sludge of 78%, 120 ℃ of dry 8h are placed in retort furnace in 550 ℃ of roasting 40min with dewatered sludge, cooling pulverize with pulverizer afterwards.Get respectively mud lime-ash 20g, flyash 35g, 32.5R composite Portland cement 25g, gypsum 15g, rice husk 5g, aluminium powder 0.21g, fully stirring and evenly mixing gets dry blend, adds water and accounts for 38% of dry blend quality, stirring and evenly mixing, then make spherical haydite again, and its diameter is in the 5-10mm left and right.Haydite at normal temperature, protected under damp condition maintenance 15 days.Test, its tap density is 826kg/m 3, the 1h water-intake rate is that 20.3%, BET specific surface area is 9.117m 2/ g, ultimate compression strength is 4.1Mpa.
The comparison of the non-sintered haydite Leaching Heavy Metals of table 1 and " Hazardous wastes judging standard leaching characteristic identification "

Claims (5)

1. a method of utilizing chemical engineering sludge to prepare non-sintered haydite, is characterized in that, concrete steps are as follows:
(1) dry chemical engineering sludge, obtain dewatered sludge;
(2) roasting dewatered sludge, gained mud lime-ash is pulverized with pulverizer;
(3) various raw materials are mixed by proportioning, the dry blend that stirs to get, the mass percent that wherein in dry blend, each component and each component account for the dry blend total amount is respectively: mud lime-ash 20%-50%, flyash 25%-40%, cement 10%-25%, gypsum 5%-15%, light material 1%-5%, whipping agent 0.2%-0.6%;
(4) add water also stirring, mixing in above-mentioned dry blend, its amount of water is the 30%-40% of dry blend weight;
(5) make spheroidal particle, its particle diameter is 5-10mm;
(6) natural curing 7-15 days.
2. method according to claim 1, is characterized in that described light material is pearlstone, rice husk or wood chip.
3. method according to claim 1, is characterized in that selected whipping agent is aluminium powder or zinc powder.
4. method according to claim 1, is characterized in that the temperature of sludge-drying in step (1) is 105-120 ℃, and be 8-24h time of drying.
5. method according to claim 1, is characterized in that the temperature of roasting dewatered sludge in step (2) is 550 ℃-700 ℃, and roasting time is 20-40min.
CN201310105707.4A 2013-03-28 2013-03-28 Method for preparing non-sintered ceramisites by using chemical sludge CN103145442B (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103588431A (en) * 2013-11-04 2014-02-19 盐城工学院 Formula and method for preparation of straw cement insulation brick
CN104230301A (en) * 2014-09-18 2014-12-24 河海大学 Biocompatible hydrophilic magnetic sludge fine aggregate carrier and preparation method thereof
CN104291859A (en) * 2014-10-14 2015-01-21 中建三局集团有限公司 Energy storage unfired sludge ceramsite and preparation method thereof
CN105016767A (en) * 2015-08-18 2015-11-04 长沙鼎成新材料科技有限公司 Light non-sintered ceramsite for road capital construction and preparing method thereof
CN105060832A (en) * 2015-08-20 2015-11-18 长沙鼎成新材料科技有限公司 Zeolite ceramsite for roof greening and preparing method of zeolite ceramsite
CN105060924A (en) * 2015-08-17 2015-11-18 长沙鼎成新材料科技有限公司 Light burn-free ceramsite for roof greening and preparation method thereof
CN105819887A (en) * 2016-03-08 2016-08-03 武汉大学 Preparation method of non-sintered ceramsite with ammonia nitrogen adsorption function
CN106082734A (en) * 2016-06-14 2016-11-09 马鞍山十七冶工程科技有限责任公司 A kind of municipal sludge baking-free ceramicite and preparation method thereof
CN106278039A (en) * 2016-08-15 2017-01-04 马鞍山十七冶工程科技有限责任公司 A kind of baking-free ceramicite lightweight concrete and preparation method thereof
CN106630815A (en) * 2016-10-09 2017-05-10 南京天合嘉能再生资源有限公司 Non-sintered ceramsite prepared from waste incineration bottom ashes and preparation method of non-sintered ceramsite
CN106673705A (en) * 2017-02-13 2017-05-17 常州大学 Treatment technology for waste incineration fly ash and excess sludge
CN107021734A (en) * 2017-03-29 2017-08-08 南京师范大学 Haydite prepared by a kind of utilization domestic refuse incineration ash sludge and preparation method thereof
CN109665805A (en) * 2019-01-08 2019-04-23 东南大学 A kind of core-shell structure curing sludge baking-free ceramicite and preparation method thereof
CN109761633A (en) * 2019-03-09 2019-05-17 大连地拓环境科技有限公司 A kind of unburned boron mud PVC haydite and preparation method thereof
CN111377628A (en) * 2020-03-20 2020-07-07 磊基环保高科股份有限公司 Method for preparing aggregate and concrete by using industrial solid waste
CN111470879A (en) * 2020-03-24 2020-07-31 北京科技大学 Preparation method of normal-temperature foamed high-temperature fired foamed ceramic

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5346549A (en) * 1992-10-23 1994-09-13 Johnson William B Environmentally stabilized products formed from ash and papermill waste
KR100562169B1 (en) * 2003-08-25 2006-03-20 전북대학교산학협력단 Manufacturing method of lightweight aggregate using ash from municipal and industrial solid waste incinerators
CN102249730A (en) * 2011-06-03 2011-11-23 南京工业大学 Method for preparing haydite from sludge incineration ash in chemical industry
CN102285786A (en) * 2011-06-03 2011-12-21 南京工业大学 Process for preparing hadite by utilizing chemical residual sludge
CN102617107A (en) * 2012-04-01 2012-08-01 浙江大学宁波理工学院 Building silt soil non-sintered ceramic aggregate and preparation method thereof
CN102617097A (en) * 2012-04-09 2012-08-01 武汉科技大学 Non-sintered ceramic aggregate with stone coal vanadium extraction tailings as main raw material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5346549A (en) * 1992-10-23 1994-09-13 Johnson William B Environmentally stabilized products formed from ash and papermill waste
KR100562169B1 (en) * 2003-08-25 2006-03-20 전북대학교산학협력단 Manufacturing method of lightweight aggregate using ash from municipal and industrial solid waste incinerators
CN102249730A (en) * 2011-06-03 2011-11-23 南京工业大学 Method for preparing haydite from sludge incineration ash in chemical industry
CN102285786A (en) * 2011-06-03 2011-12-21 南京工业大学 Process for preparing hadite by utilizing chemical residual sludge
CN102617107A (en) * 2012-04-01 2012-08-01 浙江大学宁波理工学院 Building silt soil non-sintered ceramic aggregate and preparation method thereof
CN102617097A (en) * 2012-04-09 2012-08-01 武汉科技大学 Non-sintered ceramic aggregate with stone coal vanadium extraction tailings as main raw material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
舒伟 等: "污泥焚烧灰制砖可行性及其效益分析", 《净水技术》 *

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CN103588431A (en) * 2013-11-04 2014-02-19 盐城工学院 Formula and method for preparation of straw cement insulation brick
CN104230301A (en) * 2014-09-18 2014-12-24 河海大学 Biocompatible hydrophilic magnetic sludge fine aggregate carrier and preparation method thereof
CN104230301B (en) * 2014-09-18 2016-03-23 河海大学 A kind of biocompatible hydrophilic magnetic sludge pottery sand carrier and preparation method thereof
CN104291859A (en) * 2014-10-14 2015-01-21 中建三局集团有限公司 Energy storage unfired sludge ceramsite and preparation method thereof
CN105060924A (en) * 2015-08-17 2015-11-18 长沙鼎成新材料科技有限公司 Light burn-free ceramsite for roof greening and preparation method thereof
CN105060924B (en) * 2015-08-17 2017-10-31 河南新封生态环境工程股份有限公司 It is a kind of for light non-fired haydite of roof greening and preparation method thereof
CN105016767A (en) * 2015-08-18 2015-11-04 长沙鼎成新材料科技有限公司 Light non-sintered ceramsite for road capital construction and preparing method thereof
CN105060832A (en) * 2015-08-20 2015-11-18 长沙鼎成新材料科技有限公司 Zeolite ceramsite for roof greening and preparing method of zeolite ceramsite
CN105060832B (en) * 2015-08-20 2017-06-06 刘欣萌 A kind of zeolite ceramsite for roof greening and preparation method thereof
CN105819887A (en) * 2016-03-08 2016-08-03 武汉大学 Preparation method of non-sintered ceramsite with ammonia nitrogen adsorption function
CN106082734A (en) * 2016-06-14 2016-11-09 马鞍山十七冶工程科技有限责任公司 A kind of municipal sludge baking-free ceramicite and preparation method thereof
CN106278039A (en) * 2016-08-15 2017-01-04 马鞍山十七冶工程科技有限责任公司 A kind of baking-free ceramicite lightweight concrete and preparation method thereof
CN106630815B (en) * 2016-10-09 2019-07-02 南京师范大学 Waste incineration bottom ash baking-free ceramicite and preparation method thereof
CN106630815A (en) * 2016-10-09 2017-05-10 南京天合嘉能再生资源有限公司 Non-sintered ceramsite prepared from waste incineration bottom ashes and preparation method of non-sintered ceramsite
CN106673705A (en) * 2017-02-13 2017-05-17 常州大学 Treatment technology for waste incineration fly ash and excess sludge
CN107021734A (en) * 2017-03-29 2017-08-08 南京师范大学 Haydite prepared by a kind of utilization domestic refuse incineration ash sludge and preparation method thereof
CN107021734B (en) * 2017-03-29 2020-04-21 南京师范大学 Ceramsite prepared from domestic garbage incineration ash sludge and preparation method thereof
CN109665805A (en) * 2019-01-08 2019-04-23 东南大学 A kind of core-shell structure curing sludge baking-free ceramicite and preparation method thereof
CN109761633A (en) * 2019-03-09 2019-05-17 大连地拓环境科技有限公司 A kind of unburned boron mud PVC haydite and preparation method thereof
CN111377628A (en) * 2020-03-20 2020-07-07 磊基环保高科股份有限公司 Method for preparing aggregate and concrete by using industrial solid waste
CN111470879A (en) * 2020-03-24 2020-07-31 北京科技大学 Preparation method of normal-temperature foamed high-temperature fired foamed ceramic

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