CN105967752B - Utilize the method for municipal sludge and carbide slag preparation low pollution plate - Google Patents
Utilize the method for municipal sludge and carbide slag preparation low pollution plate Download PDFInfo
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- CN105967752B CN105967752B CN201610301166.6A CN201610301166A CN105967752B CN 105967752 B CN105967752 B CN 105967752B CN 201610301166 A CN201610301166 A CN 201610301166A CN 105967752 B CN105967752 B CN 105967752B
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- carbide slag
- municipal sludge
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The present invention relates to a kind of preparation methods using municipal sludge and carbide slag preparation low pollution plate, by basic material wet basis municipal sludge, flyash, carbide slag and chip ballast measure respectively, the heavy metal ion in wet basis municipal sludge is solidified first, municipal sludge after a portion curing process carries out cracking carbonization pretreatment, municipal sludge and carbide slag after remainder curing process carry out mixed-sintering method pretreatment, then pretreated basic material is mixed, it is formed again using compression moulding method, it is dried after molding to constant weight, then green body is put into microwave sintering apparatus, extract vacuum, it is passed through CO2Keep system pressure constant, can be prepared by plate after maintenance.Beneficial effects of the present invention：Heavy metals immobilization effect is good, and the removal rate of each heavy metal species is greater than 90%, and is not limited by heavy metal type；Utilization rate of solid waste is high, and plate obtained can be suitably used in widely life production and application.
Description
Technical field
The invention belongs to recycling sludges to utilize technical field, in particular to a kind of to be prepared using municipal sludge and carbide slag
The preparation method of low pollution plate.
Background technique
China be one have a large population and a few land, the country of resource anxiety.In China, with constantly pushing away for level of urbanization construction
Into more and more stronger to the consciousness of environmental protection and from State-level to vast society, the number of sewage treatment plant in recent years
Amount sets level and sharply increases, and the sludge quantity (comprising various heavy metal ion etc.) generated therewith is also increasing.According to statistics, it arrives
The year two thousand twenty, China's municipal sludge discharge amount (dry weight) are up to 60,000,000 tons.It is how efficient and rational using these wastes, it is real
The now rationalization of waste, the utilization of recycling, have become current urgent problem.And in sludge organic matter contains
Amount is high, perishable smelly containing various pathogenic bacteria, not only can be right if a large amount of untreated sludge are piled up arbitrarily and discharge
Environment causes new pollution, but also can waste the useful resources in sludge.Therefore, how big, complicated component the dirt by yield
Mud makes its minimizing, innoxious, stabilisation and recycling after scientific disposal, it is extensive to have become China or even the whole world
The hot issue of concern.
Carbide slag quantity is big, and alkalinity is high, and containing harmful substances such as sulphur, arsenic, can block sewer without processing discharge,
Stop up product riverbed, endangers fish production.Then land occupation is stacked on land, pollutes environment.Work of some construction in strand or mountain area
Carbide slag is exhausted directly in seawall or mountain valley by factory all the time, is filled out sea and is filled out the regular stacking of ditch, several exhale is not made at antiseepage
Reason.This method takes up a large area, seriously polluted.According to calculating, often make the pure calcium carbide of 1t, will be about generating 1.16t carbide slag, currently,
Main to the utilization of carbide slag there are two aspects, are on the other hand to pass through these for environmental improvement first is that being used for building industry
Approach still has a large amount of carbide slags unutilized merely with part carbide slag.A large amount of stackings of carbide slag had both occupied a large amount of
Land resource, and polluted environment, therefore, how carbide slag to be turned waste into wealth have been very urgent at this stage.
In recent years, the yield rapid growth of China's sludge and carbide slag.How efficiently utilize municipal sludge, carbide slag this
Class solid waste prepares environment-friendly materials, studies existing document, has had certain report, has still had at the same time
Problem, such as：
1. containing a large amount of heavy metal ion in municipal sludge, these ions can cause greatly human lives and production
Injury, for current technique, there are no good solution, and sludge is made into construction material and is applied to by blindness
In daily life production, over time, heavy metal ion therein can slowly leach exudation, to the health of people
It causes damages
2. also a large amount of house refuse and urban pollutant in municipal sludge, contain a large amount of germs and harmful micro- life
Object, various organic matters are allowed to form flocculation glue, and at this stage in industry, burning sludge is main processing means, but this is not only
A large amount of resource and fuel are wasted, and burn the pernicious gas generated to pollute air, caused serious injury to neighbouring crowd,
Certain achievement has been obtained using the equal construction materials that municipal sludge prepares plate at present.Such as Xi'an benefit is raw dirty
One Chinese patent (patent publication No. of mud processing Co., Ltd：CN104649650A a kind of new city sludge system) is disclosed
The preparation method of brick.It carries out dehydration and deodorizing process, the green day environment work in Zhejiang to sludge using sludge dehydrating agent and deodorant
A kind of degradable sludge plastics environment protecting plate disclosed in journey Co., Ltd and preparation method thereof (patent publication No.：
CN104591682A), using sludge and wood powder, PP powder, various additives and carry out secondary demoulding and be granulated, injection forming, but
The plate that this method obtains, durability and thermal insulation property are unable to get guarantee, and this method is to the heavy metal in sludge
Ion and organic matter are not also handled well, are only added additive and are allowed to be fixed up, it is difficult to be used for a long time.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to above-mentioned deficiency of the prior art, provide a kind of using city
The method of city's sludge and carbide slag preparation low pollution plate, contains a large amount of heavy metal ion and organic matter for sludge itself,
The pollutant secondary cycle for polluting environment is utilized, realizes the dual increment of economic benefit and social benefit.
The present invention be solve the problems, such as it is set forth above used by technical solution be：It is prepared using municipal sludge and carbide slag
The method of low pollution plate measures basic material wet basis municipal sludge, flyash, carbide slag and chip ballast respectively, right first
Heavy metal ion in wet basis municipal sludge is solidified, and the municipal sludge after a portion curing process carries out cracking carbonization
It pre-processes, the municipal sludge and carbide slag after remainder curing process carry out mixed-sintering method pretreatment, then will pretreatment
Basic material mixing afterwards, then formed using compression moulding method, it dries after molding to constant weight, green body is then put into microwave sintering
In equipment, vacuum is extracted, CO is passed through2Keep system pressure constant, can be prepared by plate after maintenance.
According to the above scheme, the quality group of the basic material becomes：Wet basis municipal sludge 40~60%, flyash 10~
20%, carbide slag 25~40%, chip ballast 5~10%.
According to the above scheme, the curing process is first into wet basis municipal sludge, and addition concentration is 2wt.% dioxygen
The phosphoric acid mixed solution that water and concentration are 42wt.%, stirs 1h, stands reaction for 24 hours, passes through adsorption column and an adsorption tanks recycling huge sum of money
Belong to, the sludge slurry after recovery processing is spare.
According to the above scheme, the wet basis municipal sludge, initial moisture >=50wt.%, wherein the pre- place of cracking carbonization
Sludge quantity≤20wt.% of reason, temperature is at 240~300 DEG C when low temperature pyrolyzer, 10~15Mpa of pressure；Mixed-sintering method pretreatment
Sludge quantity >=80wt.%, content 12%≤θ≤20% of carbide slag, sintering temperature be 900~950 DEG C.
According to the above scheme, the carbide slag is slurry, water content≤50wt.%.
According to the above scheme, the chip ballast partial size 5mm≤r≤30mm.
According to the above scheme, the maintenance is using microwave carbonized maintaining, curing time 2h, and curing temperature is 200 ± 5
DEG C, CO2Gas pressure is 0.4Mpa.
Main technical principle of the invention is：For the heavy metal and organic matter this two large problems in processing sludge,
In terms of heavy metals immobilization, 1, catalysis with valence state control technology, using in sludge each heavy metal species and phosphoric acid it is anti-
Soluble metal salt should be generated, then exchanges the heavy metal ion in phosphoric acid solution with acid cation exchange resin, with removal
Heavy metal in sludge, and recycle phosphoric acid；2, steam press maintenance technology is utilized, it is contemplated that remaining heavy metal ion can be in sludge
When blanks and moulding and conserving ion concentration and overflow the case where, admittedly use microwave curing and carbonized maintaining technology；Microwave curing technology is with it
The entirety of unique no temperature gradient heats, and plate slurry quickly, is uniformly dried, on the other hand, what microwave generated
Electromagnetic field improves the crystallization reaction rate of chemical substance and the rule degree of crystal lattice in material greatly, so that slurry
In a short time can depanning, in this way can in slurry it is middle residue heavy metal overflow surface before solidify, stablize weigh
Metal；3, it using surface densification technology, is passed through after carbon dioxide gas in maintenance bin, carbon dioxide can be with slurry mineral
React, while releasing a large amount of heat, the fast reaction phase be formed by reactant be covered on non-reacted parts surface and
Slow down reaction rate, so carbonized maintaining improves the compactness of product surface, not only can increase the intensity of plate in this way, but also
It can be reduced heavy metal volume spilling；
In terms of mud organic substance processing, 1, proportionally mixed using carbide slag and sludge after calcine, in calcination process
Middle carbide slag and sludge can form a large amount of active CaO-SiO in the high temperature process2System provides by force for late phase reaction
Degree；2, the low-temperature carbonization of sludge, it is main that influence of the organic matter to timber intensity is eliminated by carbonization, meanwhile, sludge is carbonized to be formed
Porous structure, on the one hand can say the thermal coefficient for reducing material, on the other hand can have again and absorb moisture or pernicious gas
Ability, obtain functionalization for material and basis be provided.
The present invention is obtained to be had the beneficial effect that：Heavy metals immobilization effect is good, processes agent with the phosphoric acid containing hydrogen peroxide
Removal sludge heavy-metal works well, and the removal rate of each heavy metal species is greater than 90%, and is not limited by heavy metal type；Solid
Waste utilization rate is high, and material based on municipal sludge and carbide slag is largely used in this technology, is modified processing to sludge,
Two kinds of nuisances are not only utilized, but also plate obtained can be suitably used in widely life production and application；Material property is good, tool
Functional property cracks in carbonisation by sludge, has reached porous structure not available for other plates, improves in this way and be
The thermal insulation property and functionalization of system are used, and used chip ballast serves as the effect of aggregate, transmits pressure at the time of molding, makes base
Body is closely knit, reduces the cubic deformation of product later period and improves frost resistance.
Specific embodiment
The invention of the application is further illustrated below with reference to example, but embodiment is not construed as the limit to right of the present invention
It is fixed.
Embodiment 1：
The wet basis municipal sludge that the present invention uses, initial moisture >=50wt.%, carbide slag are slurry, water content≤
50wt.%, the chip ballast partial size 5mm≤r≤30mm.
The present invention relates to a kind of preparation methods that plate is prepared using municipal sludge and carbide slag, according to parts by weight,
Its raw-material weight percentage is：40wt.% wet basis municipal sludge, 20wt.% flyash, 30wt.% carbide slag, 10wt.%
Chip ballast, if the phosphoric acid mixed liquor of the hydrogen peroxide of dry measure 2wt.% concentration and 42wt.% concentration.Preparation process is：By wet basis city
City's sludge is mixed with the phosphoric acid solution of the hydrogen peroxide of 2% concentration and 42% concentration, agitated reaction 1h, stand for 24 hours after, through acidity
Cationic exchange resin adsorption recycles heavy metal and phosphoric acid solution, and taking 18wt.% sludge slurry through temperature is 280 DEG C, pressure is
The carbonization of 15Mpa low temperature pyrolyzer, the sludge slurry of remaining 82wt.% are blended in the carbide slag that its mass percent is 20% is accounted for
It is sintered in 950 DEG C of tunnel oven, it is levigate spare through roller after sintering, then each raw material is proportionally used after mixing
Compression moulding method compression moulding in corresponding molding die, briquetting pressure 20Mpa, molding cycle 17s, after molding
Dry in 100 DEG C of environment, drying time for 24 hours, is sent into steam press maintenance room after the completion of dry, is passed through CO in extracting bin after vacuum2,
Curing temperature is set as 200 DEG C, power 3kw, temperature rises 90min, keeps the temperature 30min, obtained plate compression strength
In 60Mpa, tensile strength 28Mpa, Leaching Heavy Metals measurement experiment is according to standard GB/T 5086.2-1997《Solid
Waste Leaching leaching method-horizontal vibration method》It executes, it is as follows to obtain leaching rate of heavy metals, Zn：4mg/L, Hg：
0.002mg/L, Pb：0.17mg/L,Cd：0.03mg/L,Cr(Ⅵ)：0.11mg/L；Thermal coefficient is 0.14 [W (mK)-1]。
Embodiment 2：
The wet basis municipal sludge that the present invention uses, initial moisture >=50wt.%, carbide slag are slurry, water content≤
50wt.%, the chip ballast partial size 5mm≤r≤30mm.
The present invention relates to a kind of preparation methods that plate is prepared using municipal sludge and carbide slag, according to parts by weight,
Its raw-material weight percentage is：50wt.% wet basis municipal sludge, 15wt% flyash, 30wt%. carbide slag, 5wt.% are broken
Rock ballast, if the phosphoric acid mixed liquor of the hydrogen peroxide of 2% concentration of dry measure and 42% concentration.Preparation process is：By wet basis municipal sludge with
The hydrogen peroxide of 2wt.% concentration and the mixing of the phosphoric acid solution of 42wt.% concentration, agitated reaction 1h, after standing for 24 hours, through acid positive
Ion exchange resin adsorption recovery heavy metal and phosphoric acid solution, taking 15wt.% sludge slurry through temperature is 270 DEG C, pressure is
The carbonization of 12Mpa low temperature pyrolyzer, the sludge slurry of remaining 85wt.% are blended in the carbide slag that its mass percent is 20% is accounted for
It is sintered in 900 DEG C of tunnel oven, it is levigate spare through roller after sintering, it is counted respectively after various raw material are pre-processed as requested
Amount, proportionally uses compression moulding method compression moulding in corresponding molding die after mixing, and briquetting pressure is
15Mpa, molding cycle 17s, dry in 100 DEG C of environment after molding, drying time for 24 hours, is sent into steam pressure after the completion of dry and supports
It protects in room, is passed through CO in extracting bin after vacuum2, curing temperature is set as 200 DEG C, power 3kw, and temperature rises 90min, heat preservation
30min, obtained plate compression strength is in 58Mpa, tensile strength 34Mpa, Leaching Heavy Metals measurement experiment
According to standard GB/T 5086.2-1997《Solid waste Leaching leaching method-horizontal vibration method》It executes, obtains a weight
Metal leaching rate is as follows, Zn：:6mg/L, Hg：0.003mg/L, Pb：0.2mg/L,Cd：0.06mg/L,Cr(Ⅵ)：0.18mg/L；
Thermal coefficient is 0.12 [W (mK)-1].
Embodiment 3
The wet basis municipal sludge that the present invention uses, initial moisture >=50wt.%, carbide slag are slurry, water content≤
50wt.%, the chip ballast partial size 5mm≤r≤30mm.
The present invention relates to a kind of preparation methods that plate is prepared using municipal sludge and carbide slag, according to parts by weight,
Its raw-material weight percentage is：50wt%. wet basis municipal sludge, 10wt%. flyash, 35wt%. carbide slag, 5wt%. are broken
Rock ballast, if the phosphoric acid mixed liquor of the hydrogen peroxide of 2% concentration of dry measure and 42% concentration.Preparation process is：By wet basis municipal sludge with
The hydrogen peroxide of 2wt.% concentration and the mixing of the phosphoric acid solution of 42wt.% concentration, agitated reaction 1h, standing for 24 hours after, through through acidity
Cationic exchange resin adsorption recycles heavy metal and phosphoric acid solution, and taking 20wt.% sludge slurry through temperature is 300 DEG C, pressure is
The carbonization of 15Mpa low temperature pyrolyzer, the sludge slurry of remaining 80wt.% are blended in the carbide slag that its mass percent is 20% is accounted for
It is sintered in 950 DEG C of tunnel oven, it is levigate spare through roller after sintering, it is counted respectively after various raw material are pre-processed as requested
Amount, proportionally uses compression moulding method compression moulding in corresponding molding die after mixing, and briquetting pressure is
15Mpa, molding cycle 17s, dry in 100 DEG C of environment after molding, drying time for 24 hours, is sent into steam pressure after the completion of dry and supports
It protects in room, is passed through CO in extracting bin after vacuum2, curing temperature is set as 200 DEG C, power 3kw, and temperature rises 90min, heat preservation
30min, obtained plate compression strength is in 50Mpa, tensile strength 31Mpa, Leaching Heavy Metals measurement experiment
According to standard GB/T 5086.2-1997《Solid waste Leaching leaching method-horizontal vibration method》It executes, obtains a weight
Metal leaching rate is as follows, Zn：:4mg/L, Hg：0.002mg/L, Pb：0.15mg/L,Cd：0.04mg/L,Cr(Ⅵ)：0.13mg/
L；Thermal coefficient is 0.11 [W (mK)-1].
Embodiment 4
The wet basis municipal sludge that the present invention uses, initial moisture >=50wt.%, carbide slag are slurry, water content≤
50wt.%, the chip ballast partial size 5mm≤r≤30mm.
The present invention relates to a kind of preparation methods that plate is prepared using municipal sludge and carbide slag, according to parts by weight,
Its raw-material weight percentage is：45wt%. wet basis municipal sludge, 10wt%. flyash, 40wt%. carbide slag, 5wt%. are broken
Rock ballast, if the phosphoric acid mixed liquor of the hydrogen peroxide of 2% concentration of dry measure and 42% concentration.Preparation process is：By wet basis municipal sludge with
The hydrogen peroxide of 2wt.% concentration and the mixing of the phosphoric acid solution of 42wt.% concentration, agitated reaction 1h, after standing for 24 hours, through acid positive
Ion exchange resin adsorption recovery heavy metal and phosphoric acid solution, taking 12wt.% sludge slurry through temperature is 240 DEG C, pressure is
The carbonization of 10Mpa low temperature pyrolyzer, the sludge slurry of remaining 88wt.% are blended in the carbide slag that its mass percent is 20% is accounted for
It is sintered in 900 DEG C of tunnel oven, it is levigate spare through roller after sintering, it is counted respectively after various raw material are pre-processed as requested
Amount, proportionally uses compression moulding method compression moulding in corresponding molding die after mixing, and briquetting pressure is
10Mpa, molding cycle 17s, dry in 100 DEG C of environment after molding, drying time for 24 hours, is sent into steam pressure after the completion of dry and supports
It protects in room, is passed through CO in extracting bin after vacuum2, curing temperature is set as 200 DEG C, power 3kw, and temperature rises 90min, heat preservation
30min, obtained plate compression strength is in 56Mpa, tensile strength 30Mpa, Leaching Heavy Metals measurement experiment
According to standard GB/T 5086.2-1997《Solid waste Leaching leaching method-horizontal vibration method》It executes, obtains a weight
Metal leaching rate is as follows, Zn：:5mg/L, Hg：0.003mg/L, Pb：0.17mg/L,Cd：0.05mg/L,Cr(Ⅵ)：0.14mg/
L；Thermal coefficient is 0.13 [W (mK)-1]。
Claims (6)
1. using municipal sludge and carbide slag preparation low pollution plate method, by basic material wet basis municipal sludge, flyash,
Carbide slag and chip ballast measure respectively, and the quality group of the basic material becomes：Wet basis municipal sludge 40~60%, flyash
10~20%, carbide slag 25~40%, chip ballast 5~10%；The heavy metal ion in wet basis municipal sludge is consolidated first
Change, the municipal sludge after a portion curing process carries out cracking carbonization pretreatment, the city after remainder curing process
Sludge and carbide slag carry out mixed-sintering method pretreatment, then mix pretreated basic material and untreated basic material
It closes, then is formed using compression moulding method, dry after molding to constant weight, then green body is put into microwave sintering apparatus, extract true
Sky is passed through CO2Keep system pressure constant, can be prepared by plate after maintenance.
2. the method according to claim 1 using municipal sludge and carbide slag preparation low pollution plate, which is characterized in that
The curing process is first into wet basis municipal sludge, and addition concentration is 2wt.% hydrogen peroxide and concentration is 42wt.%'s
Phosphoric acid mixed solution stirs 1h, stands reaction for 24 hours, recycles heavy metal by adsorption column and adsorption tanks, the sludge after recovery processing
Mud is spare.
3. the method according to claim 1 using municipal sludge and carbide slag preparation low pollution plate, which is characterized in that
The wet basis municipal sludge, initial moisture >=50wt.%, wherein the pretreated sludge quantity of cracking carbonization≤
20wt.%, temperature is at 240~300 DEG C when low temperature pyrolyzer, 10~15Mpa of pressure；The pretreated sludge quantity of mixed-sintering method >=
80wt.%, content 12wt.%≤θ≤20wt.% of carbide slag, sintering temperature are 900~950 DEG C.
4. the method according to claim 1 using municipal sludge and carbide slag preparation low pollution plate, it is characterised in that
The carbide slag is slurry, water content≤50wt.%.
5. the method according to claim 1 using municipal sludge and carbide slag preparation low pollution plate, it is characterised in that
The chip ballast partial size 5mm≤r≤30mm.
6. the method according to claim 1 using municipal sludge and carbide slag preparation low pollution plate, it is characterised in that
The maintenance is using microwave carbonized maintaining, curing time 2h, and curing temperature is 200 ± 5 DEG C, CO2Gas pressure is
0.4Mpa。
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| CN107540322B (en) * | 2017-09-22 | 2020-02-07 | 广州市建筑科学研究院有限公司 | Inorganic artificial stone containing high-performance ceramsite and super absorbent resin and preparation method thereof |
| CN115611543B (en) * | 2022-10-24 | 2023-06-13 | 河南理工大学 | High-activity coal gasification slag mineral admixture and preparation method and application thereof |
| CN115772013B (en) * | 2023-02-15 | 2023-04-28 | 河北工业大学 | Concrete containing silt powder and solid carbide slag |
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