CN107233861A - A kind of micro-nano mineral material of purification of heavy metal sludge and preparation method thereof - Google Patents
A kind of micro-nano mineral material of purification of heavy metal sludge and preparation method thereof Download PDFInfo
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- CN107233861A CN107233861A CN201610177509.2A CN201610177509A CN107233861A CN 107233861 A CN107233861 A CN 107233861A CN 201610177509 A CN201610177509 A CN 201610177509A CN 107233861 A CN107233861 A CN 107233861A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/004—Sludge detoxification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Sludge (AREA)
- Fertilizers (AREA)
- Water Treatment By Sorption (AREA)
Abstract
A kind of micro-nano mineral material of purification of heavy metal sludge and preparation method thereof, it is characterised in that micro-nano mineral material is the layer aluminosilicate classes such as bentonite, zeolite powder, concave convex rod.Clay mineral has very strong adsorption capacity to the molecular state in sludge, ionic state pollutant or heavy metal ion, can produce huge surface can and internal surface area, therefore, it is possible to adsorb the pollutant and heavy metal ion in crossover fixation sludge.Clay mineral is negatively charged, and isomorphous replacement is acted between crystal layer, and crystalline surface hydroxyl dissociation goes out H when being derived partly from colloid isoelectric point+The variable charge soil produced afterwards.The permanent negative electrical charge of smectites accounts for the 95% of total negative charge amount.The heavy metal alkali ionic portions of absorption are located at intracell, are difficult desorption.Micro-nano mineral material improves sludge dewatering, decrement, deammoniation, fixes 50% or so heavy metal ion and eliminate flocculant pollution, reach the effect of purification sludge, through Overheating Treatment, intermediary water of going out increases clay mineral internal surface area using preceding.
Description
Technical field
The sludge treating agents such as zeolite, bentonite, concave convex rod are a kind of high activity filter in itself, pollutant generation is filtered,
The physical effects such as dilution.Sludge treating agent have physical property, colloidal nature, coordination and chelation, redox property and
Self cleaning of class soil etc..Organic and inorganic pollutant in sludge cannot directly enter soil system, due to being wadded a quilt with cotton in sludge
The incobation solidification of solidifying agent, energy heavy damage soil texture, makes soil become waterproof, air-locked soil that is allowed to lie waste；Contain
The sludge of heavy metal can not make fertilizer and enter crop system, grain, vegetables can be made by heavy metal pollution, harm crowd body is good for
Health；Sludge containing heavy metal can not do garbage loading embeading, and water content is high, makes soil gleying, rotten hair is smelt, a large amount of greenhouse gases two
Carbonoxide and discharge of methane, destruction soil, polluted underground water and atmospheric environment.The dirts such as sludge treating agent suction-operated heavy metal
Chemistry, biochemical reaction produced by the Transport And Transformation of dye thing have significant purification, metabolism.Sludge treating agent it is scattered
Degree is higher, and grogs diameter is smaller, and its total surface area is bigger, and the material bigger than surface has higher surface energy, shows
Cementing, absorption and other different physics and physicochemical properties.For example, fine grained has king-sized cementing properties and energy of adsorption
Power.General sludge treating agent inner space, which does not have, to be all filled, and it is always arranged by certain way, there is many holes therebetween
Gap, pore system includes the different intergranular pore of a large amount of form and dimensions, by also small more logical than hole diameter itself between them
Road is mutually linked.It is in collosol state after Adsorption of Heavy Metals ion, the flocculation state material of indissoluble is respectively formed with other metal ions,
The also poisonous heavy metal ion of sticking, alleviates its murder by poisoning to plant simultaneously.Inorganic colloid includes secondary clay mineral, iron aluminium
Hydrous oxide, oxidizing aqueous silicon amphoteric colloid.Secondary clay mineral mainly has montmorillonite, illite, kaolinite, is particle diameter
Layer aluminosilicate less than 5nm, has very strong adsorption capacity to molecular state, ionic state pollutant in soil.Its reason is：It is glutinous
Native mineral grain is fine, with very big surface area, wherein with smectites largest surface area (600~800 m2/g), it is not
Only outer surface, and have huge inner surface；Illite takes second place (100~200 m2/g), kaolinite minimum (7~30 m2/
g)；Huge surface area supervenes huge surface energy, therefore, it is possible to adsorb the air-liquid state pollutant in sludge.
Background technology
Clay mineral is negatively charged, and cation exchange capacity (CEC) is high, has stronger exchange to consolidate for sludge intermediate ion state pollutant
Capability；Montmorillonite and kaolinic cation exchange capacity are respectively 80~120,3~15 mequiv/100g.It was found that
The permanent negative electrical charge of smectites accounts for the 95% of total negative charge amount, and illite accounts for 60%, and kaolinite accounts for 25%.The metal of kaolinite absorption
Cation-bit is easily desorbed on crystalline surface ion exchange point；And the base cation part of montmorillonite, illite absorption is located at
Intracell, is difficult desorption.Cation exch ange adsorption refers to that absorption and holding of the colloid to ionic state material are acted on, really glue
Cation in body decentralized system in the cation and sludge solutions of diffusion layer is exchanged with each other the process for reaching balance.It has following
Three features, Cation adsorption process is a kind of dynamic equilibrium of reversible reaction.Into the concentration of metal ions of sludge treating agent
Higher, valence state is higher, then is more easily adsorbed by colloid.Cation exchange capacity (CEC) is that equivalent is carried out.Various cations are by colloidal substance
The affinity size of absorption is different.To coion, ionic radius is smaller, more adsorbed, colloid adsorbing metal ions
Ability be also frequently subjected to the influence of sludge treating agent conditions of mixture ratios.The permutable cation amount of different colloidal substance institutes is different.
The factor for determining heavy metal-polluted soil adsorbance is sludge treating agent exchange capacity, absorption of the different clay minerals to metal ion first
Affinity order is different.For example：Montmorillonite is to the absorption of bivalent metal ion order：Ca2+ ＞ Pb2+ ＞ Cu2+
＞ Mg2+>Cd2+ ＞ Zn2+；Kaolinite is：Pb2+ ＞ Ca2+ ＞ Cu2+ ＞ Mg2+ ＞ Zn2+ ＞ Cd2+；Illite is：Pb2+
＞ Ca2+ ＞ Zn2+ ＞ Cu2+ ＞ Cd2+.The suction-operated of sludge treating agent heavy metal ion etc. and chelation can be sent out simultaneously
It is raw.When concentration of heavy metal ion is high based on exchange adsorption, during low concentration based on chelation.Sludge treating agent combines gold
Category ion energy order be：Pb ＞ Cu ＞ Ni ＞ Co ＞ Zn ＞ Mn ＞ Mg ＞ Ba ＞ Ca ＞ Hg ＞ Cd.So organic colloid pair
The absorption of metal ion always contribution is less than inorganic colloid, but soil organic colloid moving to pollutant, particularly organic pollution
Transferization and biological effect have important influence.The absorption of sludge treating agent heavy metal and agricultural chemicals, for controlling them in soil
Migration in earth botanical system plays an important role.Activity such as heavy metals in soil depends greatly on soil
Suction-operated.Clay mineral and humus heavy metal in soil have very strong adsorption capacity, can reduce the work of heavy metal
Property.The above-mentioned property of soil has a great impact to the Transport And Transformation of pollutant.As soil colloid can adsorb various pollutants simultaneously
Its activity is reduced, microorganism has special degradation to organic pollution so that soil has itself superior updating ability,
And need not be by external force.Itself this updating ability of soil, the referred to as self purification of soil.Pollutant enters after soil, its
Self purification process approximately as：Pollutant reduces its concentration in soil through physical processes such as diffusion, dilution, volatilizations；Through biological and
Chemical degradation is nontoxic or low toxicity material, or is converted into by chemical precipitation, cooperation or chelation, redox insoluble
Property compound, or firmly adsorbed by soil colloid, it is difficult to be plant absorption, and temporarily exit small biological cycle, depart from food
In chain or the air or water body that are discharged to outside the soil body.Montmorillonite and kaolinite etc. are better than the self-purification capacity of soil, montmorillonite and
Kaolinite detergent power is relevant with the material composition of sludge and other characteristics and the species of pollutant, property.Different mineral materials
Self-purification capacity be different, same mineral material is also discrepant to the detergent power of different pollutants.Generally speaking, ore deposit
The self-cleaning speed ratio of matter sludge scavenging material is very fast, and pollutant, which enters relatively to be difficult to resolve after mineral scavenging material, to be separated out.
The content of the invention
One kind purification micro-nano nonmetallic serial mineral material of sludge, it is characterised in that contain a certain amount of soap in the material
The micro-nano nonmetallic ore material such as soil, concave convex rod, zeolite, above-mentioned mineral material is formed by micro-nano technique process technology
The sludge scavenging material of cocrystallization complex or mixture.Micro-nano nonmetallic sludge mineral scavenging material, it is characterised in that dirty
The preferred proportion that mud chats material addition accounts for sludge gross weight is 35%~55%.Preferably sludge moisture content will be controlled
70%~80%.Preferably nonmetallic ore material feed additives, micro-nano-scale is controlled at 200 ~ 2000 nanometers, and processing technology is optional
With airslide disintegrating mill and the related precisely technique process technology such as disintegrating apparatus.Preferably micro-nano nonmetallic ore material kind soap
Soil is the ultrafiltration agent of biological sludge, particularly to dyeing waste water, biogas waste water, food plant wastewater, paper waste, slaughterhouse's waste water
Biological sludge processing has good effect, and the material of organic matter sludges processing prepares bentonite content and wants ＞ 60%, unclassified stores content
For less than 40%, reference formulation ratio is：Bentonite：Concave convex rod：Zeolite=6.0:3.0:1.0.Preferably micro-nano nonmetallic mineral
Material concave convex rod, is a kind of heavy metal pollution eliminated in sludge, purifying eutrophic sludge ammoniacal nitrogen, organophosphor and poisonous is had
The main material of evil bacterium class, attapulgite its huge surfaces externally and internally product, tiny bar-shaped, needle-like and fibrous porous structure
It is the important indicator of its physical absorption, the material of eutrophication Treatment of Sludge prepares concave convex rod content and wants ＞ more than 60%, other things
It is less than 40% to expect content, and reference formulation ratio is：Concave convex rod：Bentonite：Zeolite=6.0:2.0:2.0.Preferably micro-nano non-gold
Belong to material zeolite, be that the organic matter in the sedimentary rock that volcano is sprayed, rock is liquefied or vaporized and produces fine hole, these
The size in aperture about in below 1nm, possesses the adsorption function to organic molecule and cation, can eliminate the mercury cadmium lead in sludge
The poisonous and harmful heavy metallic ion such as arsenic, zeolite is to ammonia（NH4+）With higher absorption and exchange force, reference formulation ratio is：Boiling
Stone：Bentonite：Concave convex rod=4.0:3.0:3.0. micro-nano mineral sludge scavenging material, it is characterised in that the material will pass through high temperature
Heat, processing control temperature is in 130 ~ 180 degree, and sludge water content content is high or content of beary metal is high, sludge scavenging material control
Temperature processed is in 150 ~ 180 degree, and sludge water content content is low or content of beary metal is low, and sludge scavenging material controls temperature 130 ~ 150
Scavenging material after degree, high-temperature heating treatment has small-size effect, high surface area effect and tunnel-effect, can promote in sludge
Eutrophication ion and the absorption of the lattice of heavy metal ion, chelating, flocculation and precipitation, reach the heavy metal ion entered in lattice
To the purpose permanently sealed up for safekeeping.The preparation method of sludge scavenging material bentonite, concave convex rod, zeolite etc., is to have selected the general non-gold of production
Belong to the mineral processing circuit of mineral material, disintegrating process flow, micro/nano level superfine Me flows quantitatively input the electricity of additive
Brain control device, material mixes equipment.Additive pulverizer, storagetank, computer-metering pump, stirring are set up in the technique
The supporting production lines such as machine, material conveyer, weighing machine, packing machine, freeze-day with constant temperature warehouse.Bentonite, concave convex rod, zeolite etc. are
Row sludge scavenging material in the form of mixing powder to be added in the technological process that sludge material is handled, bentonite, concave convex rod, zeolite
Configuration proportion Deng serial sludge scavenging material processing sludge can flexibly be grasped according to sludge moisture content or content of beary metal, sludge
It is with scavenging material reference formulation ratio：Heavy metal serious pollution sludge：Scavenging material：Sludge=50:50；Heavy metal moderate is dirty
Stain mud：Scavenging material：Sludge=40:60；Heavy metal slight pollution sludge：Scavenging material：Sludge=30:70.Serial sludge is net
Change the sludge handled by material, it is characterised in that the incobation solidification of flocculant in sludge can be broken, eliminate flocculant
The harm of soil texture is destroyed, the sludge water content content after processing can be reduced to 20% or so, and it is left that the content of organic matter can be reduced to 5%
The right side, content of beary metal can reduce by 30% ~ 70%, and the cation exchange capacity (CEC) such as ammonia can reduce more than 30%, and the sludge after processing can be used for
Land remediation, desert transformation, meadow is reclaimed, and urban afforestation and directly makes organic Fertilizer application.
Subordinate list illustrates the clean-up effect before and after the micro-nano mineral material process of the heavy metal sewage sludge of table 1
The measurement result of table 1 shows, the micro-nano nonmetallic ore matter sludge scavenging material that this patent is provided, to all heavy metals all
There is purification absorption fixation, except content is bordering on outside trace, purification negligible amounts in mercury, cadmium heavy metal sewage sludge, remaining sludge
The high heavy metal purifying rate of middle content is both greater than more than 75%.The cation exchange capacity (CEC) such as ammonia purifying rate more than 87% in sludge.
Embodiment
Micro-nano mineral sludge scavenging material will pass through high-temperature heating treatment, and processing control temperature is in 130 ~ 180 degree.Sludge
Moisture is high or content of beary metal is high, and sludge scavenging material controls temperature in 150 ~ 180 degree.Sludge water content content it is low or a huge sum of money
Belong to content low, sludge scavenging material controls temperature at 130 ~ 150 degree.Scavenging material after high-temperature heating treatment has small size effect
Should, high surface area effect and tunnel-effect, eutrophication ion and the absorption of the lattice of heavy metal ion, chela in sludge can be promoted
Close, flocculate and precipitate, the heavy metal ion entered in lattice is reached the purpose permanently sealed up for safekeeping.Sludge scavenging material bentonite,
The preparation method of concave convex rod, zeolite etc., is the mineral processing circuit for having selected the general nonmetallic ore material of production, disintegrating process stream
Journey, micro/nano level superfine Me flows quantitatively input the computer controling equipment of additive, and material mixes equipment.The technique
In set up additive pulverizer, storagetank, computer-metering pump, mixer, material conveyer, weighing machine, packing machine, freeze-day with constant temperature
The supporting production line such as warehouse.The series sludge scavenging material such as bentonite, concave convex rod, zeolite is added in the form of mixing powder
In the technological process of sludge material processing, the configuration proportion of sludge scavenging material and processed sludge can according to sludge moisture content or
Content of beary metal is flexibly grasped, and sludge and scavenging material reference formulation ratio are：Heavy metal serious pollution sludge, scavenging material：
Sludge=50:50；Heavy metal intermediate pollution sludge, scavenging material：Sludge=40:60；Heavy metal slight pollution sludge, purifies material
Material：Sludge=30:70.Sludge handled by serial sludge scavenging material, the incobation solidification that can break flocculant in sludge is made
With elimination flocculant destroys the harm of soil texture, and the sludge water content content after processing can be reduced to 20% or so, and organic matter contains
Amount can be reduced to 5% or so, and Heavy Metal Level In Sludge can reduce by more than 50%, and the sludge after processing can be used for soil remediation,
Meadow is reclaimed, urban afforestation, can also make organic Fertilizer application.
Claims (10)
1. a kind of micro-nano nonmetallic serial mineral material of purification of heavy metal sludge, it is characterised in that containing a certain amount of in the material
The micro-nano nonmetallic ore material such as bentonite, concave convex rod, zeolite, above-mentioned mineral material passes through micro-nano technique process technology, shape
Into cocrystallization complex or the sludge scavenging material of mixture.
2. the micro-nano nonmetallic sludge mineral scavenging material of series according to claim 1, it is characterised in that sludge chats
The preferred proportion that material addition accounts for sludge gross weight is 35%~55%, and preferably sludge moisture content will be controlled 70% ~ 80%.
3. micro-nano nonmetallic ore material according to claim 2, it is characterised in that preferably nonmetallic ore material
Additive, micro-nano-scale control is at 200 ~ 2000 nanometers, and processing technology can select airslide disintegrating mill and related precisely crush sets
The technique process technology such as standby.
4. preferably micro-nano nonmetallic ore material kind bentonite according to claim 3 is the ultrafiltration of biological sludge
Agent, particularly has very well to dyeing waste water, biogas waste water, food plant wastewater, paper waste, slaughterhouse's wastewater biological Treatment of Sludge
Effect, the material of organic matter sludges processing prepares bentonite content and want ＞ 60%, and unclassified stores content is less than 40%, reference formulation
Ratio is：Bentonite：Concave convex rod：Zeolite=6.0:3.0:1.0.
5. preferably micro-nano nonmetallic ore material concave convex rod according to claim 3, is a kind of eliminate in sludge
Heavy metal pollution, the main material of purifying eutrophic sludge ammoniacal nitrogen, organophosphor and poisonous and harmful bacterium class, attapulgite its
Huge surfaces externally and internally product, tiny bar-shaped, needle-like and fibrous porous structure are the important indicator of its physical absorption, eutrophy
The material preparation concave convex rod content for changing Treatment of Sludge wants ＞ more than 60%, and unclassified stores content is less than 40%, reference formulation ratio
For：Concave convex rod：Bentonite：Zeolite=6.0:2.0:2.0.
6. preferably micro-nano nonmetallic materials zeolite according to claim 3, in being the sedimentary rock that volcano is sprayed, rock
Organic matter be liquefied or vaporize and produce fine hole, the size in these apertures possesses to organic point about in below 1nm
The adsorption function of son and cation, can eliminate the poisonous and harmful heavy metallic ions such as mercury cadmium lead arsenic in sludge, zeolite is to ammonia（NH4
+）With higher absorption and exchange force, reference formulation ratio is：Zeolite：Bentonite：Concave convex rod=4.0:3.0:3.0.
7. the preferably micro-nano mineral sludge scavenging material according to claim 4,5,6, it is characterised in that the material will
By high-temperature heating treatment, processing control temperature is in 130 ~ 180 degree, and sludge water content content is high or content of beary metal is high, and sludge is net
Change control of material temperature in 150 ~ 180 degree, sludge water content content is low or content of beary metal is low, sludge scavenging material control temperature exists
130 ~ 150 degree, the scavenging material after high-temperature heating treatment has small-size effect, high surface area effect and tunnel-effect, can promote
Enter eutrophication ion and the absorption of the lattice of heavy metal ion, chelating, flocculation and precipitation in sludge, make the huge sum of money entered in lattice
Category ion reaches the purpose permanently sealed up for safekeeping.
8. the preparation method of serial sludge scavenging material bentonite according to claim 7, concave convex rod, zeolite etc., is to have selected life
Produce the mineral processing circuit of general nonmetallic ore material, disintegrating process flow, micro/nano level superfine Me flows, quantitative input
The computer controling equipment of additive, material mixes equipment, and uniform cocrystallization complex or well mixed in order is made
Eutectiform product, set up additive pulverizer, storagetank, computer-metering pump, mixer, material conveyer, title in the technique
The supporting production lines such as amount machine, packing machine, freeze-day with constant temperature warehouse.
9. the series sludge scavenging material such as bentonite according to claim 8, concave convex rod, zeolite is added in the form of mixing powder
Enter into the technological process of sludge material processing, the series sludge scavenging material such as bentonite, concave convex rod, zeolite handles the preparation of sludge
Ratio can flexibly be grasped according to sludge moisture content or content of beary metal, and sludge and scavenging material reference formulation ratio are：Heavy metal
Serious pollution sludge, scavenging material：Sludge=50:50；Heavy metal intermediate pollution sludge, scavenging material：Sludge=40:60；With much money
Belong to slight pollution sludge, scavenging material：Sludge=30:70.
10. the sludge handled by serial sludge scavenging material according to claim 9, it is characterised in that sludge can be broken
The incobation solidification of middle flocculant, eliminates the harm that flocculant destroys soil texture, the sludge water content content after processing can
20% or so is reduced to, the content of organic matter can be reduced to 5% or so, and content of beary metal can reduce by 30% ~ 70%, the cation exchange such as ammonia
Amount can reduce more than 30%, the sludge after processing can be used for land remediation, and desert transformation, meadow is reclaimed, urban afforestation and directly
Make organic Fertilizer application, can also be directly used in Marine Planktonic agricultural and island reclaim agricultural make with fertilizer.
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| CN201610177509.2A CN107233861A (en) | 2016-03-28 | 2016-03-28 | A kind of micro-nano mineral material of purification of heavy metal sludge and preparation method thereof |
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| CN201610177509.2A CN107233861A (en) | 2016-03-28 | 2016-03-28 | A kind of micro-nano mineral material of purification of heavy metal sludge and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110451759A (en) * | 2019-09-06 | 2019-11-15 | 黄海星 | A kind of method that coal slime removes moisture removal |
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| CN110451759A (en) * | 2019-09-06 | 2019-11-15 | 黄海星 | A kind of method that coal slime removes moisture removal |
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