CN108079937A - A kind of adsorbent based on discarded gangue and its preparation method and application - Google Patents

A kind of adsorbent based on discarded gangue and its preparation method and application Download PDF

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Publication number
CN108079937A
CN108079937A CN201810075110.2A CN201810075110A CN108079937A CN 108079937 A CN108079937 A CN 108079937A CN 201810075110 A CN201810075110 A CN 201810075110A CN 108079937 A CN108079937 A CN 108079937A
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gangue
adsorbent
discarded
adsorbent based
discarded gangue
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CN108079937B (en
Inventor
包红旭
张欣
张�浩
杨华
苏弘治
张馨月
吕志忠
李良玉
黄颖芝
刘唯玉
杨雨萌
陈阳
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Liaoning University
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Liaoning University
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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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • 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
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of adsorbents based on discarded gangue and its preparation method and application, belong to solid waste resource utilization field.The present invention be using the gangue that is discharged during coal mining process and coal washing after drying, crushing with potassium carbonate in mass ratio 5:1 adds water combination drying, then calcines 40min in 600 DEG C, is heated to 850 DEG C, calcines 50min, you can obtains one kind and is based on discarded gangue processing containing Zn2+The new adsorbent of waste water.Discarded gangue is applied to containing heavy metal Zn by the present invention2+In the processing of waste water, simplicity is prepared, of low cost, removal efficiency can reach 92% or so.

Description

A kind of adsorbent based on discarded gangue and its preparation method and application
Technical field
The present invention relates to a kind of based on discarded gangue, Zn in industrial wastewater can be efficiently removed2+Adsorbent, belong to solid Body changing waste into resources utilizes field.
Background technology
With the progress of China's industrial production modernization level, sanitary wastewater and industrial wastewater largely increase, heavy metal-polluted Dye is on the rise.Due to its non-biodegradable, metal ion constantly accumulates, and is gradually increased along food chain quantity.Therefore they Toxic side effect showed in high nutrition grade animal more obvious, nervous function can be caused to lack of proper care, skeleton softening, the dirty function of stomach declines It exhausts, animals and plants is made to be poisoned.How the heavy metal efficiently removed in waste water is current urgent task.
Gangue is the solid waste generated in coal production and process, and annual discharge capacity is equivalent to coal then 10% or so of carbon yield has added up more than 30 hundred million tons of stockpiling at present, takes up an area about 1.2 ten thousand hectares, is that current China's discharge capacity is maximum One of industrial solid castoff.Coal in China system will also give off nearly 100,000,000 tons of gangues every year now.With national economy Development, coal demand total amount is continuously increased, and the yield of gangue can also be significantly increased, and gangue environmental pollution has become One of coal in China industry environmental problem the most prominent.Gangue is a kind of natural resources for development and utilization again, must It must rely on scientific and technological advances and sufficient recycling is carried out to gangue, turn waste into wealth, reduce gangue to caused by environment Harm.
Gangue is referred to as low taste humic acid, containing functional group, bridged bond in humic acid, have excellent absorption, exchange, Complex performance.Gangue all has good adsorptivity to the pollutant in water, soil, air, it may have before good application Scape, current research of the related gangue as adsorbent in heavy metal containing wastewater treatment does not carry out deeply also, under test, It is very unripe, and there are many method of modifying is also more complicated.For this purpose, to work out, a kind of preparation process is simple, and cost is just Suitable adsorbent.
The content of the invention
An object of the present invention be to provide it is a kind of discarded gangue is made full use of to prepare new adsorbent, the new suction Attached dose handles the problem of removal of heavy metal ions rate is relatively low for traditional wastewater, passes through the functional group enriched in gangue, bridged bond Excellent absorption, exchange, complex performance, to the Zn in industrial wastewater2+It is adsorbed, while the other components contained in waste water (such as organic matter, inorganic salts) can have an effect with gangue, improve the removal rate of dirty pollutant in water, have preferable Prospects for commercial application.
The second object of the present invention is to provide a kind of preparation method of the adsorbent based on discarded gangue.
The third object of the present invention is to provide the Zn in industrial wastewater is adsorbed of the adsorbent based on discarded gangue2+In should With.
The technical solution adopted by the present invention is：A kind of adsorbent based on discarded gangue, by bastard coal mountain flour and potassium carbonate It is made.
Preferably, above-mentioned a kind of adsorbent based on discarded gangue, in mass ratio, bastard coal mountain flour:Potassium carbonate=5: 1。
A kind of above-mentioned adsorbent based on discarded gangue in the bastard coal mountain flour, by weight percentage, contains 53 ~60%SiO2, 20~25%Al2O3, 4~8%CaO, 2~5%MgO, 5~10%Fe2O3。
A kind of preparation method of the adsorbent based on discarded gangue, includes the following steps：
1) by gangue distilled water flushing 2~3 times, impurity is removed, is put into baking oven, in 55 DEG C of bakings for 24 hours, crushed, 200 mesh sieves are crossed, extracting screen underflow is bastard coal mountain flour.
2) bastard coal mountain flour and potassium carbonate are taken, adds in suitable quantity of water, is uniformly mixed, in 55 DEG C of bakings for 24 hours.
3) mixture after drying is put in Muffle furnace and calcined, obtain adsorbent.
Preferably, the preparation method of above-mentioned a kind of adsorbent based on discarded gangue, step 3) will be mixed after drying It closes object to be put in Muffle furnace, prior to 600 DEG C calcining 40min are heated to 850 DEG C of calcining 50min, obtain adsorbent.
The above-mentioned adsorbent based on discarded gangue Zn in industrial wastewater is removed2+In application.Method is as follows：It adjusts PH=7~8 of industrial wastewater by adsorbent in the ratio of every cubic metre of 2~2.5kg, are uniformly added in industrial wastewater, stir React 1.5~2h.
The beneficial effects of the invention are as follows：
1) raw material sources are extensive, of low cost；
2) the raw materials used in the present invention is coal mining solid waste, belongs to resource reutilization, to environment nonhazardous.
3) preparation of gangue adsorbent of the present invention is easy, significant effect, to Zn in industrial wastewater2+Removal rate be up to 92% or so, there is good industrial prospect.
Description of the drawings
Fig. 1 is the adsorbent addition and Zn of the present invention2+Adsorption rate relational graph.
Fig. 2 is pH value of waste water and Zn2+Adsorption rate relational graph.
Fig. 3 is to be stirred to react time and heavy metal ion adsorbed rate relational graph.
Specific embodiment
Below by specific embodiment, the present invention will be further described, but the present invention is not limited thereto.Due to various regions Difference, pretreatment parameter can also generate respective change for sewage quality and used treatment process, therefore without prejudice to originally On the premise of the essence and scope of invention, key parameter in the present invention can be made the appropriate adjustments.
Embodiment 1
Take the gangue fetched from Tieling coal mining area, chemical composition such as table 1.With distilled water flushing 2~3 times, Impurity is removed, is put it into afterwards in baking oven, in 55 DEG C of bakings for 24 hours, makes its drying.And crushed in grinder, cross 200 mesh Sieve, extracting screen underflow obtains bastard coal mountain flour, spare.
In mass ratio 5:1, bastard coal mountain flour and potash solid are taken, adds suitable quantity of water mixing, in 55 DEG C of bakings for 24 hours, makes it dry It is dry；Dried mixture is put in Muffle furnace, prior to 600 DEG C calcining 40min are heated to 850 DEG C, calcine 50min, obtain Adsorbent of the target product based on discarded gangue.
Table 1
Ingredient SiO2 Al2O3 CaO MgO Fe2O3 Na2O+K2O Loss on ignition
Ratio (%) 55 21 6 3 7 1.5 6.5
Embodiment 2
(1) sewage source
Sewage is from industrial production wastewater of the Zinc Factory of Huludao containing heavy metal ion, pH 6.57, Zn2+Concentration be 136.11mg/L。
(2) addition of adsorbent is to removing configuration metal ions Zn2+Influence
Method：Take sewage 100ml, be separately added into embodiment 1 preparation the adsorbent 0.05g based on discarded gangue, 0.10g, 0.15g, 0.20g, 0.25g, 0.30g when reaction 2 is small, then measure Zn in solution2+Content.As a result such as Fig. 1.
With the increase of adsorbent addition it can be seen from the result of the test in Fig. 1, to Zn2+Adsorption rate therewith It increases.Have when the addition of the adsorbent based on discarded gangue is 0.20g to Zn2+Preferable adsorption effect.
(3) pH of waste water is to removing configuration metal ions Zn2+Influence
Method：Sewage 100ml is taken, is respectively 6,7,8,9,10 with dilute HCl and NaOH adjustment pH value, adds in embodiment 1 and make The standby adsorbent 0.20g based on discarded gangue when reaction 2 is small, then measures Zn in solution2+Content.As a result such as Fig. 2.
With the increase of pH value of waste water it can be seen from the result in Fig. 2, the adsorbent based on discarded gangue is to Zn2+ Adsorption rate increase therewith.There is preferable adsorption effect in the range of pH=7~8, to Zn2+Adsorption rate can reach 90.0 ~92.0%.
(4) adsorption time is to removing configuration metal ions Zn2+Influence
Method：Sewage 100ml is taken, adjustment pH value is 7, adds in the adsorbent based on discarded gangue prepared by embodiment 1 0.20g reacts 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, then measures Zn in solution2+Content.As a result such as Fig. 3.
With the extension of adsorption time it can be seen from the result of the test in Fig. 3, the adsorbent pair based on discarded gangue Zn2Adsorption rate increase therewith.When absorption proceed to 1.5~2.0 it is small when, to Zn2Adsorption rate reach maximum adsorption rate 92.1%.
By the screening of condition, optimal process conditions are：PH=7~8 of industrial wastewater are adjusted, by adsorbent by often standing The ratio uniform of square 2~2.5kg of rice is added in industrial wastewater, is stirred to react 1.5~2h, gangue adsorbent is to Zn2Suction Attached rate reaches the 92.1% of maximum adsorption rate.

Claims (7)

1. a kind of adsorbent based on discarded gangue, which is characterized in that be made of bastard coal mountain flour and potassium carbonate.
2. a kind of adsorbent based on discarded gangue according to claim 1, which is characterized in that in mass ratio, bastard coal Mountain flour:Potassium carbonate=5:1.
A kind of 3. adsorbent based on discarded gangue according to claim 1 or 2, which is characterized in that the bastard coal In mountain flour, by weight percentage, contain 53~60%SiO2, 20~25%Al2O3, 4~8%CaO, 2~5%MgO, 5~10% Fe2O3。
4. a kind of preparation method of the adsorbent based on discarded gangue, which is characterized in that include the following steps：
1) by gangue distilled water flushing 2~3 times, impurity is removed, is put into baking oven, in 55 DEG C of bakings for 24 hours, crushed, cross 200 Mesh sieve, extracting screen underflow are bastard coal mountain flour；
2) bastard coal mountain flour and potassium carbonate are taken, adds in suitable quantity of water, is uniformly mixed, in 55 DEG C of bakings for 24 hours；
3) mixture after drying is put in Muffle furnace and calcined, obtain adsorbent.
A kind of 5. preparation method of adsorbent based on discarded gangue according to claim 4, which is characterized in that step 3), the mixture after drying is put in Muffle furnace, prior to 600 DEG C calcining 40min are heated to 850 DEG C of calcining 50min, obtain Adsorbent.
6. the Zn in industrial wastewater is removed of the adsorbent based on discarded gangue described in claim 1 or 22+In application.
7. application according to claim 6, which is characterized in that method is as follows：PH=7~8 of industrial wastewater are adjusted, will be inhaled The attached dose of ratio in every cubic metre of 2~2.5kg is uniformly added in industrial wastewater, is stirred to react 1.5~2h.
CN201810075110.2A 2018-01-26 2018-01-26 Adsorbent based on waste coal gangue and preparation method and application thereof Active CN108079937B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012569A (en) * 2018-07-18 2018-12-18 东南大学 A kind of Ca-base adsorbent and preparation method thereof
CN109384254A (en) * 2018-07-24 2019-02-26 山西大学 The method that crystal aluminum chloride and white carbon black are prepared by flyash or gangue
CN109603743A (en) * 2019-01-10 2019-04-12 辽宁大学 A kind of preparation method and application of Preparation & Application of Modified Gangue Absorbent

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012569A (en) * 2018-07-18 2018-12-18 东南大学 A kind of Ca-base adsorbent and preparation method thereof
CN109384254A (en) * 2018-07-24 2019-02-26 山西大学 The method that crystal aluminum chloride and white carbon black are prepared by flyash or gangue
CN109384254B (en) * 2018-07-24 2021-05-14 山西大学 Method for preparing crystalline aluminum chloride and white carbon black from fly ash or coal gangue
CN109603743A (en) * 2019-01-10 2019-04-12 辽宁大学 A kind of preparation method and application of Preparation & Application of Modified Gangue Absorbent

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