CN107032439A - A kind of method that modified copper tailing adsorbs phosphate in waste water pollutant - Google Patents
A kind of method that modified copper tailing adsorbs phosphate in waste water pollutant Download PDFInfo
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- CN107032439A CN107032439A CN201710469553.5A CN201710469553A CN107032439A CN 107032439 A CN107032439 A CN 107032439A CN 201710469553 A CN201710469553 A CN 201710469553A CN 107032439 A CN107032439 A CN 107032439A
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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
- 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- B01J2220/48—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
- C02F2101/105—Phosphorus compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a kind of method that modified copper tailing adsorbs phosphate in waste water pollutant, compared with prior art, copper tailing is first carried out 2 dryings by the present invention, the water for first removing copper tailing surface is dried for the first time, then after grinding, second of dry profound water removal of progress, reduces resistance of the water to absorption, improves the absorption property of copper tailing.1 2h is calcined at 330 340 DEG C by designing, obtain modified copper tailing, phosphate solution initial concentration is 150~200mg/L in adsorption process, 0.5~1g/100mL of modified mine tailing dosage, 10~100min of reaction time, the modification copper tailing prepared, makes adsorption reaction under conditions of pH 2~11, and high adsorption rate and clearance can be achieved.The modification copper tailing scope of application that the present invention is provided is wider, and cost is lower, and adsorption effect is more preferable.
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of modified copper tailing absorption phosphate in waste water pollutant
Method.
Background technology
Copper tailing, also known as copper tailings, by ore it is size-reduced, it is selected after the remaining fine powder grains of sand constitute.These mine tailings
Except on a small quantity as the inserts of old mine in addition to, remaining it is most also by fill depression or stacking of building a dam in the way of store, heap
The copper tailing put not only occupies a large amount of soils, and covers original vegetation, and the ecosystem is destroyed.
Mine tailing is because of its special physicochemical property, and content of beary metal is especially high, and plant is difficult to be grown naturally on mine tailing.Simultaneously
Mine tailing because being flown upward with the wind, rain water runoff, and the resident living environment of surrounding area is polluted.In the governance process of mine tailing,
Revegetation is the best way that mine tailing is administered, and in vegetation recovery procedure, the raising of soil nutrient, toxicant concentration
Reduction, the formation of tolerant plant kind are all a long-term processes, therefore the key reclaimed is improvement and the patience of matrix
The selection of species.
Mainly there are the precipitation method, Coagulation Method, bioanalysis and absorption method etc. to the minimizing technology of phosphorus at present.Wherein absorption method is operated
Simply receive much concern.There is provided a kind of low phosphorus adsorbent of efficient, cost necessary.
The content of the invention
It is an object of the invention to provide a kind of method that modified copper tailing adsorbs phosphate in waste water pollutant, pass through control
The modified technique of copper tailing processed, improves the adsorption efficiency to phosphorus, while reducing production cost.
The method that a kind of modified copper tailing that the present invention is provided adsorbs phosphate in waste water pollutant, comprises the following steps：
1) after copper tailing is dried, grinding sieving then proceedes to dry to constant weight；
2) copper tailing dried to constant weight is calcined, carries out heat modification；
3) modified copper tailing is placed in phosphate solution, adsorbed；Adsorption conditionses are：Phosphate solution is initial
Concentration is 150~200mg/L, modified mine tailing 0.5~1g/100mL of dosage, 10~100min of reaction time.
Further, step 1) in second step drying carried out at 105 DEG C.
Step 1) described in grinding sieving refer to grinding after cross 100 mesh sieves；
Further, step 2) described in calcining be in 330-340 DEG C, time 1-2h.
Further, step 3) in the initial pH 2~11 of phosphate solution.
Compared with prior art, copper tailing is first carried out 2 dryings by the present invention, dries first remove copper tailing surface for the first time
Water, after then grinding, second dries and carries out profound water removal, reduces resistance of the water to absorption, improves the absorption of copper tailing
Performance.It is 150~200mg/L by designing phosphate solution initial concentration in adsorption process, modified mine tailing dosage 0.5~
1g/100mL, 10~100min of reaction time, the modification copper tailing prepared make adsorption reaction in pH 2~11 condition
Under, high adsorption rate and clearance can be achieved.The modification copper tailing scope of application that the present invention is provided is wider, and cost is lower, absorption
Effect is more preferable.
Brief description of the drawings
Fig. 1 is the influence of modified mine tailing Phosphate Adsorption amount under 50~650 DEG C of temperature conditionss；
Fig. 2 is the influence of modified mine tailing removal rate of phosphate under 50~650 DEG C of temperature conditionss；
Fig. 3 is the influence that pyrolysis time is modified mine tailing Phosphate Adsorption capacity；
Fig. 4 is the influence that pyrolysis time is modified mine tailing removal rate of phosphate；
Fig. 5 is influence of the modified mine tailing to Phosphate Adsorption capacity under 300~350 DEG C of temperature conditionss；
Fig. 6 is influence of the modified mine tailing to removal rate of phosphate under 300~350 DEG C of temperature conditionss；
Fig. 7 is influence of the different initial phosphate concentrations to mine tailing Phosphate Adsorption capacity；
Fig. 8 is influence of the different initial phosphate concentrations to mine tailing removal rate of phosphate；
Fig. 9 is influence of the different dosages to modified mine tailing Phosphate Adsorption capacity；
Figure 10 is influence of the different dosages to modified mine tailing removal rate of phosphate；
Figure 11 is influence of the reaction time to modified mine tailing Phosphate Adsorption capacity；
Figure 12 is influence of the reaction time to modified mine tailing removal rate of phosphate；
Figure 13 is influences of the different pH to mine tailing Phosphate Adsorption capacity；
Figure 14 is influences of the different pH to mine tailing removal rate of phosphate；
Figure 15 is the adsorption isotherm under the conditions of unmodified mine tailing 298K；
Figure 16 is the adsorption isotherm of modified 340 DEG C of mine tailing.
Embodiment
Embodiment 1
A kind of method that modified copper tailing adsorbs phosphate in waste water pollutant, comprises the following steps：
1) native copper mine tailing is derived from Tongling, Anhui Province copper mine factory, is dried after fetching, and grinding crosses 100 mesh sieves, by the copper tail after sieve
Miberal powder end is inserted in 105 DEG C of drying boxes and dried to constant weight, is put into flask for medicinal preparations, standby.
2) take step 1) processing after copper tailing be put into crucible, then insert Muffle furnace high temperature calcining, control calcining
Temperature is in 330-340 DEG C, time 2h, you can.
3) modified copper tailing is placed in phosphate solution, adsorbed；Adsorption conditionses are：Phosphate solution is initial
Concentration is 100~150mg/L, 0.5~1g/100mL of modified mine tailing dosage, 10~100min of reaction time, initial phosphate
PH value of solution 2~11, then detects Phosphate Adsorption capacity, the influence of clearance.
Embodiment 2
By following experimental verification, calcining heat is in 330-340 DEG C, time 1-2h, the Modified Cu tail of acquisition in the present invention
Ore deposit adsorption effect is best.
Change embodiment 1 step 2) sintering temperature and time, it is real that the modification copper tailing prepared carries out Phosphate Adsorption
Test, experiment condition is as follows：
Initial phosphate concn 50mg/L, the pH initial pH5.38 of phosphate solution, adsorbent dosage 1.5g/100mL, instead
3h, reaction temperature 298K between seasonable.
Mine tailing will be obtained being modified to phosphatic adsorption capacity and clearance (Fig. 1 and Fig. 2), best modification time is shown in Fig. 3
And Fig. 4.From Fig. 1 and 2：When temperature control is at 50 DEG C~650 DEG C, modified copper tailing is to phosphatic adsorption capacity and goes
Except the trend that rate is all gradually reduced afterwards in first increasing, temperature is at 350 DEG C, and adsorption capacity is 3.12mg/g, and phosphate is removed
93.80%.When temperature continues to increase, adsorption capacity and removal rate of phosphate are on a declining curve, when temperature reaches 650 DEG C, inhale
Attached capacity is 0.49mg/g, and removal rate of phosphate is 14.90%.Drawn by Fig. 3 and Fig. 4：When pyrolysis time is more than 1h, obtain
Modification mine tailing adsorption capacity and removal rate of phosphate change it is little, pyrolysis time of the present invention is 1-2h, it is ensured that high adsorption rate and
Cost is reduced while clearance.
The modification copper tailing prepared carries out Phosphate Adsorption experiment, obtains being modified copper tailing to phosphatic absorption appearance
Amount and clearance (see Fig. 5 and Fig. 6).From Fig. 5 and Fig. 6：The modification mine tailing adsorption capacity prepared in this temperature range
All higher with removal rate of phosphate, the adsorption capacity and removal rate of phosphate prepared using at 330 DEG C and 340 DEG C of temperature is most
Height, respectively 3.32 and 3.33mg/g, 99.60% and 99.70%.
Embodiment 3
By following experimental verification, initial phosphate concentration is controlled to be 150~200mg/L in the present invention, adsorption effect is most
It is good.
Modification copper tailing prepared by embodiment 1, which is placed in, to be taken in phosphate solution, fixed modified mine tailing dosage 1.5g/
100mL, phosphate solution pH 5.38, reaction time 210min.Choose initial phosphate concentration 10,30,50,80,100,150,
200mg/L each 100mL of simulated wastewater.25 DEG C, 150r/min oscillating reactions.After reaction terminates, stand, residual phosphorus is surveyed in filtering
Hydrochlorate concentration.Obtain shown in Phosphate Adsorption capacity and clearance as Fig. 7 and 8.
From Fig. 7 and 8, modified mine tailing (TMCT) is strong compared with mine tailing to phosphate removal ability, with phosphate concn
Increase, modified mine tailing adsorption capacity gradually increases, though clearance is reduced, reduction amplitude is smaller, but initial phosphate concentration
During for 200mg/L, adsorption capacity is up to 12.54mg/g, and removal rate of phosphate is 94.09%；Unmodified mine tailing (UMCT) is in phosphorus
When hydrochlorate concentration is 200mg/L, adsorption capacity is 1.59mg/g, and removal rate of phosphate is 11.96%.
Embodiment 4
By following experimental verification, modified mine tailing 0.5~1g/100mL of dosage is controlled in the present invention, adsorption effect is most
Good, cost is minimum.
Fixed phosphate initial concentration 50mg/L, phosphate solution pH5.38, reaction time 210min, choose mine tailing and add
Amount 0.5,1.0,1.5,2.0,2.5,3.0g, reaction condition be the same as Example 4.Obtain adsorption capacity and phosphoric acid clearance see Fig. 9 and
10。
It can be seen from Fig. 9 and 10 when mine tailing dosage is 0.5~1g/, to modified mine tailing Phosphate Adsorption capacity most
Greatly, removal efficiency highest, modified mine tailing is best to phosphate removal effect.Unmodified mine tailing is to phosphate removal effect with adding
The increase of amount is in increase trend, and when mine tailing dosage is 1.5g/100mL, adsorption capacity is 1.92mg/g, and clearance is
57.77%, when mine tailing dosage is 3.0g/mg, adsorption capacity is 1.47mg/g, and clearance is 88.72%.
Embodiment 5
By following experimental verification, 10~100min of reaction time is controlled in the present invention, preferably, cost is most for adsorption effect
It is low.
Fixed phosphate initial concentration 50mg/L, mine tailing dosage 1.5g/100mL, phosphate solution pH5.38, choose anti-
Be 10 between seasonable, 30,60,90,120,150,180,210,240,270,300min.Reaction condition is the same.Its experimental result is shown in
Figure 11 and Figure 12.
As seen from the figure, for modified mine tailing, when reacted between when being 30min, its adsorption capacity reaches 3.20mg/g, phosphoric acid
Salt clearance is 96.21%, and the time continues to extend, and adsorption capacity and clearance increasing degree less, after 100min, are adsorbed
Capacity and clearance have declined；Compared to more modified mine tailing, unmodified mine tailing reaction reaches that the time of balance is longer, when reacted
Between be 150min when, its adsorption capacity reaches 2.33mg/g, and removal rate of phosphate is 69.96%, continue extend the reaction time, inhale
Attached capacity and clearance change is little.
Embodiment 6
By following experimental verification, initial soln pH 2~11 is controlled in the present invention, adsorption effect is best.The present invention relates to
Modification copper tailing, its pH is applied widely, simple to operate
Fixed phosphate initial concentration 50mg/L, mine tailing dosage 1.5g/100mL, reaction time 210min.Choose, phosphorus
Acid salt solution pH 2.55,3.52,4.50,5.38,6.31,7.32,8.37,9.43,10.29,11.23.Reaction condition is the same.
Its experimental result is as shown in Figs. 13 and 14.
PH is little on modified mine tailing absorption property influence it can be seen from Figure 13 and 14, with pH increase, adsorption capacity
Be in increase tendency with clearance, when pH is more than 4, its adsorption capacity and clearance preferably, when pH is 7.32, adsorption capacity and
Clearance respectively reaches 3.28mg/g, 98.30%.For unmodified mine tailing, influences of the pH to absorption property and modified mine tailing phase
Seemingly, when pH is 4.50, adsorption capacity and clearance are respectively 1.58mg/g, 64.30%, continue to increase pH, adsorption capacity and
Clearance has increase by a small margin, and when pH is 11.23, adsorption capacity and clearance are respectively 1.59mg/g, 84.47%.
Embodiment 7
Configuration initial concentration be 0mg/L, 2,4,8,10,30,50,100,200,300,400,500mg/L phosphate it is molten
Liquid, reaction time 210min, phosphate solution pH6.31, mine tailing dosage 1.5g/100mL.Reaction condition is the same.Unmodified tail
Figure 15 and Figure 16 are shown in ore deposit and modified mine tailing adsorption isotherm fitting.Langmuir equations and Freundlich equation model parameters are shown in
Table 1.
The modified more unmodified mine tailing absorption property of mine tailing absorption property will get well it can be seen from figure and table, through 340 DEG C, heat
Its maximum saturation adsorption capacity of the mine tailing of solution 2h modifications is up to 14,69mg/g, and unmodified mine tailing maximum saturation adsorption capacity is
2.26mg/g.Hence it is demonstrated that the copper tailing by pyrolysis activation has very strong absorption property to phosphate in waste water.
Table 1：Langmuir and Freundlich Tellurium determinations and parameter
Claims (5)
1. a kind of method that modified copper tailing adsorbs phosphate in waste water pollutant, it is characterised in that methods described includes following
Step：
1) after copper tailing is dried, grinding sieving then proceedes to dry to constant weight；
2) copper tailing dried to constant weight is calcined, carries out heat modification；
3) modified copper tailing is placed in phosphate solution, adsorbed；Adsorption conditionses are：Phosphate solution initial concentration
For 150~200mg/L, modified mine tailing 0.5~1g/100mL of dosage, 10~100min of reaction time.
2. the method that modified copper tailing according to claim 1 adsorbs phosphate in waste water pollutant, it is characterised in that step
It is rapid 1) in second step drying carried out at 105 DEG C.
3. the method that modified copper tailing according to claim 1 or 2 adsorbs phosphate in waste water pollutant, its feature exists
In step 1) described in grinding sieving refer to grinding after cross 100 mesh sieves.
4. the method that the modification copper tailing according to claim any one of 1-3 adsorbs phosphate in waste water pollutant, it is special
Levy and be, step 2) described in calcining be in 330-340 DEG C, time 1-2h.
5. the method that the modification copper tailing according to claim any one of 1-3 adsorbs phosphate in waste water pollutant, it is special
Levy and be, step 3) in the initial pH 2~11 of phosphate solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355607A (en) * | 2018-02-09 | 2018-08-03 | 长江水利委员会长江科学院 | It is a kind of to utilize the functional material for selecting copper tailings to prepare and its preparation process |
| CN109663563A (en) * | 2018-12-10 | 2019-04-23 | 河北省科学院生物研究所 | Modified Iron CHARACTERISTICS OF TAILINGS SAND, preparation and its application |
| CN110028125A (en) * | 2019-04-25 | 2019-07-19 | 郑州大学 | A method of water body intermediate ion state organic matter is separated by carrier adsorption of waste residue source nanoparticle |
| CN114307946A (en) * | 2022-01-05 | 2022-04-12 | 成都大学 | Modified copper ore tailing slag and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355607A (en) * | 2018-02-09 | 2018-08-03 | 长江水利委员会长江科学院 | It is a kind of to utilize the functional material for selecting copper tailings to prepare and its preparation process |
| CN108355607B (en) * | 2018-02-09 | 2020-10-27 | 长江水利委员会长江科学院 | Functional material prepared by using copper-selecting tailings and preparation process thereof |
| CN109663563A (en) * | 2018-12-10 | 2019-04-23 | 河北省科学院生物研究所 | Modified Iron CHARACTERISTICS OF TAILINGS SAND, preparation and its application |
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| CN110028125A (en) * | 2019-04-25 | 2019-07-19 | 郑州大学 | A method of water body intermediate ion state organic matter is separated by carrier adsorption of waste residue source nanoparticle |
| CN110028125B (en) * | 2019-04-25 | 2021-10-29 | 郑州大学 | Method for adsorbing and separating ionic organic matters in water body by using waste residue source nanoparticles as carriers |
| CN114307946A (en) * | 2022-01-05 | 2022-04-12 | 成都大学 | Modified copper ore tailing slag and preparation method and application thereof |
| CN114307946B (en) * | 2022-01-05 | 2023-08-15 | 成都大学 | Modified copper mine tailing slag and preparation method and application thereof |
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