CN104724806A - Polymer zinc-based aluminum chloride ferric flocculant and preparation method thereof - Google Patents

Polymer zinc-based aluminum chloride ferric flocculant and preparation method thereof Download PDF

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Publication number
CN104724806A
CN104724806A CN201510175026.4A CN201510175026A CN104724806A CN 104724806 A CN104724806 A CN 104724806A CN 201510175026 A CN201510175026 A CN 201510175026A CN 104724806 A CN104724806 A CN 104724806A
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zinc
ferric chloride
flyash
base aluminum
add
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CN104724806B (en
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李荣喜
雷敏
宋勇
杨珊
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Changsha University
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Changsha University
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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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron

Abstract

The invention relates to a polymer zinc-based aluminum chloride ferric flocculant and a preparation method thereof. The method includes the steps of firstly, soaking fly ash with hydrochloric acid in constant-temperature water bath of 70-100 DEG C, and filtering to obtain fly ash lixivium; secondly, taking iron-containing waste acid to add into the fly ash lixivium, adding zinc chloride to allow the mole ratio of Zn, Al and Fe in solution to be 1:1.0-2.5:1.0-3.5, adding sodium tetraborate as stabilizer, adjusting pH to 4-6, stirring, adding excessive amount of hydrogen peroxide, and standing and curing under normal temperature to obtain the polymer zinc-based aluminum chloride ferric flocculant. The polymer zinc-based aluminum chloride ferric flocculant is efficient, low in consumption, safe, harmless, free of secondary pollution, good in preprocessing effect of waste water hard to degrade, and the like. The preparation method is simple and wide in material source, waste acid recycling is achieved, and environment pollution is reduced.

Description

A kind of polymerization zinc-base aluminum ferric chloride flocculant and preparation method thereof
Technical field
The present invention relates to a kind of flocculation agent and preparation method thereof, be specifically related to a kind of polymerization zinc-base aluminum ferric chloride flocculant and preparation method thereof.
Background technology
Acid is used widely in industries such as metallurgy, machinery and metal products processing as a kind of clean-out system.But when the concentration of acid in acid solution is reduced to a certain degree, its cleaning performance significantly declines and becomes spent acid solution or claim spent pickle liquor.Spent pickle liquor is acid strong also containing a large amount of metal ion, is listed in Hazardous wastes and manages, conduct oneself well to comprehend cause serious environmental pollution and the wasting of resources as improper.Owing to containing a large amount of hydrochloric acid and ferrous iron in spent pickle liquor, if only carry out simple neutralizing treatment, need a large amount of alkaline matter, processing costs is higher, and is difficult to realize the innoxious of ferrous waste acid and comprehensive utilization.And ferrous iron is the good metallic salt source of preparing flocculation agent, be that inorganic polymer coagulant prepared by raw material with ferrous waste acid, a feasible approach can be provided for the comprehensive utilization of spent pickle liquor, can produce for coagulating agent again and cheap raw material is provided, reach the object of the treatment of wastes with processes of wastes against one another, there is good economic benefit, social benefit and environmental benefit.Flocculation agent prepared by prior art spent acid has polysilicon acid bimetallic salt complex, single metal polymerization salt etc., but under a high concentration condition, easily produce precipitation and gel, effect declines; The method of preparation mainly contains calcination method and lixiviation process, and wherein, calcination method needs larger heat, and inconvenient operation.
At present, main coagulating agent has aluminium iron polychloride, poly-aluminum-ferric-silicate-sulfate, polymeric aluminium ferrum silicate etc.Compound inorganic high molecular flocculant has charge neutrality and adsorption bridging effect simultaneously, and flocculating effect is better, and preparation method is simple, low price and being favored.And in current wastewater treatment, especially at pretreatment stage, mostly use flocculation agent to strengthen pretreating effect, but conventional flocculation agent particularly inorganic salt or polymer/metallic saline flocculating agent existence and stability poor, the problem that flocculation time is shorter, practical application effect is unsatisfactory, especially in waste water difficult for biological degradation process, is often very restricted.
Summary of the invention
Technical problem to be solved by this invention is, polymerization zinc-base aluminum ferric chloride flocculant providing a kind of product performance stable and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows: a kind of polymerization zinc-base aluminum ferric chloride flocculant, makes in accordance with the following methods:
(1) in 70 ~ 100 DEG C of waters bath with thermostatic control, use salt acid soak flyash, filter, obtain flyash leach liquor;
(2) ferrous waste acid is got, add step (1) gained flyash leach liquor, add zinc chloride again, make the mol ratio of element Zn:Al:Fe in solution be 1:1.0 ~ 2.5:1.0 ~ 3.5, then add stablizer sodium borate decahydrate, adjust ph to 4 ~ 6, stir, finally add excessive hydrogen peroxide, leave standstill slaking under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized.Gained flocculation agent is liquid.
In step (1), after using salt acid soak flyash in a water bath, the aluminum oxide in flyash and ferric oxide are constantly dissolved, and generate [Al (H 2o) 6] Cl 3[Fe (H 2o) 6] Cl 3, its reaction equation is as follows:
Al 2O 3+6HCl+9H 2O→2[Al(H 2O) 6]Cl 3
Fe 2O 3+6HCl+9H 2O→2[Fe(H 2O) 6]Cl 3。
Further, in step (2), the add-on of described sodium borate decahydrate is 0.17 ~ 0.30mmol/L.The effect adding stablizer does not produce precipitation to make flocculation agent stable, and add-on is all not good higher or lower than this range stabilises effect.
Further, in step (1), Al in described flyash 2o 3mass content be 22 ~ 40%, Fe 2o 3mass content be 7 ~ 15%.Also containing a large amount of SiO in flyash 2with a small amount of FeO, CaO, TiO 2deng, for the inventive method, the impact of these materials is little.
Further, in step (1), the concentration of described hydrochloric acid is 3 ~ 5mol/L.Concentration of hydrochloric acid is lower higher or lower than this scope aluminium, iron leaching yield.
Further, in step (1), the consumption of described hydrochloric acid is 15 ~ 25mL/g flyash.
Further, in step (1), the time of described immersion is 2 ~ 4h.Constantly measure the leaching content of aluminium, iron in immersion process, seek the maximum leaching content of aluminium, iron level, finally determine the time of soaking.
Further, in step (2), described ferrous waste acid refers to Fe 2+content is the acid solution of 3 ~ 5mol/L.
In step (2), select the mol ratio of element Zn:Al:Fe to be the reason of 1:1.0 ~ 2.5:1.0 ~ 3.5 to be: because iron is the important component in flocculation agent, decide the flocculating property of flocculation agent, so mainly determine according to the content of iron, is secondly the content of aluminium; Add according to this ratio, mainly in order to make iron, aluminium plays maximum throwing out, reduces again the consumption of zinc simultaneously, cost-saving; Zinc chloride mainly plays the effect of modification in this flocculation agent, and after adding zinc, flocculation agent goes the performance of turbidity to be improved.
In step (2), the effect of pH after adding sodium tetraborate, is regulated to be that improves flocculation agent goes turbidity and the performance of falling colourity in order to make the flocculating effect of flocculation agent reach best; Adding excessive hydrogen peroxide is in order to by Fe 2+be converted into Fe 3+, by continuous detection, when no longer including Fe 3+it is excessive to be during precipitation.
Further, in step (2), the temperature of described stirring is 70 ~ 90 DEG C.The reason of this temperature range is selected to be the reaction that higher temperature contributes to hydrochloric acid and aluminium, iron.
Further, in step (2), the time of described slaking is 20 ~ 24h.The effect of slaking makes the performance of flocculation agent more stable, and along with the growth of time, flocculation agent slaking is more abundant.
Flocculation agent of the present invention selects flyash to be medium, and utilize flyash to contain aluminium and the iron of certain weight proportion, after using salt acid soak flyash in a water bath, the aluminum oxide in flyash and ferric oxide are constantly dissolved, and generates [Al (H 2o) 6] Cl 3[Fe (H 2o) 6] Cl 3; These two kinds of leachables are added in Fe-laden acid waste water, after adding zinc chloride again, three is made to reach certain proportion, when pH value is 4 ~ 6, reaction generates ferrous type flocculation agent, makes the ferrous type flocculation agent generated keep stable state by sodium tetraborate, after adding hydrogen peroxide, ferrous iron is converted into iron ion, thus generates a kind of stable, efficient polymerization zinc-base aluminum ferric chloride flocculant, contained Zn 2+be conducive to the stability improving iron, aluminium.
The invention has the beneficial effects as follows:
(1) About Flocculating Effect of Flocculant of the present invention is good, stable performance, can be used for the pre-treatment of waste water difficult for biological degradation as paper waste, waste water from dyestuff, leather waste water, deinking wastewater, heavy metal wastewater thereby etc., compared with polyacrylamide conventional in water treatment, flocculant dosage of the present invention is less, the alumina blossom particles formed in treating processes is large and closely knit, and settling velocity is fast, better for the treatment effect reducing COD and colourity;
(2) flocculation agent of the present invention has the advantages such as efficient low-consume, safe and harmless, non-secondary pollution;
(3) preparation method of flocculation agent of the present invention is simple, and the material source utilized is extensive, achieves the recycling of spent acid, decreases environmental pollution.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Al in the flyash that the embodiment of the present invention uses 2o 3mass content be in 32%(50g flyash containing 0.157mol Al 2o 3), Fe 2o 3mass content be in 12%(50g flyash containing 0.038mol Fe 2o 3), the hydrogen peroxide mass concentration used is 30wt%, other chemical reagent used, and if no special instructions, is all obtained by routine business approach.
embodiment 1
(1) in 70 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 2h of 1L 3mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.41 mol/L, Fe 3+concentration is 0.06 mol/L);
(2) 60mL ferrous waste acid (Fe is got 2+content 3mol/L), add step (1) gained 0.5L flyash leach liquor, add 28g(0.2mol again) zinc chloride, then 0.04g(0.1mmol is added) stablizer sodium borate decahydrate, adjust ph to 4, stirs at 70 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 20h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 1.
embodiment 2
(1) in 70 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 3h of 1L 4mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.41 mol/L, Fe 3+concentration is 0.06mol/L);
(2) 45mL ferrous waste acid (Fe is got 2+content 4mol/L), add step (1) gained 0.5L flyash leach liquor, add 14g(0.1mol again) zinc chloride, then 0.05g(0.13mmol is added) stablizer sodium borate decahydrate, adjust ph to 4, stirs at 80 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 22h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 2.
embodiment 3
(1) in 70 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 4h of 1L5mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.46mol/L, Fe 3+concentration is 0.07mol/L);
(2) 62mL ferrous waste acid (Fe is got 2+content 5mol/L), add step (1) gained 0.5L flyash leach liquor, add 14g(0.1mol again) zinc chloride, then 0.06g(0.16mmol is added) stablizer sodium borate decahydrate, adjust ph to 4, stirs at 90 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 24h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 3.
embodiment 4
(1) in 80 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 3h of 1L3mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.52 mol/L, Fe 3+concentration is 0.08 mol/L);
(2) 50mL ferrous waste acid (Fe is got 2+content 4mol/L), add step (1) gained 0.5L flyash leach liquor, add 18g(0.13mol again) zinc chloride, then 0.05g(0.13mmol is added) stablizer sodium borate decahydrate, adjust ph to 5, stirs at 80 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 24h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 4.
embodiment 5
(1) in 80 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 4h of 1L4mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.56 mol/L, Fe 3+concentration is 0.09 mol/L);
(2) 115mL ferrous waste acid (Fe is got 2+content 3mol/L), add step (1) gained 0.5L flyash leach liquor, add 18g(0.13mol again) zinc chloride, then 0.06g(0.16mmol is added) stablizer sodium borate decahydrate, adjust ph to 5, stirs at 90 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 22h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 5.
embodiment 6
(1) in 80 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 2h of 1L5mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.52 mol/L, Fe 3+concentration is 0.07mol/L);
(2) 60mL ferrous waste acid (Fe is got 2+content 4mol/L), add step (1) gained 0.5L flyash leach liquor, add 36g(0.26mol again) zinc chloride, then 0.04g(0.1mmol is added) stablizer sodium borate decahydrate, adjust ph to 5, stirs at 70 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 20h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 6.
embodiment 7
(1) in 100 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 4h of 1L3mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.59mol/L, Fe 3+concentration is 0.11 mol/L);
(2) 100mL ferrous waste acid (Fe is got 2+content 4mol/L), add step (1) gained 0.5L flyash leach liquor, add 21g(0.15mol again) zinc chloride, then 0.06g(0.16mmol is added) stablizer sodium borate decahydrate, adjust ph to 6, stirs at 90 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 22h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 7.
embodiment 8
(1) in 100 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 2h of 1L4mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.44 mol/L, Fe 3+concentration is 0.07mol/L);
(2) 40mL ferrous waste acid (Fe is got 2+content 5mol/L), add step (1) gained 0.5L flyash leach liquor, add 30g(0.22mol again) zinc chloride, then 0.04g(0.1mmol is added) stablizer sodium borate decahydrate, adjust ph to 6, stirs at 70 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 20h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 8.
embodiment 9
(1) in 100 DEG C of waters bath with thermostatic control, use the salt acid soak 50g flyash 3h of 1L5mol/L, filter, obtain flyash leach liquor 0.5L(Al 3+concentration is 0.37 mol/L, Fe 3+concentration is 0.06 mol/L);
(2) 50mL ferrous waste acid (Fe is got 2+content 3mol/L), add step (1) gained 0.5L flyash leach liquor, add 13g(0.095mol again) zinc chloride, then 0.05g(0.13mmol is added) stablizer sodium borate decahydrate, adjust ph to 6, stirs at 80 DEG C, finally add 15mL hydrogen peroxide, leave standstill slaking 24h under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized, be designated as flocculation agent 9.
Flocculation agent 1 ~ 9 prepared by embodiment 1 ~ 9 being respectively used to process turbidity is the solution of 100NTU, treatment process condition is: in 1L solution, add 2mL flocculation agent, pH is 4.0 times, stir 2min, stirring frequency is 150r/min, after precipitation, get supernatant liquor and measure turbidity, test result is as shown in table 1.
Table 1 flocculation agent 1 ~ 9 flocculating effect contrast table
As shown in Table 1, flocculation agent 7 pairs of turbidity are that the flocculating effect of the solution of 100NTU is best, and be secondly flocculation agent 5, from condition prepared by flocculation agent, when Zn content is identical, the content of aluminium, iron is higher, and the flocculating effect of flocculation agent is better.
Get 500mL waste water from dyestuff (COD700mg/L) and be placed in 1000mL beaker, 150r/min rapid stirring, flocculation agent 5 and flocculation agent 7 is added in water sample, continue to stir 1min soon, then proceed to 35r/min and stir 10min at a slow speed, after leaving standstill 30min, get supernatant liquor and measure turbidity, colourity and COD, test result is as shown in table 2.
Table 2 polyacrylamide and embodiment of the present invention About Flocculating Effect of Flocculant contrast table
As shown in Table 2, (1) flocculation agent 5 and the COD of 7 pairs of waste water from dyestuff and the treatment effect of colourity are obviously better than polyacrylamide, the dosage of the amount ratio polyacrylamide of flocculation agent 5 and 7 is less, greatly save cost, and when add-on is identical, along with the consumption of flocculation agent increases, the effect of flocculation is increasing trend; (2) to add the alumina blossom particles of rear formation large and closely knit for flocculation agent 7, and settling velocity is fast, illustrates flocculation agent 7 to reduce dyestuff COD and colourity effect better.

Claims (9)

1. be polymerized a zinc-base aluminum ferric chloride flocculant, it is characterized in that, make in accordance with the following methods:
(1) in 70 ~ 100 DEG C of waters bath with thermostatic control, use salt acid soak flyash, filter, obtain flyash leach liquor;
(2) ferrous waste acid is got, add step (1) gained flyash leach liquor, add zinc chloride again, make the mol ratio of element Zn:Al:Fe in solution be 1:1.0 ~ 2.5:1.0 ~ 3.5, then add stablizer sodium borate decahydrate, adjust ph to 4 ~ 6, stir, finally add excessive hydrogen peroxide, leave standstill slaking under normal temperature, zinc-base aluminum ferric chloride flocculant must be polymerized.
2. be polymerized zinc-base aluminum ferric chloride flocculant according to claim 1, it is characterized in that: in step (2), the add-on of described sodium borate decahydrate is 0.17 ~ 0.30mmol/L.
3. according to claim 1 or 2, be polymerized zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (1), Al in described flyash 2o 3mass content be 22 ~ 40%, Fe 2o 3mass content be 7 ~ 15%.
4. according to one of claims 1 to 3 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (1), the concentration of described hydrochloric acid is 3 ~ 5mol/L.
5. according to one of Claims 1 to 4 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (1), the consumption of described hydrochloric acid is 15 ~ 25mL/g flyash.
6. according to one of Claims 1 to 5 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (1), the time of described immersion is 2 ~ 4h.
7. according to one of claim 1 ~ 6 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (2), described ferrous waste acid refers to Fe 2+content is the acid solution of 3 ~ 5mol/L.
8. according to one of claim 1 ~ 7 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (2), the temperature of described stirring is 70 ~ 90 DEG C.
9. according to one of claim 1 ~ 8 described polymerization zinc-base aluminum ferric chloride flocculant, it is characterized in that: in step (2), the time of described slaking is 20 ~ 24h.
CN201510175026.4A 2015-04-14 2015-04-14 A kind of polymerization zinc-base aluminum ferric chloride flocculant and preparation method thereof Expired - Fee Related CN104724806B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105600893A (en) * 2015-11-18 2016-05-25 常州市清流水处理剂有限公司 Polyferric chloride production method and device
CN110182995A (en) * 2019-06-06 2019-08-30 武汉钢铁有限公司 Advanced treatment method for carbonization wastewater

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CN102815773A (en) * 2012-03-22 2012-12-12 赵佳 Preparation method of composite polysulfide ferric chloride coagulant
CN102942237A (en) * 2012-11-15 2013-02-27 天津市鑫昌科技有限公司 Preparation method for water purifier capable of synchronously removing ammonia nitrogen and phosphorus in waste water

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CN1403388A (en) * 2001-08-31 2003-03-19 姚钢 Production process of inorganic Al-Fe polymerized coagulant with flyash
CN101412559A (en) * 2008-10-31 2009-04-22 乔占印 Poly(ferric zinc aluminum sulphrate), and preparation thereof and method for treating sewerage by using same
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CN102942237A (en) * 2012-11-15 2013-02-27 天津市鑫昌科技有限公司 Preparation method for water purifier capable of synchronously removing ammonia nitrogen and phosphorus in waste water

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105600893A (en) * 2015-11-18 2016-05-25 常州市清流水处理剂有限公司 Polyferric chloride production method and device
CN110182995A (en) * 2019-06-06 2019-08-30 武汉钢铁有限公司 Advanced treatment method for carbonization wastewater
CN110182995B (en) * 2019-06-06 2021-12-17 武汉钢铁有限公司 Coking wastewater advanced treatment method

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