CN105461042A - Preparation method of carbon based nano-iron alloy water treatment material - Google Patents

Abstract

The invention belongs to the field of water treatment technologies, relating to a preparation method of a carbon based nano-iron alloy water treatment material by utilizing carbon based nano-iron alloy to activate hypochlorous acid and hypochlorite, and generate chlorine radical and hydroxyl radical to remove p-chlorotoluene. The preparation method comprises the following steps: 1) an activation process of granular active carbon; the granular active carbon is activated by adopting a boiling water activation method; 2) nano-iron alloy is loaded in the activated granular active carbon; inorganic iron salt and activated active carbon are mixed according to the iron-carbon mass ratio of (1:1) to (1:5), nickel chloride or palladium acetate is mixed with the inorganic iron salt, and the molar ratio of the nickel chloride or the palladium acetate to iron in ferric salt is (1:5) to (1:10), then iron alloy is produced by being reduced by adopting a potassium borohydride liquid phase method and is loaded on the granular active carbon. The material obtained by the invention has less secondary pollution in a water treatment process, good treatment effect, and is liable to be realized.

Description

The preparation method of charcoal base nanosized iron alloy material for water treatment

Technical field

The invention belongs to water-treatment technology field, relating to one can activate hypochlorous acid and hypochlorite by sharp charcoal base nanosized iron alloy, produces the preparation method of the charcoal base nanosized iron alloy material for water treatment of chlorine radical and hydroxyl radical free radical removal parachlorotoluene.

Background technology

Parachlorotoluene and benzene, toluene, vinylbenzene are contaminant trace species common in tap water water source, larger to the Health hazard of people.

Present technology much all adopts nano zero valence iron and the inorganics in the nano zero valence iron removal water of doping noble metal or organism, this existing a lot of bibliographical information.Mohammed etc. have studied nano zero valence iron and activate Potassium Persulphate and to degrade other organic pollutants, result of study shows that Sodium Persulfate is activated by nano zero valence iron and is better than to the effect removing organic pollutant the effect that nano zero valence iron removes organic pollutant, meanwhile, the effect of nano zero valence iron activation Sodium Persulfate removal naphthalene can reach 99%.Yusulf etc. also use Fe ²⁺with the product such as the method for hot activation Potassium Persulphate degraded nitrogen protoxide, result of study shows that temperature is elevated to 70-100 DEG C, the Fe of 0.01M ²⁺with Potassium Persulphate can by degradable for the NO of 100% fall.Meanwhile, bibliographical information chlorine radical and hydroxyl radical free radical synergy is also had can to degrade trichloronitromethane and phenylformic acid.

The defect that existing method exists is: nano zero valence iron nanosized iron alloy activity is not high, and easily causes secondary pollution, not easily reclaims; Further, existing methodical treatment effect still needs to improve.

Summary of the invention

Technical problem to be solved by this invention is, provides that a kind of secondary pollution is little, treatment effect good, is easy to the preparation method of the charcoal base nanosized iron alloy material for water treatment realized.

The preparation method of charcoal base nanosized iron alloy material for water treatment of the present invention, comprises the following steps:

1) activation procedure of granulated active carbon; Adopt boiling water activation method activated particle gac.It comprises the steps:

A1. granulated active carbon is mixed with deionized water, be heated to boiling state and keep 20 ~ 30 minutes;

A2. naturally cool to room temperature and place 5 ~ 8 hours;

A3. get and precipitate and use washed with de-ionized water 2 ~ 4 times;

A4. at 110 ~ 130 DEG C, be dried to constant weight, obtain the granulated active carbon after described activation.

2) loaded with nano iron alloy in granulated active carbon after activation; Gac after inorganic molysite and activation is mixed with the iron carbon mass ratio of 1:1 ~ 1:5; nickelous chloride or acid chloride are mixed with inorganic molysite; the mol ratio of the iron in nickelous chloride or acid chloride and molysite is 1:5 ~ 1:10, then adopts POTASSIUM BOROHYDRIDE liquid phase method to be reduced into iron alloy load on granulated active carbon.

Further, described inorganic molysite is FeSO ₄7H ₂o, FeCl ₃7H2O, FeCl ₂4H ₂o and Fe ₂(SO ₄) ₃9H ₂any one in O.

Owing to adopting such scheme, the invention has the beneficial effects as follows:

1, in product, charcoal base nano zero valence iron can carry out deoxidization, degradation to the contaminative organism in water, and iron Carbon Materials can form galvanic cell degradation of organic substances; 2, noble metal nickel and palladium have katalysis on nano zero valence iron, can accelerate nano zero-valence Fe3+ reduction organism; 3, cooperative with ultraviolet radiation effect in water treatment procedure, can activate chlorine radical and hydroxyl radical free radical degraded parachlorotoluene or vinylbenzene that chlorine water hydrolysis products hypochlorous acid and hypochlorite generate; 4, by nano zero valence iron and nickel or palladium load on granulated active carbon, nano zero valence iron secondary pollution can be reduced.

Embodiment

Below in conjunction with embodiment, the present invention is further illustrated.

Embodiment:

The present embodiment provides a kind of charcoal base nanosized iron alloy material, and adopts this material to work in coordination with chlorine radical parachlorotoluene in degradation water under ultraviolet catalytic effect.This material is also applicable to the degraded to the material being similar to parachlorotoluene.The present embodiment is to be described as the parachlorotoluene of one of contaminative organism.

The present embodiment additionally provides a kind of preparation method of charcoal base nanosized iron alloy material, mainly comprises following three operations:

(1), the activation procedure of gac;

(2), the preparation section of charcoal base nanosized iron alloy;

The object of operation (1) is to activate granulated active carbon to obtain the gac after activating.Boiled water washing out method can be selected to activate granulated active carbon; this method comprises the following steps: take a certain amount of granulated active carbon as required and be placed in a clean beaker; on electric furnace, boiling is heated to after deionized water mixing; keep boiling state 30 minutes; then naturally cool to room temperature and continue placement 8 hours; outwell supernatant liquid; continuation washed with de-ionized water precipitates 4 times; be placed in thermostatic drying chamber again and be dried to constant weight at 120 DEG C; namely obtain the gac after activating, loaded in port grinding bottle for subsequent use.

Gac after the object of operation (2) is to adopt inorganic molysite and nickelous chloride or acid chloride and activation prepares charcoal base nanosized iron alloy, comprises the following steps: by inorganic molysite FeSO ₄7H ₂o and the gac after activating mix with the iron carbon mass ratio of 1:4, add nickelous chloride or acid chloride mixes with molysite, wherein the mol ratio of nickel or palladium and iron is 1:8, Homogeneous phase mixing resulting mixture in a clean beaker also adds deionized water and stirring and mixes, the deionized water added and the mass ratio of mixture are 8:1, and add in aqueous molecular weight be the PVOH of 6000 as dispersion agent, the concentration 1-3mol/l of dispersion agent.Then add relative to inorganic molysite and nickelous chloride or the excessive sodium borohydride solution (2mol/L-5mol/L) of acid chloride, the molar weight of sodium borohydride is greater than 3:1 relative to inorganic molysite and nickelous chloride (or acid chloride) amount, and wherein the equation of ferric iron and sodium borohydride reduction is as follows:

2Fe ³⁺+6BH ₄ ^-+6H ₂O＝2Fe ⁰+6B(OH) ₃+9H ₂

Stir reduction after 0.5-1 hour, in oxygen-free environment, use water and washed with methanol totally, then nano zero valence iron is kept in the solution of dehydrated alcohol.

P-dichlorobenzene in the aqueous solution of degrading under charcoal base nanosized iron alloy assistance UV-light in the present embodiment activates the strong oxidizing property chlorine radical and hydroxyl radical free radical effect produced, and other need the similar organism of reduction.Its principle is shown in reaction formula (1) ~ (7):

${\mathrm{Cl}}_2+H_{2}O\↔HOCl+HCl---\left(1\right)$

HOCl+UVphotons→ ^·OH+ ^·Cl(3)

OCl ^-+UVphotons→ ^·O ^-+ ^·Cl(4)

^·O ^-+H ₂O→ ^·OH+OH ^-(5)

^·Cl+H ₂O→ ^·OH+Cl ^-+H ⁺(6)

$C_{\·}l+{\mathrm{Cl}}^{-}\↔{{\mathrm{Cl}}_2}^{\·-}---\left(7\right)$

Carry out testing inspection to the material that the embodiment of the present invention obtains, when former state concentration is 0.85mg/L, the concentration of clorox is under the same terms of 100mg/L:

1) when the concentration adding charcoal base iron-nickel alloy is again 0.1-1g/L, the clearance of parachlorotoluene is 40%-79%.

2) when the concentration adding charcoal base creeper alloy is again 0.1-1g/L, the clearance of parachlorotoluene can reach more than 95%.

Claims (3)

1. a preparation method for charcoal base nanosized iron alloy material for water treatment, is characterized in that: comprise the following steps,

1) activation procedure of granulated active carbon; Adopt boiling water activation method activated particle gac;

2) loaded with nano iron alloy in granulated active carbon after activation; Gac after inorganic molysite and activation is mixed with the iron carbon mass ratio of 1:1 ~ 1:5; nickelous chloride or acid chloride are mixed with inorganic molysite; the mol ratio of the iron in nickelous chloride or acid chloride and molysite is 1:5 ~ 1:10, then adopts POTASSIUM BOROHYDRIDE liquid phase method to be reduced into iron alloy load on granulated active carbon.

2. the preparation method of charcoal base nanosized iron alloy material for water treatment according to claim 1, is characterized in that: its step 1) in the step of activated particle gac as follows:

A1. granulated active carbon is mixed with deionized water, be heated to boiling state and keep 20 ~ 30 minutes;

A2. naturally cool to room temperature and place 5 ~ 8 hours;

A3. get and precipitate and use washed with de-ionized water 2 ~ 4 times;

A4. at 110 ~ 130 DEG C, be dried to constant weight, obtain the granulated active carbon after described activation.

3. the preparation method of charcoal base nanosized iron alloy material for water treatment according to claim 1, is characterized in that: described inorganic molysite is FeSO ₄7H ₂o, FeCl ₃7H2O, FeCl ₂4H ₂o and Fe ₂(SO ₄) ₃9H ₂any one in O.