CN105645551A

CN105645551A - Treatment method for reducing nitrosodimethylamine in water by catalyzing zero-valent iron through copper corrosion product

Info

Publication number: CN105645551A
Application number: CN201511024159.8A
Authority: CN
Inventors: 韩莹; 王济禾; 李军; 张瑶; 李微微
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2015-12-31
Filing date: 2015-12-31
Publication date: 2016-06-08

Abstract

The invention relates to a treatment method for reducing nitrosodimethylamine in water by catalyzing zero-valent iron through a copper corrosion product. The method comprises the following steps of adding 5 to 10mmol/L of copper corrosion product and 10 to 20g/L of iron powder into water containing the nitrosodimethylamine; adjusting a pH value to be 6.5 to 7.5, placing on a rotating reactor for rotating at the rotating speed of 40 to 80r/min and reacting for 3 to 24 hours, wherein the copper corrosion product is one of copper oxide, cuprous oxide, copper hydroxide, basic cupric carbonate and copper ions. According to the treatment method disclosed by the invention, in the process of using the copper corrosion product to catalyze the zero-valent iron for reducing NDMA (Nitrosodimethylamine), an obvious catalytic effect (the removal rate of the NDMA can reach 99.9 percent) is realized, and the NDMA as a strongly carcinogenic substance in the water can be effectively controlled, so that the safety of drinking water is guaranteed.

Description

The processing method of nitrosodimethylamine in copper corrosion product catalyst Zero-valent Iron reductive water

(1) technical field

The present invention relates to the processing method of nitrosodimethylamine in a kind of copper corrosion product catalyst Zero-valent Iron reductive water.

(2) background technology

Nitrosodimethylamine (NDMA) is a kind of material with high carcinogenic risk, after NDMA drinking near the rocket engine checkout area of Canadian drinking water plant water outlet and the U.S. is detected in well, drink the researcher of hydrosphere, the community service department of America & Canada improves the attention rate to it. Investigation and research afterwards show all there is generation in NDMA water after chlorine, chloramines disinfection and ozone oxidation. Except North America, some countries in Europe and Asia have also detected NDMA successively in the water outlet of source water, drinking water plant water outlet and sewage treatment plant. The Source water and drinking water treatment plant water outlet of China also has the existence of NDMA. In view of NDMA being widely present in water body, very necessary look for effective technology it is controlled.

Due to the special nature (highly dissoluble, low volatility and less Octanol/water Partition Coefficients, molecule little and not charged) of NDMA, it all can not be effectively treated by volatilization, air stripping, soil and activated carbon adsorption, reverse osmosis etc. naturally. Then, it is necessary to adopt intensive treatment technology that it is controlled, mainly include bioanalysis, film process, absorption, ozone oxidation, ultraviolet photolysis and Zero-valent Iron reducing process. Bioanalysis reaction carries out even needing very slowly the time of several years. NDMA in water is all had crown_interception but does not reach and retain completely by commercial brackish water reverse osmosis membrane, NF membrane. NDMA is not had basic degraded by absorption method, is simply enriched with on the adsorbent material. Ozone degradation NDMA poor effect, can only obtain the clearance that NDMA is relatively low when ozone dosage is significantly high. Ultraviolet photolysis can effectively be degraded NDMA, but exists when being unfavorable for the material that ultraviolet penetrated or disturbed shortwave in water body, and the method treatment effect is poor. And apply to 10 times when the ultraviolet throwing amount during actual water processes is to be generally used for sterilization, and consuming energy huge, expense is also significantly high accordingly.

In sum, in order to be applied in processing at actual water, it is necessary to set up and a kind of new can effectively remove the simple processing method of NDMA in water.Zero-valent Iron reduction technique raw material sources are extensive, cheap and easy to get, have been applied to removing NDMA. But its response time is long, clearance is too low, does not reach satisfied standard. If a class material catalysis Zero-valent Iron can be found out thus effectively reducing NDMA, it will become a kind of new simple water technology.

(3) summary of the invention

It is an object of the present invention to provide the processing method of nitrosodimethylamine in a kind of simple, quick, easy control water.

The technical solution used in the present invention is:

The processing method of nitrosodimethylamine in copper corrosion product catalyst Zero-valent Iron reductive water, described method includes: add the copper corrosion product of 5��10mmol/L and the iron powder of 10��20g/L in the water containing nitrosodimethylamine, regulating pH value is 6.5��7.0 (regulating pH with buffer solution), is placed on rotatable reactor in the rotating speed revolving reaction 3��24h of 40��75r/min; Described copper corrosion product is one of following: copper oxide (powder), Red copper oxide (powder), Copper hydrate (powder), basic copper carbonate (powder), (anion is generally Cl to copper ion^-)��

Preferably, described copper corrosion product is copper oxide or copper ion (when using copper oxide, react 12 hours NDMA clearances and can reach more than 98%, use copper ion, react 3 hours NDMA clearances and can reach more than 99%).

Concrete, described method is as follows: add the copper corrosion product of 5mmol/L and the iron powder of 10g/L in the water containing nitrosodimethylamine, and regulating pH value is 7, is placed on rotatable reactor in the rotating speed revolving reaction 3h of 45r/min; Described copper corrosion product is copper ion.

Potable water system uses the corrosion product that can produce copper when copper pipe or copper alloy, including copper ion (Cu²⁺), Red copper oxide (Cu₂O), copper oxide (CuO), Copper hydrate (Cu (OH)₂) and basic copper carbonate (Cu₂(OH)₂CO₃)). These copper-containing substances have catalytic capability in a lot of reactions, use it for catalysis Zero-valent Iron reduction NDMA, can be effectively improved NDMA clearance.

The beneficial effects are mainly as follows: the corrosion product of copper is used in the process of catalysis Zero-valent Iron reduction NDMA by the present invention, there is obvious catalytic effect (NDMA clearance can reach 99.9%), can effectively control strong carcinogenecity material nitrosodimethylamine (NDMA) in water, thus having ensured the safety of drinking water.

(4) accompanying drawing explanation

Fig. 1 is that the efficiency ratio of deoxidization, degradation NDMA is relatively under the corrosion product catalysis of copper for metallic iron.

Fig. 2 is the reaction of the corrosion product of copper and NDMA.

(5) detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to that:

Embodiment 1:

The brown extraction flask of 40mL adds 40mLHEPES buffer solution (25mmol L^-1, pH value is 7.0), add 10g L^-1Iron powder, then be separately added into the copper oxide of 12.7mg, 28.6mg, 19.5mg, 44.2mg, Red copper oxide, Copper hydrate, (wherein the corrosion product content of copper is 5mmol L to basic copper carbonate^-1); For copper ion (Cu²⁺), in buffer solution, first add Cu²⁺Mother solution make the Cu in solution²⁺Reach 5mmol L^-1, add 10g L afterwards^-1Ferrum powder; Adding NDMA mother solution after above step makes its initial concentration reach 100 �� g L^-1, cover tightly bottle cap, be placed on QB-328 rotary incubator (Haimen City its woods Bel instrument manufacturing company limited) with 45r min^-1Rotating speed rotate; Timing sampling, taken sample employing vacuum pump carries out the corrosion product of the sucking filtration unreacted iron powder of separation and copper thus terminating reaction through the filter membrane of 0.22 ��m, and gained water sample is tested for the analysis for NDMA concentration.Reaction total time is 18h, temperature 20 DEG C.

Fig. 1 is the corrosion product (Red copper oxide (Cu being respectively adopted Zero-valent Iron, several copper₂O), basic copper carbonate (Cu₂(OH)₂CO₃), copper oxide (CuO), Copper hydrate (Cu (OH)₂), copper ion (Cu²⁺) situation of NDMA in catalysis Zero-valent Iron reductive water. Fig. 2 is the situation (each response parameter is consistent with the above, is simply not added with iron powder) of the corrosion product of independent copper and NDMA reaction.

As it is shown in figure 1, reaction carries out 18h, the clearance of NDMA is only 12.9% by Zero-valent Iron, and the residual concentration of NDMA is 87.1 �� g L^-1; And through the identical response time, Zero-valent Iron is at Cu₂O��Cu₂(OH)₂CO₃��CuO��Cu(OH)₂��Cu²⁺Catalysis under the clearance of NDMA is respectively reached 67.8%, 73.1%, 75.9%, 98.8%, 99.9%. As shown in Figure 2 in the 18h that reaction is investigated, Cu₂O��Cu₂(OH)₂CO₃��CuO��Cu(OH)₂��Cu²⁺The clearance of NDMA is respectively smaller than 8.4%, 9.2%, 9.4%, 7.5% and 8.0%, it can thus be appreciated that when not having Zero-valent Iron, NDMA is not had obvious degradation effect by the corrosion product of copper.

It is comprehensive above it can be seen that the corrosion product of copper has obvious catalytic effect in the process of Zero-valent Iron reduction NDMA.

Embodiment 2:

Toward containing nitrosodimethylamine (concentration 100 �� g L^-1) water in add the copper ion of 5mmol/L (anion be Cl^-) and the iron powder of 10g/L, regulating pH value is 7.0, and reacting 3h, NDMA clearance with the rotating speed Stirring of 50r/min is more than 95%.

Claims

1. the processing method of nitrosodimethylamine in copper corrosion product catalyst Zero-valent Iron reductive water, described method includes: add the copper corrosion product of 5��10mmol/L and the iron powder of 10��20g/L in the water containing nitrosodimethylamine, regulating pH value is 6.5��7.0, with the rotating speed revolving reaction 3��24h of 40��75r/min; Described copper corrosion product is one of following: copper oxide, Red copper oxide, Copper hydrate, basic copper carbonate, copper ion.

2. the method for claim 1, it is characterised in that described copper corrosion product is copper oxide or copper ion.

3. the method for claim 1, it is characterised in that described method is as follows: add the copper corrosion product of 5mmol/L and the iron powder of 10g/L in the water containing nitrosodimethylamine, regulating pH value is 7, with the rotating speed revolving reaction 3h of 45r/min; Described copper corrosion product is copper ion.