KR101536965B1 - The titania supported palladium-copper of catalysts for the reduction of nitrate water and method thereof - Google Patents
The titania supported palladium-copper of catalysts for the reduction of nitrate water and method thereof Download PDFInfo
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Abstract
The present invention relates to a palladium-copper catalyst for reducing nitrate nitrogen contained in a titania carrier and a method for producing the same, which is characterized in that palladium and copper are supported on a titania carrier calcined at a temperature of 350 to 950 ° C.
Description
The present invention relates to a palladium-copper catalyst (Pd-Cu / TiO 2 ) for reducing nitrogenous nitrogen in water supported on a titania carrier and to a method for producing the same. More specifically, the present invention relates to a palladium- And a copper-supported palladium-copper catalyst and a method for producing the same.
As recent industry develops, new synthetic substances that do not exist in nature are introduced into nature, and pollution is diversified and water pollution becomes serious.
Water Nitrate Nitrogen is generated mainly from agricultural fertilizers, manure, livestock manure, synthetic detergent, and when sewage or factory wastewater containing large amount of wastewater flows into a lake or a lake including a dam, eutrophication, red tide phenomenon, ammonia fish toxin, Of dissolved oxygen. In addition, nitrate nitrogen in water at high concentrations in drinking water can cause diseases such as blue-baby syndrome (methemoglobinemia), which can affect health.
Conventional methods for reducing nitrate nitrogen have been developed, such as physico-chemical treatment using ion exchange resins, and biological treatment using microorganisms. However, physico-chemical treatment requires additional post treatment due to the brine that occurs when the ion exchange resin is regenerated, and the biological treatment has a disadvantage in that it requires a large treatment area due to a long residence time. Therefore, there is a need to develop a technique for reducing nitrogenous nitrogen in water in a short time without requiring additional post-treatment. Therefore, recently, a technique utilizing a catalyst for removing nitrogenous nitrogen in the water has been attracting attention. Catalyst-based technology has the advantage of being able to react under mild conditions as compared to biological treatment requiring strict control of reaction conditions.
However, the conventional catalyst application technique has a problem in that it takes about 3 hours to completely remove nitrogenous nitrogen in the water, and thus it does not have a better performance than biological treatment.
In order to solve the above problems, it is an object of the present invention to provide a palladium-copper catalyst for nitrate-nitrogen reduction in water supported on a titania carrier which can remove nitrogenous nitrate in water in a short time, and a method for producing the same.
In order to achieve the above object,
The present invention provides a titania carrier supported on a titania carrier calcined at a temperature of 350 to 950 DEG C, wherein the titania carrier is supported on palladium and copper.
(1) baking titania at a temperature of 350 to 950 DEG C to produce a titania carrier;
(2) immersing the calcined titania carrier in an aqueous acid solution, and then introducing a palladium precursor and a copper precursor;
(3) adding an alkali aqueous solution to the titania carrier into which the palladium precursor and the copper precursor have been added to adjust the pH to 9 or more, and then heating;
(4) washing, drying and firing a titania carrier to which a palladium precursor and a copper precursor having a pH of 9 or more are added; And
(5) reducing the titania carrier into which the calcined palladium precursor and the copper precursor have been introduced, and carrying out the step of reducing the nitrate-nitrogen-containing palladium-copper catalyst supported on the titania carrier.
The palladium-copper catalyst supported on the titania carrier of the present invention does not require additional post-treatment and has the effect of removing nitrate nitrogen in water in a short time.
1 is an XRD graph of the titania carrier prepared in Examples 1 and 2 and Comparative Example 1. Fig.
Fig. 2 is an XRD graph of a palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier prepared in Examples 1 and 2 and Comparative Example 1. Fig.
FIG. 3 is a graph showing changes in concentration of nitrate nitrogen in water with time using a palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier prepared in Examples 1 and 2 and Comparative Example 1. FIG.
FIG. 4 is a graph showing the concentration of nitrogenous nitrate in water and the pH of a reactant according to the carbon dioxide flow rate using a palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier prepared in Example 1. FIG.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a catalyst for reducing nitrate nitrogen in water, which causes eutrophication, red tide phenomenon and dissolved oxygen in water, wherein the catalyst comprises palladium and copper supported on a titania carrier calcined at a temperature of 350 to 950 ° C The present invention relates to a palladium-copper catalyst for reducing nitrate nitrogen contained in a titania carrier.
The titania carrier is prepared by firing at 350 to 950 캜 for 3 to 5 hours. The fouling may physically remove contaminants that are adsorbed on the titania carrier, and the titania carrier may be changed in the temperature range of 350 to 950 ° C. The titania carrier phase is changed into anatase phase and rutile phase on the anatase through baking. The palladium and copper are supported at 0.25 to 7 wt% and 0.1 to 5 wt%, preferably 2.5 to 3.5 wt% and 0.8 to 1.2 wt%, respectively, based on the total weight of the titania carrier.
The present invention also provides a process for producing a palladium-copper catalyst for nitrate-nitrogen-reduction in water carried on a titania carrier, and the process is as follows.
(1) baking titania at a temperature of 350 to 950 占 폚 to prepare a titania carrier;
(2) immersing the calcined titania carrier in an aqueous acid solution, and then introducing a palladium precursor and a copper precursor;
(3) adding an alkali aqueous solution to the titania carrier into which the palladium precursor and the copper precursor have been added to adjust the pH to 9 or more, and then heating;
(4) washing, drying and firing a titania carrier to which a palladium precursor and a copper precursor having a pH of 9 or more are added; And
(5) A step of reducing the titania carrier into which the calcined palladium precursor and the copper precursor have been introduced is reduced to prepare a palladium-copper catalyst for nitrate-nitrogen reduction in water supported on a titania carrier.
The titania used in the step (1) is anatase titania, and is calcined at a temperature of 350 to 950 ° C for 3 to 5 hours to produce an anatase phase and a rutile phase, thereby changing the phase of titania. In the step (2), the titania carrier produced in the step (1) is immersed in an aqueous acid solution, followed by the addition of a palladium precursor and a copper precursor. Although the acid aqueous solution is not particularly limited, , And the concentration of the hydrochloric acid aqueous solution is preferably 0.005 to 0.05M. In addition, the palladium precursor and the copper precursor are used as the active metal in the present invention, and any salts capable of providing palladium or copper may be used without any particular limitation, and palladium chloride and copper chloride are preferably used.
In the step (3), an alkaline aqueous solution is added to the titania carrier into which the palladium precursor and the copper precursor have been added to convert to an alkaline state having a pH of 9 or more. The aqueous alkaline solution used herein is 1 to 2M sodium carbonate, urea and sodium hydroxide It uses sodium carbonate to make it. Further, the alkali state in the step (3) is preferably from pH 9 to
In step (4), the palladium precursor and the copper precursor remaining after the reaction are washed using distilled water, washed, dried at a temperature of 80 to 120 ° C for 20 to 30 hours, treated at a temperature of 200 to 400 ° C for 3 to 8 Lt; / RTI >
In the step (5), the titania carrier into which the palladium precursor and the copper precursor are washed, dried and fired is reduced using H 2 gas, and the reduction temperature is 100 to 300 ° C, and the reduction is performed for 1 to 5 hours. In addition, the reduction can be performed by injecting an inert gas such as N 2 or Ar together with the H 2 gas. After the reduction step, a palladium-copper catalyst for nitrate nitrogen reduction in water is finally prepared and supported on a titania carrier.
The palladium-copper catalyst for reducing nitrate nitrogen contained in the titania carrier contains 0.25 to 7 wt% of palladium and 0.1 to 5 wt% of copper, respectively, based on the total weight of the titania carrier, and preferably 2.5 to 3.5 wt% % And 0.8 to 1.2% by weight. In addition, the palladium-copper catalyst for reducing nitrate nitrogen contained in the titania carrier contains 70 to 100% by weight of an anatase based on the total weight of the titania carrier.
Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples.
< Titania On the carrier Supported Underwater nitric acid Reduction Preparation of palladium-copper catalyst>
Example One.
10 g of pure anatase (Sigma Aldrich) was calcined at a temperature of 500 캜 for 4 hours to prepare a titania carrier. The titania carrier was immersed in 500 mL of a 0.01 M hydrochloric acid aqueous solution, and then 0.4999 g and 0.2115 g of palladium chloride and copper chloride, which are active metals, were added to the total weight of the titania carrier in an amount of 3 wt% and 1 wt%, respectively . Then, 1 M sodium carbonate was added to adjust the pH to 10, and the mixture was stirred at a temperature of 70 캜 for 21 hours. After the agitation, the titania carrier containing the palladium precursor and the copper precursor was washed with 6 L of tertiary distilled water, dried at 100 ° C. for 24 hours, and then calcined at 300 ° C. for 6 hours. The titania carrier loaded with the calcined palladium precursor and copper precursor was reduced for 2 hours at a temperature of 200 캜 using 10% H 2 / N 2 gas to prepare a palladium-copper catalyst for nitrate nitrogen reduction in water supported on a titania carrier (Pd-Cu / TiO 2 ).
Example 2.
A palladium-copper catalyst (Pd-Cu / TiO 2 ) for reducing nitrate nitrogen in water supported on a titania carrier was prepared in the same manner as in Example 1 except that the pure anatase was calcined at a temperature of 920 ° C.
Comparative Example One.
A palladium-copper catalyst (Pd-Cu / TiO 2 ) for nitrate-nitrogen reduction in water supported on a titania carrier was prepared in the same manner as in Example 1 except that pure anatase was calcined at a temperature of 1020 ° C.
Experimental Example One. Titania carrier And Taitani On the carrier Supported Underwater nitric acid Reduction Palladium-copper catalyst ( Pd - Cu / TiO 2 )of Anatase Content measurement
The anatase contents of the palladium-copper catalyst (Pd-Cu / TiO 2 ) for reducing nitrate nitrogen in water supported on the titania carrier and the titania carrier prepared in Examples 1 to 2 and Comparative Example 1 were measured by X- Respectively.
An XRD graph of a palladium-copper catalyst for reducing nitrate nitrogen in water carried on a titania carrier and a titania carrier was obtained under the above conditions (FIGS. 1 and 2), and the content of an anatase was determined by the following equation (1) 1.
X A is the weight percentage of anatase contained in the titania carrier,
I R is the characteristic peak intensity on the strongest rutile in the titania carrier,
I A is the characteristic peak intensity of the strongest anatase phase in the titania carrier.
Titania carrier (%)
The titania carrier of Comparative Example 1, in which the calcination temperature was as high as 1020 캜, and the palladium-copper catalyst for nitrate nitrogen reduction in water carried on the titania carrier showed very low anatase contents of 2% by weight and 1% by weight. On the other hand, the content of anatase in the nitrate-nitrogen-reducing palladium-copper catalyst supported on the titania carrier and the titania carrier of Examples 1 and 2 having the calcination temperatures of 500 ° C and 920 ° C was 75% It looked.
Therefore, it can be seen from the results of Table 1 that the content of anatase is higher in the palladium-copper catalyst for nitrate nitrogen reduction in the water supported on the titania carrier and the titania carrier as the firing temperature is lower.
Experimental Example 2. Titania On the carrier Supported Underwater nitric acid Reduction Nitrogen in water of palladium-copper catalyst Nitrogen Abatement Measure the response
The nitrate nitrogen-reducing palladium-copper catalyst supported on the titania carrier prepared in Examples 1 to 2 and Comparative Example 1 was filled in a batch reactor to measure the nitrate nitrogen reduction reaction in water.
To the 300 mL of the third distilled water mixture containing 2 mM nitrate nitrogen was added 0.15 g each of the nitrate-nitrogen-reducing palladium-copper catalyst supported on the titania carrier prepared in Examples 1 and 2 and Comparative Example 1, respectively. Hydrogen gas as a reducing agent was injected at a flow rate of 90 mL / min, and the reaction time was 3 hours. The reaction conditions were 25 ° C and normal pressure.
From the results of the above experiment, it was confirmed that the nitrate-nitrogen catalyst for reducing nitrogenous nitrogen contained in the titania carrier of Example 1, which was calcined at a temperature of 500 ° C, removed nitrogenous nitrate in water over about 40 minutes, It was confirmed that the nitrate nitrogen-reducing palladium-copper catalyst supported on the titania carrier of Example 2, which was calcined at a temperature, was completely removed from the water after about 80 minutes. On the other hand, in the case of the palladium-copper catalyst for nitrate-nitrogen reduction in the water supported on the titania carrier of Comparative Example 1 calcined at a temperature of 1020 ° C, the concentration of nitrate nitrogen in the water did not decrease remarkably after 3 hours, (Fig. 3).
Therefore, it was found that the palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier of the present invention calcined at a temperature of 350 to 950 ° C can reduce the concentration of nitrate nitrogen in water in a short time.
Experimental Example 3. Determination of nitric acid concentration and pH of reactant in water according to carbon dioxide flow rate
The nitrate nitrogen concentration in the water and the pH change of the reactant were measured according to the carbon dioxide flow rate using the palladium-copper catalyst for nitrate nitrogen reduction in the water supported on the titania carrier prepared in Example 1 above.
Carbon dioxide, a pH buffer, was supplied at flow rates of 0, 10, 30 and 60 mL / min, and hydrogen gas at a flow rate of 90 mL / min.
In the experiment without CO2 injection, the pH of the reactant tended to increase with the removal of nitrate nitrogen in the water. As a result, the concentration of nitrate nitrogen in the water decreased with time, The pH of the solution was maintained at a stable value of about 6. In particular, it was confirmed that the experiment results of injecting carbon dioxide at a flow rate of 30 mL / min showed the best reduction of the concentration of nitrate nitrogen in the water (FIG. 4).
Therefore, in order to reduce the concentration of nitrogenous nitrate in the water and stabilize the pH of the reactant, it is more preferable to inject carbon dioxide together with the hydrogen gas as the reducing agent, and it is preferable that the flow rate is 30 mL / min.
The nitrate conversion and the nitrogen selectivity in water of the palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier of Examples 1 to 2 and Comparative Example 1 under the supply of hydrogen of 90 mL / min and carbon dioxide of 30 mL / The results are shown in Table 2 below.
Conversion Rate (%)
The palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier of Example 1 calcined at a temperature of 500 ° C had a nitrogen selectivity of 56.3% and a conversion rate of nitrogenous nitrate in water was as high as 95%. In addition, the palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier of Example 2 calcined at a temperature of 920 ° C showed a nitrogen selectivity of 41.2%, but the conversion rate of nitrate nitrogen in water was as low as 27% Respectively. On the other hand, the nitrogen selectivity of the palladium-copper catalyst for nitrate nitrogen reduction in the water supported on the titania carrier of Comparative Example 1 calcined at a temperature of 1020 ° C was as high as 84.7%, but the conversion rate of nitrate nitrogen in water was 11% , Respectively.
Thus, it was found that the palladium-copper catalyst for nitrate-nitrogen reduction in water supported on the titania carrier of Example 1 calcined at a temperature of 500 ° C showed the highest activity, and the lower the calcination temperature, the better the activity .
Claims (9)
(2) immersing the calcined titania carrier in an aqueous acid solution, and then introducing a palladium precursor and a copper precursor;
(3) adding an alkali aqueous solution to the titania carrier into which the palladium precursor and the copper precursor have been added to adjust the pH to 9 or more, and then heating;
(4) washing, drying and firing a titania carrier to which a palladium precursor and a copper precursor having a pH of 9 or more are added; And
(5) reducing the titania carrier into which the calcined palladium precursor and the copper precursor have been introduced, the method comprising the step of reducing the nitrate-containing catalyst supported on the titania carrier.
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