CN109317200B - Pd-Cu bimetallic catalyst applied to sewage denitrification and preparation method thereof - Google Patents
Pd-Cu bimetallic catalyst applied to sewage denitrification and preparation method thereof Download PDFInfo
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Abstract
A Pd-Cu bimetallic catalyst applied to sewage denitrification and a preparation method thereof belong to the field of sewage treatment. The method is characterized in that: the catalyst comprises an active component and a carrier, wherein the content of the active component in the catalyst by mass percent comprises: pd1% -1.5%, Cu 1% -1.5%; the carrier is macroporous polystyrene resin, and the specific surface of the macroporous polystyrene resin is 400m2/g~600m2Per g, pore volume of 0.4 m3/g~2.0m3A pore diameter of 3.0 nm to 5.0 nm. The carrier is pretreated in multiple steps, so that the binding force of the carrier, EDTA (ethylene diamine tetraacetic acid) and active components is increased, a large amount of metal ions are bound and uniformly dispersed on the inner surface of micropores of the exchange resin, and the metal ions are reduced to form metal clusters which are deeply sunk in a three-dimensional network structure of the resin, so that the activity is uniformly dispersed on the resin and is firmly bound.
Description
Technical Field
A Pd-Cu bimetallic catalyst applied to sewage denitrification and a preparation method thereof belong to the field of sewage treatment.
Background
The nitrogen element in the water body is mainly ionic nitrogen, wherein nitrate nitrogen is taken as the main component, and ammonia nitrogen and nitrite nitrogen are taken as the secondary components, the salts can cause pollution to the environment, the ammonia nitrogen can cause eutrophication of the water body, and the nitrite nitrogen can cause harm to the health of human bodies, animals and plants. The nitrate source in nature mainly comprises two aspects, namely wide waste water source and complex components, such as chemical fertilizer manufacturing, steel production, gunpowder manufacturing, feed production, meat processing, electronic components, flue gas denitration absorption liquid and the like, and part of nitrate can be reduced into nitrite after being taken into human bodies and animal bodies. Nitrite can oxidize hemoglobin in blood into ferrohemoglobin which does not have the capability of combining oxygen, and when the content of the ferrohemoglobin in the blood is increased, the capability of oxygen delivery of the blood is reduced, and serious patients cause human tissue purple plague, which is clinically called as methemoglobinemia. In addition, nitrite ions can cause baby blueness after entering a human body, and particularly, baby reaction within 4 months is sensitive, and the nitrite ions are easy to cause great harm to pregnant women, old and weak sensitive people. Nitrite can react with paraammonium in stomach to form strong carcinogen nitrosamine, and British, Chile and Columbia have reports of correlation between nitrate and high incidence rate of gastric cancer; a relationship between high nitrate levels in drinking water and the incidence of hypertension is found in the united states. According to rough statistics, about 3000 thousands of people in China drink high-nitrate saline water, and nitrate pollution becomes one of the main environmental factors for cancer occurrence in China. Therefore, the national relevant standards specify the concentration of nitrate in water, wherein the drinking water health standard specifies the maximum allowable concentration of nitrate to be 20mg/L, and the surface water quality standard GB3838-2002 specifies the maximum allowable concentration of nitrate in the surface water source of the centralized domestic drinking water to be 10 mg/L. In conclusion, how to effectively treat the high-concentration nitrate wastewater and improve the quality of the effluent water becomes one of the hot spots and difficulties in the field of water pollution control, and has been widely regarded by many researchers.
The method for treating the nitrate wastewater mainly comprises a physical-chemical method, a biological denitrification method and a catalytic reduction method. The method for removing nitrate in wastewater by a physical and chemical method mainly comprises an ion exchange method, reverse osmosis, electrodialysis, a steaming house method and the like. These processes are too costly to operate, they concentrate the nitrates in the medium or waste liquid, and do not actually remove them completely, but rather transfer or concentration of the nitrate contaminants takes place.
Biological denitrification is divided into two processes of nitrification and denitrification, and NH is generated by nitrification reaction4 +The nitrate is converted into nitrate by denitrifying bacteria, nitrate is used as an electron acceptor, and nitrate is reduced into nitrogen under the condition of oxygen deficiency or oxygen-free condition and released into the atmosphere。
The chemical catalytic reduction of nitrate refers to the reduction of nitrate into nitrogen by using hydrogen, formic acid and the like as reducing agents, adding a proper catalyst in the reaction and utilizing the catalytic action of the catalyst. The process has the advantages that the reaction activity is high and is 30 times higher than that of biological denitrification, and the key point of the process is to prepare the catalyst with good performance, so that the catalyst has high reaction activity and high selectivity.
There is a prior art activated carbon cloth supported bimetallic Pd-Cu nanocatalyst comprising about 1 wt% Pd and about 0.35-0.45 wt% Cu and having a surface Cu/Pd metal ratio of about 8-10m2/m 2. The nanocatalyst is capable of removing nitrate and/or nitrite from wastewater with high selectivity to nitrogen. The preparation method of the catalyst is sputtering deposition, continuous hydrogen flow and nitrogen flow are required to be kept for high-temperature roasting reduction in the preparation process, the production process is difficult to control, and the prepared catalyst has low dispersity, so that the activity is poor and is only 77.6% at most.
Literature<<Experimental study on nitrate removal by chemical denitrification>>In the batch type complete mixing reactor, the authors carried out experimental research on catalytic reduction of nitrate by using Pd-Cu/gamma-Al 2O3 as a catalyst, and the results show that under the action of a supported metal catalyst, nitrate can be effectively reduced to generate N2The total nitrogen removal rate reaches more than 80%. In the preparation process of the catalyst, the periodic stirring and room temperature drying time are longer. In addition, for the supported catalyst, the roasting at 350 ℃ is difficult to ensure the firm combination of the active component and the carrier, and the service life of the catalyst is easy to shorten.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides N2A Pd-Cu bimetallic catalyst with high selectivity applied to sewage denitrification and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the Pd-Cu bimetallic catalyst applied to sewage denitrification is characterized in that: comprises active components and a carrier, wherein the active components are used in percentage by massThe content in the catalyst comprises: pd1% -1.5%, Cu 1% -1.5%; the carrier is macroporous polystyrene resin, and the specific surface of the macroporous polystyrene resin is 400m2/g~600m2Per g, pore volume of 0.4 m3/g~2.0m3A pore diameter of 3.0 nm to 5.0 nm.
The invention aims to provide a Pd-Cu bimetallic catalyst applied to sewage denitrification, which is applied to sewage denitrification reaction, and N2The selectivity is high, the content of total nitrogen in the sewage can be effectively reduced, the ammonia nitrogen in the sewage is ensured not to exceed the standard, and the national and local discharge indexes of the total nitrogen and the ammonia nitrogen in the sewage can be met.
Preferably, the content of Pd in the catalyst is 1.1-1.3% by mass percent.
Preferably, the content of Cu in the catalyst is 1.2-1.3% by mass percent. The preferred active component content achieves the best nitrate chemical reduction catalytic effect of the catalyst.
Preferably, the specific surface area of the macroporous polystyrene resin is 500m2/g～540m2G, pore volume of 1.4 m3/g～1.7m3(ii) in terms of/g. The physical property of the optimized macroporous polystyrene resin can load the active component with the optimal density, so that the catalytic effect is optimal, and the catalyst has longer stabilization time.
The preparation method of the Pd-Cu bimetallic catalyst applied to sewage denitrification is characterized by comprising the following preparation steps:
1) the catalyst precursor A is prepared by the activation pretreatment of a macroporous polystyrene resin carrier, and specifically comprises the following steps:
1.1 adding macroporous polystyrene resin particles into a saturated calcium hydroxide solution, stirring at room temperature for 60-120 min, and washing the resin particles to be neutral;
1.2 adding the resin particles washed to be neutral in the step 1.1 into a methanol solution for stirring treatment at room temperature, wherein the stirring time is 60-120 min, and then washing;
1.3, soaking the resin washed in the step 1.2 in an EDTA saturated solution for 6-24 h, separating the resin, and drying to obtain the activated pretreated carrier.
2) Preparation of catalyst precursor: placing the catalyst precursor A in the PdCl subjected to ultrasonic treatment2Dipping in the dipping solution for 4-8 h, separating a complex after the reaction is finished, and drying to obtain a catalyst precursor B; soaking the catalyst precursor B in a mixed solution of sodium hydroxide and hydrazine hydrate, reacting for 2-4 h, and separating a complex to obtain a catalyst precursor C;
3) preparing a composite catalyst: soaking the catalyst precursor C in an EDTA saturated solution for 6-24 h, separating, and drying to obtain a catalyst precursor D; placing the catalyst precursor D in copper sulfate dipping solution after ultrasonic treatment, dipping for 4-8 h, separating a complex after the reaction is finished, and drying to obtain a catalyst precursor E; and (3) soaking the catalyst precursor E in a mixed solution of sodium hydroxide and hydrazine hydrate, reacting for 2-4 h, separating a complex, and drying to obtain the catalyst.
The invention also provides a preparation method of the Pd-Cu bimetallic catalyst applied to sewage denitrification, and the preparation process is simple, scientific and reasonable. The carrier is pretreated in multiple steps, so that the binding force of the carrier, EDTA (ethylene diamine tetraacetic acid) and active components is increased, a large amount of metal ions are bound and uniformly dispersed on the inner surface of micropores of the exchange resin, and the metal ions are reduced to form metal clusters which are deeply sunk in a three-dimensional network structure of the resin, so that the activity is uniformly dispersed on the resin and is firmly bound. The catalyst is applied to the process of catalytic reduction of nitrate nitrogen in sewage, the removal rate of the nitrate nitrogen is improved, and the selectivity of nitrogen is better.
Preferably, the dipping time of the resin washed in the step 1.3 in the EDTA saturated solution is 9-13 h.
Preferably, the mass ratio of the saturated calcium hydroxide solution to the macroporous polystyrene resin in step 1.1 is 100: 16-24, and the stirring time is 80-100 min. The preferable mass ratio can better pre-treat the carrier, so that the carrier and the active component are combined more firmly and stably.
Preferably, the mass ratio of the methanol solution to the macroporous polystyrene resin in the step 1.2 is 100: 16-24, and the stirring time is 80-100 min. The preferable mass ratio can better pre-treat the carrier, so that the carrier and the active component are combined more firmly and stably.
Preferably, the PdCl in step 2)2The preparation method of the impregnation liquid comprises the following steps: taking 1-4 parts by weight of PdCl2Dissolving the mixture into 100 parts by weight of mixed aqueous solution of ethanol and citric acid, wherein the mass concentration of the ethanol in the mixed aqueous solution is 20-30%, and the mass concentration of the citric acid in the mixed aqueous solution is 0.5-1%; heating the mixed aqueous solution to 30-50 ℃, and then carrying out ultrasonic treatment by using an ultrasonic instrument, wherein the frequency of ultrasonic treatment is 10-20 kHz, and the time of ultrasonic treatment is 1-5 min. In the preparation process of the catalyst, a low-power ultrasonic instrument is used for treating the mixed solution of the active components at a certain temperature, and the active components have good particle dispersibility in the solution under the double-layer action of outer-layer electronic space isomerization and ultrasonic dispersion. Preferred PdCl2The preparation method of the impregnation liquid can enable the Pd to be combined on the inner surfaces of the micropores of the exchange resin more uniformly and stably.
Preferably, the mixed aqueous solution PdCl2The weight portion of (A) is 2-3. PdCl of appropriate concentration2The catalytic effect can be promoted to be stronger.
Preferably, the mass concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the hydrazine hydrate in the step 2) is 1-4%, and the mass concentration of the hydrazine hydrate is 2-3%. The preferable concentration can better promote the combination of the rest carriers of the active components, the combination is firmer, and the catalytic effect is stable for a longer period.
Preferably, the preparation method of the copper sulfate impregnation liquid in the step 3) comprises the steps of dissolving 2-8 parts by weight of copper sulfate in 100 parts by weight of a mixed aqueous solution of ethanol and citric acid, wherein the mass concentration of ethanol in the mixed aqueous solution is 20-30%, and the mass concentration of citric acid in the mixed aqueous solution is 0.5-1%; heating the mixed aqueous solution to 30-50 ℃, and then carrying out ultrasonic treatment by using an ultrasonic instrument, wherein the frequency of ultrasonic treatment is 10-20 kHz, and the time of ultrasonic treatment is 1-5 min. In the preparation process of the catalyst, a low-power ultrasonic instrument is used for treating the mixed solution of the active components at a certain temperature, and the active components have good particle dispersibility in the solution under the double-layer action of outer-layer electronic space isomerization and ultrasonic dispersion. The preferable preparation method of the copper sulfate impregnation liquid can enable Cu to be more uniformly and stably combined on the inner surfaces of the micropores of the exchange resin.
Preferably, the weight part of the copper sulfate added into the mixed water solution is 3-5 parts. The preferable weight part enables the arrangement of Cu and Pd to be more reasonable and the catalytic effect to be better.
Compared with the prior art, the Pd-Cu bimetallic catalyst applied to sewage denitrification and the preparation method thereof have the beneficial effects that:
1. the active components are highly effective and stable. The carrier is pretreated in multiple steps, so that the binding force of the carrier, EDTA (ethylene diamine tetraacetic acid) and active components is increased, a large amount of metal ions are bound and uniformly dispersed on the inner surface of micropores of the exchange resin, and the metal ions are reduced to form metal clusters which are deeply sunk in a three-dimensional network structure of the resin, so that the activity is uniformly dispersed on the resin and is firmly bound;
2. the removal rate of nitrate nitrogen and the selectivity of N2 are high. The preparation process of the catalyst uses a low-power ultrasonic instrument to treat the mixed solution of the active components, and under the action of ultrasonic cavitation, the active components have good particle dispersibility in the solution. The catalyst is applied to the process of catalytic reduction of nitrate nitrogen in sewage, the removal rate of the nitrate nitrogen reaches over 88 percent, and the selectivity of nitrogen reaches over 90 percent.
Detailed Description
The present invention is further illustrated by the following specific examples, of which example 1 is the most preferred.
Example 1
Step one, putting 100ml of saturated calcium hydroxide solution and 20g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 60min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 60min, and washing with deionized water for 3 times for later use. Preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 6 hours, taking out the resin carrier, and drying in vacuum at room temperature;
step two, taking 2.5g of PdCl2Dissolving in 100g of ethanol,The mixed solution of water and citric acid, wherein the concentration of ethanol in the mixed solution is 25%, the concentration of citric acid in the mixed solution is 0.8%, and the balance is water. Heating the mixed solution to 40 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 15kHz, and the ultrasonic reaction time is 1 min. And (3) soaking the pretreated resin carrier in the mixed solution after ultrasonic treatment for 4 hours, taking out, and drying in a vacuum drying oven. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 1.5 percent, the concentration of the hydrazine hydrate is 2 percent, separating the catalyst precursor after soaking for 2 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
and step three, soaking the catalyst precursor in an EDTA saturated solution for 6 hours, separating, drying at room temperature in vacuum, placing in a mixed solution of 100g of blue vitriol solution, heating the mixed solution to 40 ℃, and performing ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 15kHz, and the ultrasonic reaction time is 1min, wherein the blue vitriol concentration is 4%, the ethanol concentration is 25%, and the citric acid concentration is 0.7%. Taking out after dipping for 4h, and placing in a vacuum drying oven for drying. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 3 percent, the concentration of the hydrazine hydrate is 2.5 percent, separating the catalyst precursor after soaking for 2 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
the content of each active component of the prepared catalyst in the catalyst by mass percent is as follows: pd1.2%, Cu 1.25%; the carrier is macroporous polystyrene resin, and the specific surface area of the macroporous polystyrene resin is 510 m2/g～540m2G, pore volume of 1.4 m3/g～1.7m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the prepared catalyst is applied to the effluent of a certain acrylonitrile catalytic oxidation device, wherein the nitrate nitrogen of the water is 496mg/L, the pH is =5.3, and the main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 29.76mg/L of nitrate nitrogen, the ammonia nitrogen is 9mg/L, the removal rate of the nitrate nitrogen in the reaction is 94 percent, and the selectivity of the nitrogen is 95 percent.
Example 2
Step one, putting 100ml of saturated calcium hydroxide solution and 18g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 80min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 80min, and washing with deionized water for 3 times for later use. Preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 9 hours, taking out the resin carrier, and drying in vacuum at room temperature;
step two, taking 2gPdCl2Dissolving in 100g of mixed solution of ethanol, water and citric acid, wherein the concentration of ethanol in the mixed solution is 23%, the concentration of citric acid in the mixed solution is 0.6%, and the balance is water. After the temperature of the mixed solution is raised to 35 ℃, a low-power ultrasonic instrument is adopted for carrying out ultrasonic treatment, the frequency of ultrasonic reaction is 13kHz, and the time of ultrasonic reaction is 2 min. And (3) soaking the pretreated resin carrier in the mixed solution for 5 hours, then taking out, and drying in a vacuum drying oven. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 2 percent, the concentration of the hydrazine hydrate is 2.8 percent, separating the catalyst precursor after soaking for 2.3h, and drying the catalyst precursor in vacuum at room temperature for later use;
and step three, soaking the catalyst precursor in an EDTA saturated solution for 9 hours, separating, drying at room temperature in vacuum, placing in a mixed solution of 100g of blue vitriol solution, heating the mixed solution to 35 ℃, and carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 13kHz, and the ultrasonic reaction time is 2min, wherein the blue vitriol concentration is 3%, the ethanol concentration is 23%, and the citric acid concentration is 0.6%. And taking out after soaking for 5h, and placing in a vacuum drying oven for drying. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 2 percent, the concentration of the hydrazine hydrate is 2.8 percent, separating the catalyst precursor after soaking for 2.3h, and drying the catalyst precursor in vacuum at room temperature for later use;
the content of each active component of the prepared catalyst in the catalyst by mass percent is as follows: pd1.1%, Cu 1.25%; the carrier is macroporous polystyrene resin, 500m2/g～560m2Per g, pore volume of 0.9m3/g～1.6m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the prepared catalyst was applied to the effluent of a catalyst plant unit with 619mg/L of aqueous nitrate nitrogen and pH = 7.2. The main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 49.5mg/L of nitrate nitrogen, the ammonia nitrogen is 15mg/L, the removal rate of the reaction nitrate nitrogen is 92%, and the selectivity of nitrogen is 93.3%.
Example 3
Step one, putting 100ml of saturated calcium hydroxide solution and 22g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 100min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 100min, and washing with deionized water for 3 times for later use. Preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 13 hours, taking out the resin carrier, and drying in vacuum at room temperature;
step two, taking 3gPdCl2Dissolving in 100g of mixed solution of ethanol, water and citric acid, wherein the concentration of ethanol in the mixed solution is 27%, the concentration of citric acid in the mixed solution is 0.8%, and the balance is water. Heating the mixed solution to 45 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 18kHz, and the ultrasonic reaction time is 3 min. And (3) soaking the pretreated resin carrier in the mixed solution for 5 hours, then taking out, and drying in a vacuum drying oven. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 3.5 percent, the concentration of the hydrazine hydrate is 2.3 percent, separating the catalyst precursor after soaking for 2.7 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
and step three, soaking the catalyst precursor in an EDTA saturated solution for 12 hours, separating, drying at room temperature in vacuum, placing in a mixed solution of 100g of a blue vitriol solution, heating the mixed solution to 45 ℃, and carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 18kHz, and the ultrasonic reaction time is 4 min. Wherein the concentration of the blue vitriod is 5 percent, the concentration of the ethanol is 27 percent and the concentration of the citric acid is 0.8 percent, the blue vitriod is taken out after being soaked for 5 hours and then is dried in a vacuum drying oven. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 3.5 percent, the concentration of the hydrazine hydrate is 2.3 percent, separating the catalyst precursor after soaking for 2.7 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
the content of each active component of the prepared catalyst in the catalyst by mass percent is as follows: pd1.3%, Cu 1.25%; the carrier is macroporous polystyrene resin, and the specific surface area of the macroporous polystyrene resin is 490 m2/g～550m2Per g, pore volume of 1.0m3/g～1.6m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the prepared catalyst was applied to the effluent of a catalyst plant unit with 601mg/L of aqueous nitrate nitrogen and pH = 7.2. The main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 46.2mg/L of nitrate nitrogen, the ammonia nitrogen is 12mg/L, the removal rate of the nitrate nitrogen in the reaction is 92.3 percent, and the selectivity of the nitrogen is 92.9 percent.
Example 4
Step one, putting 100ml of saturated calcium hydroxide solution and 16g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 120min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 120min, and washing with deionized water for 3 times for later use. Preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 24 hours, taking out the resin carrier, and drying in vacuum at room temperature;
step two, taking 1gPdCl2Dissolving in 100g of mixed solution of ethanol, water and citric acid, wherein the concentration of ethanol in the mixed solution is 30%, the concentration of citric acid in the mixed solution is 1%, and the balance is water. Heating the mixed solution to 50 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 10kHz, and the ultrasonic reaction time is 5 min. And (3) soaking the pretreated resin carrier in the mixed solution for 7 hours, then taking out, and drying in a vacuum drying oven. Impregnating the dried catalyst precursorSoaking in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 4 percent, the concentration of the hydrazine hydrate is 2 percent, separating the catalyst precursor after 3 hours of soaking, and drying in vacuum at room temperature for later use;
and step three, soaking the catalyst precursor in an EDTA saturated solution for 20 hours, separating, vacuum-drying at room temperature, placing in a mixed solution of 100g of a blue vitriol solution, heating the mixed solution to 50 ℃, performing ultrasonic treatment by using a low-power ultrasonic instrument, wherein the ultrasonic reaction frequency is 10kHz, the ultrasonic reaction time is 5min, the blue vitriol concentration is 2%, the ethanol concentration is 30%, the citric acid concentration is 1%, soaking for 7 hours, taking out, and placing in a vacuum drying oven for drying. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 4 percent, the concentration of the hydrazine hydrate is 2 percent, separating the catalyst precursor after 3 hours of soaking, and drying the catalyst precursor in vacuum at room temperature for later use;
the content of each active component of the prepared catalyst in the catalyst by mass percent is as follows: pd1%, Cu 1%; the carrier is macroporous polystyrene resin, and the specific surface area of the macroporous polystyrene resin is 400m2/g~560m2Per g, pore volume of 0.4 m3/g~1.8m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the prepared catalyst was applied to the effluent of a catalyst plant unit with 620mg/L of aqueous nitrate nitrogen and pH = 7.2. The main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 64.48mg/L of nitrate nitrogen, the ammonia nitrogen is 14mg/L, the removal rate of the nitrate nitrogen in the reaction is 89.6%, and the selectivity of the nitrogen is 92.1%.
Example 5
Step one, putting 100ml of saturated calcium hydroxide solution and 24g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 120min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 120min, and washing with deionized water for 3 times for later use. Preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 24 hours, taking out the resin carrier, and drying in vacuum at room temperature;
step two, taking 4gPdCl2Dissolving in 100g of mixed solution of ethanol, water and citric acid, wherein the concentration of ethanol in the mixed solution is 20%, the concentration of citric acid in the mixed solution is 0.5%, and the balance is water. After the mixed solution is heated to 30 ℃, a low-power ultrasonic instrument is adopted for carrying out ultrasonic reaction, the frequency of the ultrasonic reaction is 20kHz, and the time of the ultrasonic reaction is 1 min. And (3) soaking the pretreated resin carrier in the mixed solution for 8 hours, then taking out, and drying in a vacuum drying oven. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 1 percent, the concentration of the hydrazine hydrate is 1 percent, separating the catalyst precursor after soaking for 4 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
soaking the catalyst precursor in an EDTA saturated solution for 24 hours, separating, vacuum-drying at room temperature, placing in a mixed solution of 100g of a copper sulfate pentahydrate solution, wherein the concentration of the copper sulfate pentahydrate is 8%, the concentration of ethanol is 20%, and the concentration of citric acid is 0.5%, heating the mixed solution to 30 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the frequency of the ultrasonic reaction is 20kHz, and the time of the ultrasonic reaction is 1 min; and taking out after dipping for 8h, and placing in a vacuum drying oven for drying. Soaking the dried catalyst precursor in a mixed solution of sodium hydroxide and hydrazine hydrate, wherein the concentration of the sodium hydroxide in the solution is 1 percent, the concentration of the hydrazine hydrate is 1 percent, separating the catalyst precursor after soaking for 4 hours, and drying the catalyst precursor in vacuum at room temperature for later use;
the content of each active component of the prepared catalyst in the catalyst by mass percent is as follows: pd1.5%, Cu 1.5%; the carrier is macroporous polystyrene resin, and the specific surface of the macroporous polystyrene resin is 450 m2/g~600m2Per g, pore volume of 0.4 m3/g~2.0m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the catalyst obtained was applied to the effluent of a catalyst plant unit with a nitrate nitrogen of 529mg/L and a pH = 7.2. The main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is nitre61.3mg/L of acid salt nitrogen, 11mg/L of ammonia nitrogen, 88.4 percent of removal rate of reaction nitrate nitrogen and 90.2 percent of nitrogen selectivity.
Comparative example 1:
step one, preparing an EDTA saturated solution, soaking the macroporous polystyrene resin in the EDTA saturated solution for 6 hours, taking out the resin carrier, and drying in vacuum at room temperature.
Step two and step three are the same as step two and step three of example 1.
The prepared catalyst is applied to the effluent of a certain acrylonitrile catalytic oxidation device, the nitrogen content of the water nitrate is 500mg/L, the pH =5.3, and the main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 211mg/L of nitrate nitrogen, the ammonia nitrogen is 92mg/L, the removal rate of the reaction nitrate nitrogen is 57.8 percent, and the selectivity of the nitrogen is 68.2 percent.
Comparative example 2
Step one, putting 100ml of saturated sodium hydroxide solution and 20g of macroporous polystyrene resin particles into a flask with a stirrer, stirring at room temperature for 60min, and washing with deionized water until the washing water is neutral; adding the resin particles into 100ml of methanol solution, stirring at room temperature, stirring for 60min, and washing with deionized water for 3 times for later use. And (3) preparing an EDTA saturated solution, soaking the pretreated resin in the EDTA saturated solution for 6 hours, taking out the resin carrier, and drying in vacuum at room temperature.
Step two and step three are the same as step two and step three of example 1.
The prepared catalyst is applied to the effluent of a certain acrylonitrile catalytic oxidation device, the nitrogen content of the water nitrate is 500mg/L, the pH =5.3, and the main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 105mg/L of nitrate nitrogen, the ammonia nitrogen is 78mg/L, the removal rate of the reaction nitrate nitrogen is 79%, and the selectivity of the nitrogen is 80%.
Comparative example 3:
taking gamma-Al2 O3200ml is taken as a carrier, soaked for 30min by using EDTA with the same volume, dried at 100 ℃ in vacuum, taken out and added with 1 percent palladium chloride mixed solution (the solvent is the mixed solution of ethanol, water and citric acid, the concentration of the ethanol is 23 percent, the concentration of the citric acid is 0.5 percent, and the balance is water) to be soaked with the same volume. Heating the mixed solution to 40 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the frequency of the ultrasonic reaction is 10khz, and the ultrasonic reaction time is 1 min. After the impregnation is finished, the mixture is dried in a vacuum drying oven at 100 ℃ and is placed in a muffle furnace to be roasted for 2 hours at 450 ℃. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried. And then soaking the catalyst precursor in EDTA with the same volume for 30min, performing vacuum drying at 100 ℃, taking out, adding 1% copper chloride solution for soaking with the same volume for 90min, drying in a vacuum drying oven at 100 ℃ after soaking, and roasting in a muffle furnace at 450 ℃ for 2 h. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried.
The prepared catalyst is applied to the effluent of a certain acrylonitrile catalytic oxidation device, the nitrogen content of the water nitrate is 500mg/L, the pH =5.3, and the main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 121mg/L of nitrate nitrogen, the ammonia nitrogen is 93mg/L, the removal rate of the nitrate nitrogen in the reaction is 76%, and the selectivity of the nitrogen is 75.4%.
Comparative example 4
Taking gamma-Al2 O3200ml is taken as a carrier, the carrier is put into a saturated calcium hydroxide solution of 1000ml, the carrier is soaked for 4 hours, then the carrier is washed by deionized water until the washing water is neutral, then the carrier is soaked for 60 minutes by a methanol solution at room temperature, washed by deionized water for 3 times, soaked for 30 minutes by EDTA with the same volume, dried in vacuum at 100 ℃, taken out and added with a 1% palladium chloride mixed solution (the solvent is a mixed solution of ethanol, water and citric acid, the concentration of the ethanol is 23%, the concentration of the citric acid is 0.5%, and the balance is water) for isovolumetric impregnation. Heating the mixed solution to 40 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the frequency of the ultrasonic reaction is 10khz, and the ultrasonic reaction time is 1 min. Drying at 100 deg.C in vacuum drying oven after soaking, and standingRoasting the mixture for 2 hours at 450 ℃ in a muffle furnace. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried. And then soaking the catalyst precursor in EDTA with the same volume for 30min, performing vacuum drying at 100 ℃, taking out, adding 1% copper chloride solution for soaking with the same volume for 90min, drying in a vacuum drying oven at 100 ℃ after soaking, and roasting in a muffle furnace at 450 ℃ for 2 h. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried.
In the preparation process, the surface of the obtained catalyst is covered by calcium, and the catalyst cannot be applied to a nitrate nitrogen reduction test.
Comparative example 5
Soaking 200ml of activated carbon serving as a carrier in EDTA (ethylene diamine tetraacetic acid) with the same volume for 30min, then drying the carrier in vacuum at 100 ℃, taking the carrier out, and then adding a 1% palladium chloride mixed solution (the solvent is a mixed solution of ethanol, water and citric acid, the concentration of the ethanol is 23%, the concentration of the citric acid is 0.5%, and the balance is water) to perform isovolume impregnation. Heating the mixed solution to 40 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the frequency of the ultrasonic reaction is 10khz, and the ultrasonic reaction time is 1 min. After the impregnation is finished, the mixture is dried in a vacuum drying oven at 100 ℃ and is placed in a muffle furnace to be roasted for 2 hours at 450 ℃. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried. And then soaking the catalyst precursor in EDTA with the same volume for 30min, performing vacuum drying at 100 ℃, taking out, adding 1% copper chloride solution for soaking with the same volume for 90min, drying in a vacuum drying oven at 100 ℃ after soaking, and roasting in a muffle furnace at 450 ℃ for 2 h. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried.
The prepared catalyst is applied to the effluent of a certain acrylonitrile catalytic oxidation device, the nitrogen content of the water nitrate is 500mg/L, the pH =5.3, and the main process operating conditions are as follows: h2The flow rate is 50ml/min, the pH value of inlet water is adjusted to 5.0, the volume of the reactor is 200ml, the adding amount of the catalyst is 0.15g, and the reaction time is 90 min. After treatment, the effluent is 198mg/L of nitrate nitrogen, the ammonia nitrogen is 93mg/L, the removal rate of the nitrate nitrogen in the reaction is 60 percent, and the selectivity of the nitrogen is 69.2 percent.
Comparative example 6
Taking 200ml of activated carbon as a carrier, putting 1000ml of the activated carbon into a saturated calcium hydroxide solution, soaking for 4h, washing with deionized water until washing water is neutral, soaking for 60min at room temperature with a methanol solution, washing for 3 times with deionized water, soaking for 30min with equivalent volume of EDTA, drying at 100 ℃ in vacuum, taking out, and adding a 1% palladium chloride mixed solution (the solvent is a mixed solution of ethanol, water and citric acid, the concentration of the ethanol is 23%, the concentration of the citric acid is 0.5%, and the balance is water) to perform equivalent volume impregnation. Heating the mixed solution to 40 ℃, and then carrying out ultrasonic treatment by using a low-power ultrasonic instrument, wherein the frequency of the ultrasonic reaction is 10khz, and the ultrasonic reaction time is 1 min. After the impregnation is finished, the mixture is dried in a vacuum drying oven at 100 ℃ and is placed in a muffle furnace to be roasted for 2 hours at 450 ℃. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried. And then soaking the catalyst precursor in EDTA with the same volume for 30min, performing vacuum drying at 100 ℃, taking out, adding 1% copper chloride solution for soaking with the same volume for 90min, drying in a vacuum drying oven at 100 ℃ after soaking, and roasting in a muffle furnace at 450 ℃ for 2 h. After the baking is finished, the reaction product is cooled to room temperature, reduced by hydrazine hydrate, washed by deionized water and dried.
In the preparation process, the surface of the obtained catalyst is covered by calcium, and the catalyst cannot be applied to a nitrate nitrogen reduction test.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a Pd-Cu bimetallic catalyst applied to sewage denitrification is characterized by comprising the following steps: the Pd-Cu bimetallic catalyst applied to sewage denitrification comprises an active component and a carrier, wherein the active component comprises the following components in percentage by mass:pd1% -1.5%, Cu 1% -1.5%; the carrier is macroporous polystyrene resin, and the specific surface of the macroporous polystyrene resin is 400m2/g~600m2Per g, pore volume of 0.4 m3/g~2.0m3(ii)/g, the pore diameter is 3.0 nm to 5.0 nm;
the preparation method of the Pd-Cu bimetallic catalyst applied to sewage denitrification comprises the following preparation steps:
1) the catalyst precursor A is prepared by the activation pretreatment of a macroporous polystyrene resin carrier, and specifically comprises the following steps:
1.1 adding macroporous polystyrene resin particles into a saturated calcium hydroxide solution, stirring at room temperature for 60-120 min, and washing the resin particles to be neutral;
1.2 adding the resin particles washed to be neutral in the step 1.1 into a methanol solution for stirring treatment at room temperature, wherein the stirring time is 60-120 min, and then washing;
1.3, soaking the resin washed in the step 1.2 in an EDTA saturated solution for 6-24 hours, separating the resin, and drying to obtain an activated pretreated carrier;
2) preparation of catalyst precursor: placing the catalyst precursor A in the PdCl subjected to ultrasonic treatment2Dipping in the dipping solution for 4-8 h, separating a complex after the reaction is finished, and drying to obtain a catalyst precursor B; soaking the catalyst precursor B in a mixed solution of sodium hydroxide and hydrazine hydrate, reacting for 2-4 h, and separating a complex to obtain a catalyst precursor C;
3) preparing a composite catalyst: soaking the catalyst precursor C in an EDTA saturated solution for 6-24 h, separating, and drying to obtain a catalyst precursor D; placing the catalyst precursor D in copper sulfate dipping solution after ultrasonic treatment, dipping for 4-8 h, separating a complex after the reaction is finished, and drying to obtain a catalyst precursor E; and (3) soaking the catalyst precursor E in a mixed solution of sodium hydroxide and hydrazine hydrate, reacting for 2-4 h, separating a complex, and drying to obtain the catalyst.
2. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: the content of Pd in the catalyst is 1.1-1.3% by mass percent; the content of Cu in the catalyst is 1.2-1.3% by mass percent.
3. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: the specific surface of the macroporous polystyrene resin is 500m2/g～540m2G, pore volume of 1.4 m3/g～1.7m3/g。
4. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: and (3) soaking the washed resin in the EDTA saturated solution for 9-13 h.
5. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: the mass ratio of the saturated calcium hydroxide solution to the macroporous polystyrene resin in the step 1.1 is 100: 16-24, and the stirring time is 80-100 min.
6. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: the mass ratio of the methanol solution to the macroporous polystyrene resin in the step 1.2 is 100: 16-24, and the stirring time is 80-100 min.
7. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: PdCl as described in step 2)2The preparation method of the impregnation liquid comprises the following steps: taking 1-4 parts by weight of PdCl2Dissolving the mixture into 100 parts by weight of mixed aqueous solution of ethanol and citric acid, wherein the mass concentration of the ethanol in the mixed aqueous solution is 20-30%, and the mass concentration of the citric acid in the mixed aqueous solution is 0.5-1%; heating the mixed aqueous solution to 30-50 ℃, and then carrying out ultrasonic treatment by using an ultrasonic instrument, wherein the frequency of ultrasonic treatment is 10-20 kHz, and the time of ultrasonic treatment is 1-5 min.
8. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: in the step 2), the mass concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the hydrazine hydrate is 1-4%, and the mass concentration of the hydrazine hydrate is 2-3%.
9. The method for preparing Pd-Cu bimetallic catalyst for denitrification of sewage as claimed in claim 1, wherein: the preparation method of the copper sulfate impregnation liquid in the step 3) comprises the steps of dissolving 2-8 parts by weight of copper sulfate in 100 parts by weight of mixed aqueous solution of ethanol and citric acid, wherein the mass concentration of the ethanol in the mixed aqueous solution is 20-30%, and the mass concentration of the citric acid in the mixed aqueous solution is 0.5-1%; heating the mixed aqueous solution to 30-50 ℃, and then carrying out ultrasonic treatment by using an ultrasonic instrument, wherein the frequency of ultrasonic treatment is 10-20 kHz, and the time of ultrasonic treatment is 1-5 min.
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