CN114558594B - BiOX/Mn-Fe-O ammonium catalyst, preparation method and application thereof - Google Patents

BiOX/Mn-Fe-O ammonium catalyst, preparation method and application thereof Download PDF

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CN114558594B
CN114558594B CN202210224432.5A CN202210224432A CN114558594B CN 114558594 B CN114558594 B CN 114558594B CN 202210224432 A CN202210224432 A CN 202210224432A CN 114558594 B CN114558594 B CN 114558594B
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static mixer
bismuth
ammonium
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CN114558594A (en
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陈亦力
杨恒宇
刘涛
陈弘仁
孙广东
莫恒亮
刘曼曼
李锁定
丑树人
侯琴
向春
赵文芳
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Beijing Originwater Membrane Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
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    • C02F2101/166—Nitrites
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention provides a preparation method of BiOX/Mn-Fe-O ammonium catalyst, which comprises the steps of reacting permanganate solution with salt solution containing doping materials, and reacting the obtained materials with sodium hydroxide aqueous solution to obtain nascent iron manganese oxide Mn-Fe-O precursor dispersion; reacting an alcohol solution of bismuth salt with a brine solution to obtain a nascent bismuth oxyhalide precursor dispersion; mixing the nascent state ferro-manganese oxide Mn-Fe-O precursor dispersion liquid and the nascent state bismuth oxyhalide precursor dispersion liquid, and aging to obtain the BiOX/Mn-Fe-O ammonium catalyst. The BiOX/Mn-Fe-O ammonium catalyst can be applied to water treatment to stably produce nitrous nitrogen, and can be coupled with an anaerobic ammonia oxidation technology, so that the nitrous nitrogen is further converted into nitrogen, the total nitrogen in a water body is reduced, and the water quality index of effluent is improved.

Description

BiOX/Mn-Fe-O ammonium catalyst, preparation method and application thereof
Technical Field
The invention relates to a deamination catalyst, in particular to a BiOX/Mn-Fe-O ammonium catalyst and application of the catalyst in sewage with low ammonia nitrogen concentration.
Background
The denitrification treatment of municipal sewage is an important link of water treatment, the discharge standard of municipal sewage is 5-10mg/L of total nitrogen limit value in some domestic local standards at present, and the higher discharge standard brings pressure to a sewage treatment plant in the aspect of removing total nitrogen.
At present, the most widely applied denitrification method is a biological method, and the basic principle is to remove total nitrogen in sewage through ammoniation, nitrification and denitrification of microorganisms. Compared with the physical method and the chemical direction, the method has obvious advantages in the aspects of treatment efficiency and economic benefit. But the premise of the biological method is to maintain high-efficiency denitrification is to have sufficient carbon source. However, the carbon nitrogen ratio of the urban sewage in China is generally lower, and about 70% of the BOD 5/total nitrogen of the urban sewage is lower than 4. In order to realize advanced treatment of municipal sewage and reduce total nitrogen in the sewage, a sewage treatment plant needs to add carbon source medicaments for a long time by 50 percent. Meanwhile, the sewage discharge standard of each place is further improved, so that the pressure and the economic burden of the produced water quality guarantee of a sewage treatment plant are heavier in the key link of denitrification.
The catalytic oxidation deamination technology is a novel water treatment technology developed in recent years, and has the action process that ammonia nitrogen in water is adsorbed on the surface of a catalyst taking iron-manganese oxide as a main component under the aerobic condition, and is further oxidized into nitrate nitrogen and nitrite nitrogen under the action of dissolved oxygen. The oxidation process has high oxidation efficiency, convenient operation, no secondary pollution and wide application prospect. However, in the catalytic oxidative deamination process, nitrous nitrogen in the oxidation product tends to be over-oxidized to nitrous nitrogen, making the end product of the process mainly nitrous nitrogen limiting its use in the removal of total nitrogen.
On the other hand, the use of the anaerobic ammonia oxidation technology requires that the front-end technology can stably generate and accumulate the nitrous nitrogen, and the ammonia nitrogen concentration of municipal sewage is very low, usually only 40mg/L, so that the front-end technology is difficult to stably generate and accumulate the nitrous nitrogen, and the anaerobic ammonia oxidation technology cannot be popularized in municipal sewage treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel iron-manganese oxide catalyst, so that an oxidation product of the iron-manganese oxide catalyst is stably in a nitrous nitrogen stage, and a stable nitrous nitrogen source is provided for anaerobic ammonia oxidation.
The idea of the invention is to introduce bismuth oxyhalide (BiOX, X=Cl, br, I) elements with stabilizing effect on an ammonia nitrogen oxidation intermediate product into the iron manganese oxide, inhibit the excessive oxidation of Mn-Fe-O iron manganese oxide deamination catalyst to ammonia nitrogen, and avoid the excessive oxidation of the iron manganese oxide deamination catalyst to nitrate radical from ammonium ions in sewage, so that the oxidation product is stabilized in a nitrite nitrogen stage.
To this end, the present invention provides a process for the preparation of a BiOX/Mn-Fe-O ammonium catalyst, said process comprising the steps of:
(1) Preparation of permanganate solution
Configuration of MnO 4 - An aqueous solution of permanganate having a molar concentration of 0.2 to 5 mmol/L;
(2) Preparing a salt solution containing a doping material
Adding manganese salt and ferrous salt into water under the condition of pH value of 2.7-3.5 to obtain aqueous solution of manganese salt and ferrous salt, then adding ammonium salt, calcium salt, magnesium salt and H into the aqueous solution of manganese salt and ferrous salt 3 BO 3 Obtaining a salt solution containing a doping material;
the salt solution containing the doping material contains 0.5-6mmol/L Mn 2+ 0.18-2mmol/L Fe 2+ 1-6mg/L NH 4 + Ca in 0.5-15mmol/L 2+ Mg with concentration of 0.5-15mmol/L 2+ The final concentration of the element B in the solution is 0.5-10mg/L;
(3) Alcohol solution for preparing bismuth salt
Adding bismuth salt into alcohol solvent to prepare Bi 3+ Alcohol solution with the molar concentration of 0.15-5 mmol/L;
(4) Preparing brine solution
Preparing aqueous solution of halogen salt to make the final concentration of halogen ion in the solution be 0.15-10mmol/L;
(5) Preparation of nascent iron-manganese oxide Mn-Fe-O precursor dispersion
Respectively feeding a permanganate solution and the salt solution containing the doping materials into a first static mixer at a flow rate of 2.8-28L/h, and enabling the materials to contact and react in the first static mixer for 1-3min; wherein the permanganate solution and the salt solution containing the dopant material are typically fed separately into the first static mixer at equal flow rates;
then, respectively feeding the output material of the first mixer and a sodium hydroxide aqueous solution with the concentration of 0.58-12mmol/L into a second static mixer, enabling the materials to contact and react for 1-3min in the second mixer, and outputting a nascent iron-manganese oxide Mn-Fe-O precursor dispersion liquid from the second static mixer; the flow rate of the sodium hydroxide aqueous solution fed into the second static mixer is equal to the flow rate of the permanganate solution fed into the first static mixer;
(6) Preparation of nascent bismuth oxyhalide precursor Dispersion
Respectively feeding an alcohol solution of bismuth salt and a brine solution of halogen salt into a third static mixer at a flow rate of 0.25-3L/h, enabling the materials to contact and react for 3-5min in the third static mixer, and outputting a nascent bismuth oxyhalide precursor dispersion liquid from the third static mixer;
(7) Preparation of BiOX/Mn-Fe-O ammonium catalyst
And (3) respectively feeding the nascent iron manganese oxide Mn-Fe-O precursor dispersion liquid and the nascent bismuth oxyhalide precursor dispersion liquid into a fourth static mixer at a flow rate of 8.4-84L/h and a flow rate of 0.5-6L/h, fully mixing, feeding the obtained mixture into an ageing device 15, ageing for 5-10 days at 50-90 ℃, filtering and washing the aged materials, and obtaining a filter cake which is the BiOX/Mn-Fe-O ammonium catalyst.
In the present invention, the permanganate is selected from KMnO 4 、NaMnO 4 Etc.; the manganese salt is selected from MnCl 2 Or MnSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The ferrous salt is selected from FeCl 2 Or FeSO 4 The method comprises the steps of carrying out a first treatment on the surface of the Ammonium salt of NH 4 Cl or (NH) 4 ) 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The calcium salt is a soluble calcium salt, e.g. selected from CaCl 2 Or CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The magnesium salt is selected from MgCl 2 Or MgSO 4 The method comprises the steps of carrying out a first treatment on the surface of the Bismuth nitrate, bismuth chloride or bismuth sulfate is selected as the bismuth salt; the alcohol solvent is selected from ethanol, glycol or glycerol without water. The halogen salt is selected from sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, sodium iodide,Potassium iodide or ammonium iodide.
In the present invention, the first, second, third and fourth static mixers are static mixers having a pipe diameter of DN15-DN 25. Such static mixers are commercially available products.
As a preferred embodiment, in step (2), the pH is adjusted to 2.7-3.5 with hydrochloric acid or sulfuric acid.
The invention also provides an application of the BiOX/Mn-Fe-O ammonium catalyst obtained by the preparation method in water treatment.
According to the invention, by introducing the BiOX element into the iron-manganese oxide deamination catalyst, the oxidation of nitrosamine is inhibited by utilizing the stabilization effect of the BiOX element on an intermediate product in the ammonium ion oxidation process, and the conversion of nitrosamine to nitrosamine is prevented.
The BiOX/Mn-Fe-O ammonium catalyst prepared by the invention can stably produce the nitrous nitrogen and can be coupled with an anaerobic ammonia oxidation technology, so that the nitrous nitrogen is further converted into nitrogen, the total nitrogen in a water body is reduced, and the water quality index of effluent is improved.
The method has the advantages of simple operation, mild preparation conditions, high synthesis efficiency, low raw material cost and remarkable economic benefit, and the obtained catalyst has the advantages of high deamination efficiency, mild conditions, stable product and long service life.
Drawings
FIG. 1 is a flow chart of the preparation process of example 1;
FIG. 2 is an XRD pattern of the Mn-Fe-O ammonium catalyst and BiOCl/Mn-Fe-O ammonium catalyst of example 1
FIG. 3 shows the microscopic morphology comparison of the Mn-Fe-O ammonium catalyst of example 1 with that of BiOCl/Mn-Fe-O ammonium catalyst
FIG. 4 is an XRD pattern of the Mn-Fe-O ammonium catalyst and BiOBr/Mn-Fe-O ammonium catalyst of example 1
FIG. 5 shows the microscopic morphology comparison of the Mn-Fe-O ammonium catalyst of example 2 with that of the BiOBr/Mn-Fe-O ammonium catalyst
FIG. 6 is a graph showing the results of the variation in water quality of inlet and outlet water measured by the deamination performance of the BiOX/Mn-Fe-O catalyst of example 2;
FIG. 7 shows the results of the variation of the quality of the inlet water and the outlet water of the deamination performance test of the ammonium catalyst Mn-Fe-O without adding bismuth oxyhalide.
Detailed Description
The following examples serve to illustrate the technical solution of the invention without limiting it.
Example 1
By KMnO 4 Preparing MnO 4 - Solution A at a concentration of 0.65 mmol/L. By MnCl 2 And FeCl 2 Preparation of Mn 2+ At a concentration of 1mmol/L, fe 2+ Mixed solution with concentration of 0.36mmol/L, and NH is added to the mixed solution 4 Cl，CaCl 2 ，MgSO 4 And H 3 BO 3 NH is caused to 4 + The concentration is 4mg/L, ca 2+ Concentration is 1mmol/L, mg 2+ The concentration of the element B is 1mmol/L and the concentration of the element B is 3mg/L, so that a solution B is formed. To prevent Fe in solution B 2+ Hydrolysis, the pH of the solution B was adjusted to about 2.7 with hydrochloric acid.
By adopting the process flow shown in fig. 1, a first valve 1 and a second valve 2 are opened, a peristaltic pump is used for pumping the solution A and the solution B into a first static mixer 11 with the pipe diameter DN20 respectively, the flow is 8.6L/h, and the two solutions are contacted and uniformly mixed in the first static mixer.
The third valve 3 is opened and the mixed dispersion exiting from the first static mixer flows into the second static mixer having a diameter DN 20. Simultaneously, the fourth valve 4 is opened, a peristaltic pump is used for pumping sodium hydroxide solution with the concentration of 2.6mmol/L into the second static mixer 12 at the flow rate of 8.6L/h, after the sodium hydroxide solution contacts with the second static mixer for 2min, the pH value of the effluent mixed dispersion liquid is about 8, and the nascent state Mn-Fe-O iron manganese oxide precursor dispersion liquid is obtained.
Bi (NO) 3 ) 3 Dissolving in glycerol, stirring to obtain Bi 3+ Solution C at a concentration of 0.35 mmol/L. The NaCl solution with the concentration of 0.35mmol/L is prepared by deionized water and is recorded as solution D. Simultaneously opening a fifth valve 5 and a sixth valve 6, pumping the solution C and the solution D into a third static mixer 13 at a flow rate of 1.72L/h, and enabling the solution C and the solution D to be in contact with each other for 3min to obtain the nascent bismuth oxychloride precursor.
And respectively opening a seventh valve 7, an eighth valve 8 and a ninth valve 9 to enable the nascent state iron-manganese oxide dispersion liquid and the nascent state bismuth oxychloride dispersion liquid to be pumped into a fourth static mixer 14 for contact and reaction, and after flowing out, the nascent state iron-manganese oxide dispersion liquid and the nascent state bismuth oxychloride dispersion liquid enter an ageing device 15 to be aged for 7 days at the temperature of 60 ℃. Filtering and washing the aged precipitate to obtain a filter cake, namely the BiOCl/Mn-Fe-O ammonium catalyst.
The microstructure of Mn-Fe-O ammonium catalyst and BiOCl/Mn-Fe-O ammonium catalyst was characterized by X-ray powder diffractometer (XRD) and compared with standard cards, and the results are shown in FIG. 2. Diffraction peak positions are respectively delta-MnO 2 Is consistent with the standard card of BiOCl (PDF#42-1317) and with the standard card of BiOCl (PDF#06-0249).
The microstructure of the Mn-Fe-O ammonium catalyst and the BiOCl/Mn-Fe-O ammonium catalyst is shown in FIG. 3 below.
The ammonium chloride and sodium bicarbonate are used for preparing a deamination performance test solution with the nitrogen concentration of 40mg/L and the sodium bicarbonate concentration of 6mM, and the feed ratio of the BiOCl/Mn-Fe-O ammonium catalyst is 10g/L in the test process, and the stirring aeration is continuously carried out. The water quality of the test liquid in the test process of the catalyst is shown in table 1.
TABLE 1 Ammonia nitrogen and NO in Water 3 - -N and NO 2 - -N concentration
Figure SMS_1
The result shows that when the BiOCl/Mn-Fe-O ammonium catalyst is used for treating low-concentration ammonia nitrogen water, the treated product is stable nitrosamine, and the nitrosamine concentration in the product is lower than 1mg/L.
Example 2
Like example 1, KMnO was used 4 Preparing MnO 4 - Solution A at a concentration of 4.3 mmol/L. By MnCl 2 And FeCl 2 Preparation of Mn 2+ At a concentration of 4mmol/L, fe 2+ Adding NH into the mixed solution with the concentration of 0.8mmol/L 4 Cl，CaCl 2 ，MgSO 4 H and H 3 BO 3 NH is caused to 4 + The concentration is 6mg/L, ca 2+ The concentration is 1.3mmol/L, mg 2+ Concentration of B element is 2mmol/LAt 5mg/L, solution B was formed. To prevent Fe 2+ Hydrolyzing, and adjusting pH to about 3 with hydrochloric acid.
With the process shown in fig. 1, the first valve and the second valve were opened, and the solution a and the solution B were pumped into the first static mixer 11 having the pipe diameter DN25 by peristaltic pumps, respectively, at the flow rate of 16.8L/h, and after mixing for 3min in the first static mixer 11, the two solutions were flowed into the second static mixer 12.
Simultaneously, a fourth valve is opened, a peristaltic pump is used for pumping 10mmol/L sodium hydroxide solution into the second static mixer 12 at a flow rate of 16.8L/h, and after the mixed dispersion liquid flowing out of the first static mixer 11 and the sodium hydroxide solution are in contact with each other for 2min, the pH value of the mixed dispersion liquid flowing out of the second static mixer 12 is about 8, so that the nascent state Mn-Fe-O iron manganese oxide precursor dispersion liquid is obtained.
Bi (NO) 3 ) 3 Dissolving in glycol solvent, stirring to obtain Bi 3+ Solution C at a concentration of 5 mmol/L. NaBr solution with a concentration of 5mmol/L was prepared with deionized water and was designated as solution D. Simultaneously opening a fifth valve 5 and a sixth valve 6, pumping the solution C and the solution D into a third static mixer 13 at a flow rate of 2.5L/h, and enabling the solution C and the solution D to be in contact with each other for 3min to obtain the nascent bismuth oxybromide BiOBr precursor.
And respectively opening a seventh valve, an eighth valve and a ninth valve to enable the nascent state ferro-manganese oxide dispersion liquid and the nascent state bismuth oxybromide precursor to be pumped into the fourth static mixer 14 at the same time for contact mixing, and after flowing out, the nascent state ferro-manganese oxide dispersion liquid and the nascent state bismuth oxybromide precursor enter the ageing device 15 for ageing for 5 days at 80 ℃. Filtering and washing the aged precipitate to obtain a filter cake, namely the BiOBr/Mn-Fe-O ammonium catalyst.
The microstructure of Mn-Fe-O ammonium catalyst and BiOBr/Mn-Fe-O ammonium catalyst was characterized by X-ray powder diffractometer (XRD) and compared with standard card, and the results are shown in FIG. 4. The diffraction peak positions were consistent with the standard card for delta-MnO 2 (PDF#42-1317) and the standard card for BiOBr (PDF#09-0393), respectively.
An electron microscope picture of the Mn-Fe-O ammonium catalyst and the BiOBr/Mn-Fe-O ammonium catalyst is shown in the following FIG. 5.
The catalyst was tested for its effect on water quality in the deamination performance test in the same manner as in example 1, as shown in Table 2.
TABLE 2 Ammonia nitrogen and NO in Water 3 - -N and NO 2 - -N concentration
Figure SMS_2
The result also shows that when the BiOBr/Mn-Fe-O ammonium catalyst is used for treating low-concentration ammonia nitrogen water, the treated product is stable nitrosamine, and the nitrosamine concentration in the product is lower than 1mg/L.
Example 3
The BiOBr/Mn-Fe-O ammonium catalyst prepared in example 2 was used to test the deamination performance of municipal sewage from a sewage treatment plant in Beijing city. The ammonia nitrogen concentration of the municipal sewage is 40mg/L, and the pH value is 8.07. The test mode adopts a continuous flow test mode, the hydraulic retention time is 4 hours, the catalyst feeding ratio is 10g/L, and the stirring aeration is continuously carried out in the test process. The change of the effluent quality is shown in figure 6.
After the catalyst runs continuously for 30 days, ammonia nitrogen in the water quality of the effluent can be kept below 2mg/L, the nitrous nitrogen ratio in the oxidation product can be kept above 95%, and the performance is not attenuated. The BiOX/Mn-Fe-O ammonium catalyst prepared by the method has stable deamination performance, and an oxidation product can be stabilized to be nitrous nitrogen for a long time.
The deamination performance of the ammonium catalyst Mn-Fe-O without bismuth oxyhalide added was compared as shown in FIG. 7.
Wherein an ammonium catalyst Mn-Fe-O without bismuth oxyhalide addition was prepared by a preparation method similar to that of example 2: by KMnO 4 Preparing MnO 4 - Solution A at a concentration of 4.3 mmol/L. By MnCl 2 FeCl 2 Preparation of Mn 2+ Concentration is 4mmol/L, fe 2+ Mixed solution B with concentration of 0.8mmol/L and NH 4 Cl，CaCl 2 ，MgSO 4 H and H 3 BO 3 NH is caused to 4 + The concentration is 6mg/L, ca 2+ The concentration is 1.3mmol/L, mg 2+ The concentration is 2mmol/L, and the concentration of B element is highThe degree was 5mg/L, forming solution B. To prevent Fe 2+ Hydrolysis, first, the pH was adjusted to about 3 with hydrochloric acid.
Solution A and solution B were pumped into the first static mixer 11 by peristaltic pumps at a flow rate of 16.8L/h, and the two solutions were mixed in the static mixer for 3min before flowing into the second static mixer 12. Meanwhile, pumping 10mmol/L sodium hydroxide solution into a second static mixer 12 at a flow rate of 16.8L/h by a peristaltic pump, and contacting for 2min to obtain a mixed dispersion liquid with pH of about 8, thus obtaining the nascent state Mn-Fe-O iron manganese oxide precursor dispersion liquid. Aging the dispersion liquid for 5 days at 80 ℃, and filtering and washing to obtain a filter cake which is the Mn-Fe-O ammonium catalyst.
As can be seen from fig. 7, the time for which the ammonium catalyst Mn-Fe-O without bismuth oxyhalide added was able to stably produce nitrous oxide was about 15d, and then the phenomenon of producing nitrous oxide began to appear, and the ratio of nitrous oxide was increased more and more until the final total product was nitrous oxide. Therefore, after bismuth oxyhalide is compounded with an ammonium catalyst Mn-Fe-O, the obtained BiOX/Mn-Fe-O ammonium catalyst can stably produce nitrosamine, and the BiOX compounding can inhibit ammonium ions from being excessively oxidized to become nitrosamine, so that the stabilization of nitrosamine production of the ammonium catalyst is realized.
The above results show that the bismuth oxyhalide BiOX element is introduced into the ferro-manganese oxide, and the oxidation product is stabilized in the nitrosation stage by the stabilizing effect of the BiOX compound on the intermediate product in the oxidation process of ammonia nitrogen, so that further oxidation is prevented from generating nitrosation.
The invention can maintain the oxidation product in the nitrous nitrogen stage for a long time by inhibiting the excessive oxidation of the iron-manganese oxide deamination catalyst to ammonia nitrogen, and provides a stable nitrous nitrogen source for realizing the ammonium catalytic oxidation coupling anaerobic ammonia oxidation process.

Claims (8)

1. A method of preparing a bisox/Mn-Fe-O ammonium catalyst, the method comprising the steps of:
(1) Preparation of permanganate solution
Configuration of MnO 4 - An aqueous solution of permanganate having a molar concentration of 0.2 to 5 mmol/L;
(2) Preparing a salt solution containing a doping material
Adding manganese salt and ferrous salt into water under pH of 2.7-3.5 to obtain aqueous solution of manganese salt and ferrous salt, and adding ammonium salt, calcium salt, magnesium salt and H into aqueous solution of manganese salt and ferrous salt 3 BO 3 Obtaining a salt solution containing a doping material;
the salt solution containing the doping material contains 0.5-6mmol/L Mn 2+ 0.18-2mmol/L Fe 2+ 1-6mg/L NH 4 + Ca in 0.5-15mmol/L 2+ And Mg with a concentration of 0.5-15mmol/L 2+ The final concentration of the element B in the solution is 0.5-10mg/L;
(3) Alcohol solution for preparing bismuth salt
Adding bismuth salt into alcohol solvent to prepare Bi 3+ Alcohol solution with the molar concentration of 0.15-5 mmol/L;
(4) Preparing brine solution
Preparing aqueous solution of halogen salt to make the final concentration of halogen ion in the solution be 0.15-10mmol/L;
(5) Preparation of nascent iron-manganese oxide Mn-Fe-O precursor dispersion
Feeding permanganate solution and the salt solution containing the doping material into a first static mixer at a flow rate of 2.8-28L/h respectively, enabling the materials to contact and react in the first static mixer for 1-3min,
then, respectively feeding the output material of the first static mixer and sodium hydroxide aqueous solution with the concentration of 0.58-12mmol/L into a second static mixer, enabling the materials to contact and react for 1-3min in the second static mixer, and outputting nascent iron-manganese oxide Mn-Fe-O precursor dispersion liquid from the second static mixer; the flow rate of the sodium hydroxide aqueous solution fed into the second static mixer is equal to the flow rate of the permanganate solution fed into the first static mixer;
(6) Preparation of nascent bismuth oxyhalide precursor Dispersion
Respectively feeding an alcohol solution of bismuth salt and a brine solution of halogen salt into a third static mixer at a flow rate of 0.25-3L/h, enabling the materials to contact and react for 3-5min in the third static mixer, and outputting a nascent bismuth oxyhalide precursor dispersion liquid from the third static mixer;
(7) Preparation of BiOX/Mn-Fe-O ammonium catalyst
And (3) respectively feeding the nascent iron manganese oxide Mn-Fe-O precursor dispersion liquid and the nascent bismuth oxyhalide precursor dispersion liquid into a fourth static mixer at a flow rate of 8.4-84L/h and a flow rate of 0.5-6L/h, fully mixing, feeding the obtained mixture into an ageing device 15, ageing for 5-10 days at 50-90 ℃, filtering and washing the aged materials, and obtaining a filter cake which is the BiOX/Mn-Fe-O ammonium catalyst.
2. The process according to claim 1, wherein the permanganate is selected from KMnO 4 Or NaMnO 4 。
3. The process according to claim 1, wherein in step (2), the pH is adjusted to 2.7 to 3.5 with hydrochloric acid or sulfuric acid.
4. The process according to claim 1, wherein in the step (2), the manganese salt is selected from MnCl 2 Or MnSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The ferrous salt is selected from FeCl 2 Or FeSO 4 The method comprises the steps of carrying out a first treatment on the surface of the Ammonium salt of NH 4 Cl or (NH) 4 ) 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The calcium salt is selected from CaCl 2 Or CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The magnesium salt is selected from MgCl 2 Or MgSO 4 。
5. The preparation method of claim 1, wherein the bismuth salt is bismuth nitrate, bismuth chloride or bismuth sulfate; the alcohol solvent is ethanol, glycol or glycerol.
6. The method according to claim 1, wherein the halogen salt is selected from sodium chloride, potassium chloride, ammonium chloride, sodium bromide, potassium bromide, ammonium bromide, sodium iodide, potassium iodide or ammonium iodide.
7. The method of claim 1, wherein the first, second, third and fourth static mixers are DN15-DN25 static mixers.
8. Use of a BiOX/Mn-Fe-O ammonium catalyst as obtained by the process of any one of claims 1-7 in water treatment.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113083317A (en) * 2021-04-07 2021-07-09 北京碧水源膜科技有限公司 Preparation method and preparation system of ammonium catalyst, active iron manganese oxide ammonium catalyst and deamination application
CN113648991A (en) * 2021-09-03 2021-11-16 北京碧水源膜科技有限公司 Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113083317A (en) * 2021-04-07 2021-07-09 北京碧水源膜科技有限公司 Preparation method and preparation system of ammonium catalyst, active iron manganese oxide ammonium catalyst and deamination application
CN113648991A (en) * 2021-09-03 2021-11-16 北京碧水源膜科技有限公司 Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof

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