A special broken catalyst material and its preparation method and application

Abstract

The application relates to a special broken complex catalytic material and a preparation method and application thereof, wherein the components of the special broken complex catalytic material comprise a main base material, a catalytic active substance and an auxiliary agent; the main base material is aluminum hydroxide powder and iron oxide powder; the catalytic active agent comprises titanium dioxide, nano cerium oxide, manganese oxide and lanthanum oxide; and the auxiliary agent comprises blue water gas and borax. The special broken complex catalytic material is used in cooperation with an auxiliary agent, ozone is introduced into wastewater to perform broken complex treatment, the pH of the waste liquid is adjusted, coagulation and precipitation are further performed by adding a coagulant and a flocculant, and the difficult-to-removing heavy metal complex and organic complex in the waste liquid are removed; especially, the total nickel concentration in the wastewater and sewage can be efficiently and stably reduced to below 0.1 mg / L, and the national first-level discharge standard is reached.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of wastewater treatment, and particularly relates to a special broken complex catalytic material and a preparation method and application thereof. BACKGROUND

[0002] At present, the wastewater treatment methods mainly include chemical treatment method, ion exchange method, adsorption method, membrane separation technology and biological method. The chemical treatment method includes neutralization precipitation method, sulfide precipitation method and ferrite method, and the chemical treatment method is one of the most commonly used methods because of simple process flow, convenient operation and mature technology, but the chemical treatment method has large occupied area and cannot degrade complex metal ions, and it is difficult to stably reach the standard; the ion exchange method has good effect on recycling valuable metals / ions in wastewater and improving water recycling rate, but the operation process is relatively complex, and the ion exchange resin is often affected by other organic pollutants, so that the service life is shortened and the treatment effect of the whole system is affected; the adsorption method is a method for removing heavy metal ions by using the unique structure of adsorbents, and zeolite, activated carbon and humic acid are often used as adsorbents for treating electroplating wastewater, but the adsorbents used in the industry at present are generally expensive, and the regeneration and secondary pollution of the adsorbents also need to be considered; the membrane separation technology applied to electroplating wastewater has the advantages of effectively removing heavy metal ions in wastewater, simple equipment, no need to add chemical reagents, etc., but the membrane assembly is expensive, and membrane pollution and membrane blockage will occur during use, and the operation cost is high; the biological treatment method has broad prospects, but the reaction kinetics between the biological adsorbent and the heavy metal is not fully understood, and the biological adsorbent with large adsorption capacity also needs to be developed, and it still has a distance to be widely used in the industry. Chinese patent CN105080551A discloses a high-efficiency spherical particle ozone oxidation catalyst and a preparation method thereof, which is prepared by taking iron oxide powder as base material, titanium dioxide and nano cerium dioxide as catalytic active agents, and coal powder and borax as binders. The high-efficiency spherical particle ozone oxidation catalyst can improve the ozone oxidation efficiency, and the removal rate of wastewater COD is as high as 60% or more, but the catalyst has poor effect on the metal complex which is difficult to remove and precipitate in wastewater, and it is difficult to completely remove the heavy metal; Chinese patent CN110743527A discloses a preparation method of a mesoporous ozone catalyst, which is prepared by taking base material, stabilizer, pore-forming agent, binder and synthetic active component as raw materials, and the particle size of the prepared spherical particles is 2-4mm, and the removal rate of COD in wastewater can reach 70% or more, but the catalyst still has poor effect on the metal complex which is difficult to remove and precipitate in wastewater.

[0003] In summary, the existing technology cannot basically remove the metal complex which is difficult to degrade and precipitate in wastewater and sewage, and the effluent quality is difficult to reach the standard. SUMMARY

[0004] In view of the problems in the prior art, the application provides a special complex breaking catalytic material and a preparation method and application thereof, which can efficiently and stably treat complex metals and complex organic matters in wastewater, simplifies a treatment process and realizes standard discharge of wastewater and sewage.

[0005] In a first aspect, the application provides a special complex breaking catalytic material, wherein the special complex breaking catalytic material comprises a main base material, a catalytic active agent and an auxiliary agent.

[0006] The main base material is aluminum hydroxide powder and iron oxide powder.

[0007] Further, the iron oxide powder is obtained by adding an appropriate amount of iron powder into sufficient oxygen to generate Fe2O3 by combustion, and then obtaining Fe2O3 powder by cooling and filtering.

[0008] Further, the aluminum hydroxide powder is high-purity aluminum hydroxide obtained by a series of treatments of crushing, soaking, heating, precipitation, filtering, drying and purification of waste aluminum products, and the specific steps are as follows.

[0009] The waste aluminum products are crushed into small pieces, then soaked in a sodium hydroxide solution, heated at 750-900 DEG C, then precipitated, filtered, dried, ground, dissolved by adding acid, and then filtered, washed and dried to obtain high-purity aluminum hydroxide.

[0010] The catalytic active agent comprises titanium dioxide, nano cerium oxide, manganese oxide and lanthanum oxide.

[0011] The auxiliary agent comprises blue coal and borax.

[0012] Further, the blue coal is selected from coal with high volatile matter, low ash content and low sulfur content as raw material, and pyrolysis reaction of the raw material coal is generated by heating at a high temperature of 400-600 DEG C to generate solid carbon and volatile substances, and then the high-temperature water vapor or carbon dioxide gas reacts with the carbon atoms on the surface of the blue coal to generate a microporous structure, increase the surface area and also have a bonding effect, and then the cooled and ground into a powder with a particle size of 150-250 mesh.

[0013] Further, the special complex breaking catalytic material comprises the main base material 65-90%, the catalytic active agent 2-10% and the auxiliary agent 8-25% by mass percentage.

[0014] Further, the main base material comprises aluminum hydroxide powder 80-95% and iron oxide powder 5-20% by mass percentage.

[0015] Further, the aluminum hydroxide powder is mainly obtained from recycling of waste aluminum products.

[0016] Further, the catalytically active agent comprises 70-90% of titanium dioxide, 1-10% of nano cerium oxide, 5-15% of manganese oxide and 0.5-10% of lanthanum oxide by mass percentage;

[0017] Further, the auxiliary agent comprises 45-85% of blue carbon and 15-55% of borax by mass percentage.

[0018] In the second aspect, the application provides a preparation method of the special catalytic material for breaking complex, which comprises the following steps: mixing the main substrate, the catalytically active agent and the auxiliary agent uniformly, preparing small balls with a diameter of 4-6mm, sintering at 400-1200℃ for 4-6h after drying and dehydrating, and cooling to obtain the special catalytic material for breaking complex.

[0019] In the third aspect, the application provides the application of the special catalytic material for breaking complex in the fields of wastewater treatment, sewage treatment and heavy metal adsorption.

[0020] Further, the treated wastewater and sewage contain heavy metal ions such as nickel, chromium, copper, cadmium and zinc.

[0021] In the fourth aspect, the application provides an efficient treatment method of wastewater, which comprises the following steps:

[0022] S1, pretreatment

[0023] Under the alkaline condition with a pH of 7.5-11.0, a coagulant and a flocculant are added to the wastewater for coagulation and precipitation, and the wastewater supernatant is obtained by separation.

[0024] S2, complex breaking treatment

[0025] Under the alkaline condition with a pH of 7.5-11.0, the wastewater supernatant obtained in step S1 is sent into an ozone catalytic oxidation reactor containing the special catalytic material for breaking complex, then an auxiliary agent is added, ozone is introduced into the ozone catalytic oxidation reactor for reaction, the pH of the treated wastewater is adjusted to 7.5-11.0, then a coagulant and a flocculant are added for coagulation and precipitation, and the supernatant is obtained by separation.

[0026] Further, the pH is adjusted by one or a combination of sodium hydroxide, calcium oxide or calcium hydroxide.

[0027] Preferably, the pH is 9.5-11.0.

[0028] Further, the auxiliary agent is potassium ferrate, and the addition amount is 100-200mg / L.

[0029] Further, the coagulant is polyaluminum chloride (purchased from Henan Qiyue Star Chemical Technology Co., Ltd.), and the addition amount is 50-100 mg / L.

[0030] Further, the flocculant is polyacrylamide (purchased from Henan Qiyue Star Chemical Technology Co., Ltd.), and the addition amount is 5-10 mg / L.

[0031] Further, the reaction time of the ozone reaction is 0.5-2 h.

[0032] Further, the standing time of the steps S1-S3 is not less than 0.5 h.

[0033] Further, the treated wastewater contains but is not limited to heavy metal ions such as nickel, chromium, copper, cadmium, zinc, etc.

[0034] The efficient wastewater treatment method of the present application is to first pretreat the wastewater, first adjust the pH of the wastewater to alkaline, add a coagulant and a flocculant to remove the non-complex metal ions by chemical precipitation, leave the refractory complex metal ions, and use the combined action of the special complex breaking catalyst, auxiliary reagents and ozone to specifically break the complex metal ions. This process generates hydroxyl radicals, breaks the chain reaction of most of the refractory organic matters in the wastewater to form short-chain organic matters or is directly oxidized to CO2 and H2O, destroys the organic complex in the wastewater, and makes the metal ions exist in a free state. Then, the alkalinity of the solution is adjusted, and the coagulant and the flocculant are sequentially added to coagulate and precipitate, so that the free metal ions form substances that are difficult to dissolve and are separated from the water, the heavy metal ions in the water are completely removed, and the discharge standard is achieved.

[0035] Compared with the prior art, the present application has the following advantages:

[0036] (1) The special complex breaking catalyst material of the present application can break the refractory heavy metal complex, and can efficiently and stably reduce the total nickel concentration in the wastewater and sewage to below 0.1 mg / L, reaching the national first-level discharge standard.

[0037] (2) The efficient wastewater treatment method of the present application can break a large number of complex metals through the combined action of the special complex breaking catalyst material, auxiliary reagents and ozone, and is suitable for multi-component wastewater treatment. In particular, the total nickel concentration of the treated wastewater containing nickel can be reduced to below 0.1 mg / L. The precipitate of the wastewater containing nickel mainly contains nickel hydroxide and iron hydroxide, which has a high recycling value. At the same time, the use of the special complex breaking catalyst material makes the ozone catalytic oxidation reaction require a lower condition, and the reaction process does not need to adjust the acidity, reducing the subsequent acid and alkali consumption, and eliminating the need to add heavy metal capture agents, sodium sulfide and other harmful reagents to the environment, thereby avoiding secondary pollution to the environment.

[0038] (3) The high-efficiency wastewater treatment method of the present application realizes the degradation of organic matters efficiently and stably through the action of ozone and special catalytic material for breaking up complex.

[0039] (4) The high-efficiency wastewater treatment method of the present application is simple in operation, stable in effect, and fully automatic in treatment, and has a small floor area. The aluminum hydroxide powder in the main substrate of the special catalytic material for breaking up complex is high-purity aluminum hydroxide obtained through a series of treatments such as crushing, soaking, heating, precipitation, filtration, drying and purification of waste aluminum products, and the special catalytic material for breaking up complex is not a consumable product and can be reused, and the activity can be restored after cleaning, realizing resource utilization, saving a large amount of raw materials and reducing production cost. DETAILED DESCRIPTION

[0040] The experimental methods not specified in the following examples of the present application are generally carried out under conventional conditions or under conditions recommended by the manufacturers. The various common chemical reagents used in the examples are commercially available products.

[0041] Unless otherwise defined, all technical and scientific terms used in the present application have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0042] To make the purpose, technical solutions and advantages of the present application more clear and explicit, the present application is further described in detail below with reference to specific embodiments. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present application. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present application.

[0043] The iron oxide powder, aluminum hydroxide powder and semicoke involved in the specific embodiments of the present application are obtained by the following methods:

[0044] (1) Iron oxide powder: a proper amount of iron powder is burned to generate Fe2O3 by adding sufficient oxygen, and then Fe2O3 powder is obtained by cooling and filtering;

[0045] (2) Aluminum hydroxide powder: waste aluminum products are crushed into small pieces, then soaked in sodium hydroxide solution, heated at 750-900℃, then precipitated, filtered, dried and ground, then dissolved by adding acid, and then high-purity aluminum hydroxide is obtained by filtering, washing and drying;

[0046] (3) Lan carbon: coal with high volatile matter, low ash content and low sulfur content is used as raw material, and the raw coal is pyrolyzed at 400-600°C for 12 hours to generate solid carbon and volatile matter. Then, the lan carbon is reacted with carbon dioxide for 12 hours to form microporous structure. After cooling, the lan carbon is ground into powder with particle size of 150-250 mesh.

[0047] Preparation of special broken bond catalytic material in Example 1

[0048] The specific formulation components of the special broken bond catalytic material prepared in this example are shown in Table 1.

[0049] Table 1: Formulation components of special broken bond catalytic material

[0050] Ingredients Content Aluminum hydroxide powder / g 24.6 Iron oxide powder / g 5.2 Titanium dioxide / g 3.35 Nano cerium dioxide / g 0.068 Manganese oxide / g 0.46 Lanthanum oxide / g 0.074 Lan carbon / g 4.45 Borax / g 1.798

[0051] The special broken bond catalytic material is prepared according to the component formulation in Table 1 above, and the specific preparation steps are as follows:

[0052] The main substrate (aluminum hydroxide powder, iron oxide powder), catalytic active agent (titanium dioxide, nano cerium dioxide, manganese oxide, lanthanum oxide) and auxiliary agent (lan carbon, borax) are mixed uniformly, put into a mold, pressed into small balls with a diameter of 4mm, and then sintered at 1000°C for 6h after drying and dehydrating. The special broken bond catalytic material is obtained after cooling.

[0053] Test Example 1: Wastewater treatment process of special broken bond catalytic material prepared in Example 1

[0054] The special broken bond catalytic material prepared in Example 1 is used for wastewater treatment, and the high-concentration electroplating nickel-containing wastewater from a certain factory in Huizhou is used as the treatment object. The original water quality is: total nickel 450mg / L, total copper 40mg / L, COD 572mg / L, and pH=8.5.

[0055] The specific treatment steps are as follows:

[0056] S1, pretreatment

[0057] 100mg / L coagulant (polyaluminum chloride) and 5mg / L flocculant (polyacrylamide) are added to the wastewater for coagulation and sedimentation, and the wastewater supernatant is obtained after standing for 30min and separation.

[0058] S2, broken bond treatment

[0059] The supernatant of the wastewater obtained in step S1 is sent into an ozone catalytic oxidation reactor containing the special catalytic material for breaking up the complex prepared in Example 1, the special catalytic material is added in an amount of 1000 g / L, then 150 mg / L of the auxiliary agent potassium ferrate is added, and 100 mg / L of ozone is introduced into the ozone catalytic oxidation reactor to perform ozone reaction for 1 h, the pH of the wastewater after the ozone reaction is adjusted to 10.5 (using 30% sodium hydroxide to adjust), then 100 mg / L of the coagulant and 5 mg / L of the flocculant of the same composition as in step S1 are added to perform coagulation and precipitation, and the supernatant obtained after standing for 30 min is the final effluent.

[0060] Wastewater treatment process of comparative test example one and conventional ozone catalytic material

[0061] A conventional ozone catalyst (main components: alumina, silica, titanium oxide) on the market is used to treat wastewater, and high-concentration electroplating wastewater containing nickel from a factory in Huizhou is taken as the treatment object, the original water quality: total nickel 450 mg / L, total copper 40 mg / L, COD 572 mg / L, pH = 8.5.

[0062] The specific treatment steps are as follows:

[0063] S1, pretreatment

[0064] 100 mg / L of a coagulant (polyaluminum chloride) and 5 mg / L of a flocculant (polyacrylamide) are added to the wastewater to perform coagulation and precipitation, and the supernatant of the wastewater obtained after standing for 30 min is used;

[0065] S2, ozone treatment

[0066] The supernatant of the wastewater obtained in step S1 is sent into an ozone catalytic oxidation reactor containing the special catalytic material for breaking up the complex prepared in Example 1, the special catalytic material is added in an amount of 1000 g / L, then 150 mg / L of the auxiliary agent potassium ferrate is added, and 100 mg / L of ozone is introduced into the ozone catalytic oxidation reactor to perform ozone reaction for 1 h, the pH of the wastewater after the ozone reaction is adjusted to 10.5 (using 30% sodium hydroxide to adjust), then 100 mg / L of the coagulant and 5 mg / L of the flocculant of the same composition as in step S1 are added to perform coagulation and precipitation, and the supernatant obtained after standing for 30 min is the final effluent.

[0067] Wastewater treatment effect determination and analysis of test example one and comparative test example one:

[0068] The average concentration and removal rate of total nickel, the average concentration and removal rate of total copper, and the COD content and removal rate in the final effluent of the wastewater treated by the catalytic material in test example one and comparative test example one are determined, the specific determination method of COD is potassium dichromate method, the determination method of total nickel is flame atomic absorption spectrometry, and the determination method of total copper is atomic absorption spectrophotometry, and the results are shown in Table 2.

[0069] Table 2: Final effluent content determination of wastewater treatment of test example one and comparative test example one

[0070]

[0071] From the results of Table 2, it can be seen that after the treatment of the raw water containing nickel wastewater by the special broken catalyst material prepared in Example 1 of the present application, the total nickel is reduced from 450 mg / L to 0.03 mg / L, the total copper is reduced from 40 mg / L to 0.08 mg / L, and the COD content is reduced from 572 mg / L to 102.4 mg / L. The removal rates of the total nickel, the total copper and the COD content are 99.99%, 99.8% and 82.1% respectively. Especially, the removal effect of the total nickel content is excellent, which ensures that the total nickel concentration of the treated effluent of the nickel-containing wastewater is below 0.1 mg / L, reaching the national first-level discharge standard. In comparison, in the comparative test example one, the conventional ozone catalyst in the market is used for treatment, and the removal rates of the total nickel, the total copper and the COD content are 99.88%, 96% and 60.68% respectively. The effect is far inferior to the treatment effect of the special broken catalyst material prepared in Example 1 of the present application. Moreover, the total nickel content of the final effluent of the wastewater is 0.52 mg / L, which cannot reach below 0.1 mg / L.

[0072] Preparation of the special broken catalyst material in Example 2

[0073] The formula components of the special broken catalyst material prepared in this example are specifically shown in Table 3;

[0074] Table 3: Formula components of the special broken catalyst material

[0075] Ingredients Content Aluminum hydroxide powder / g 27.4 Iron oxide powder / g 4.8 Titanium dioxide / g 2.75 Nano cerium dioxide / g 0.072 Manganese oxide / g 0.32 Lanthanum oxide / g 0.018 Lan carbon / g 2.09 Borax / g 2.55

[0076] The special broken catalyst material is prepared according to the above-mentioned component formula, and the specific preparation steps are as follows:

[0077] The main substrate (aluminum hydroxide powder, iron oxide powder), the catalytic active agent (titanium dioxide, nano cerium dioxide, manganese oxide, lanthanum oxide) and the auxiliary agent (semi-coke, borax) are fully mixed and uniformly placed in a mold, and then pressed into small balls with a diameter of 5 mm. After drying and dehydration, the small balls are sintered at 800℃ for 5h, and then cooled to obtain the special broken catalyst material.

[0078] Wastewater treatment process of the special broken catalyst material prepared in Example 2

[0079] The special broken catalyst material prepared in Example 2 is used for wastewater treatment, and the nickel-containing wastewater in a certain industrial park in Meizhou is taken as the treatment object. The raw water quality is as follows: the total nickel is 677 mg / L, the COD is 966.4 mg / L, and the pH is 8.0.

[0080] The specific treatment steps are as follows:

[0081] S1, pretreatment

[0082] 100 mg / L coagulant (polyaluminum chloride) and 5 mg / L flocculant (polyacrylamide) were added to the wastewater for coagulation and sedimentation, and the wastewater supernatant was separated after standing for 30 min and was used as needed;

[0083] S2, breakage treatment

[0084] The wastewater supernatant obtained in step S1 was sent to an ozone catalytic oxidation reactor containing the special breakage catalytic material prepared in Example 2, and the special breakage catalytic material was added in an amount of 1200 g / L, then 180 mg / L of auxiliary agent potassium ferrate was added, and 100 mg / L of ozone was introduced into the ozone catalytic oxidation reactor for ozone reaction for 1.5 h. The pH of the waste liquid after ozone reaction was adjusted to 10.5 (using 30% sodium hydroxide for adjustment), and then 100 mg / L of coagulant and 5 mg / L of flocculant with the same composition as in step S1 were added for coagulation and sedimentation. After standing for 30 min, the supernatant was separated to obtain the final effluent.

[0085] Comparative Test Example Two, wastewater treatment process without ozone catalytic material

[0086] Ozone treatment was used without ozone catalytic material, and wastewater containing nickel from a certain industrial park in Meizhou was used as the treatment object. The raw water quality was as follows: total nickel 677 mg / L, COD 966.4 mg / L, and pH 8.0.

[0087] The specific treatment steps are as follows:

[0088] S1, pretreatment

[0089] 100 mg / L coagulant (polyaluminum chloride) and 5 mg / L flocculant (polyacrylamide) were added to the wastewater for coagulation and sedimentation, and the wastewater supernatant was separated after standing for 30 min and was used as needed;

[0090] S2, ozone treatment

[0091] The wastewater supernatant obtained in step S1 was sent to an ozone catalytic oxidation reactor, 100 mg / L of ozone was introduced into the ozone catalytic oxidation reactor for reaction for 1.5 h, the pH of the waste liquid after ozone reaction was adjusted to 10.5 (using 30% sodium hydroxide for adjustment), and then 100 mg / L of coagulant and 5 mg / L of flocculant with the same composition as in step S1 were added for coagulation and sedimentation. After standing for 30 min, the supernatant was separated to obtain the final effluent.

[0092] Wastewater treatment effect determination and analysis of Test Example Two and Comparative Test Example Two:

[0093] The average concentration and removal rate of total nickel, the content and removal rate of COD in the final effluent of the treated wastewater of test example two and comparative test example two were determined. The content of COD was determined by potassium dichromate method, and the content of total nickel was determined by flame atomic absorption spectrometry. The results are shown in Table 4.

[0094] Table 4: Determination of the content of the final effluent of the wastewater treatment of test example two and comparative test example two

[0095]

[0096]

[0097] As shown in Table 4, after the raw wastewater containing nickel was treated by the special broken bond catalytic material prepared in test example two, the content of total nickel was reduced from 677 mg / L to 0.07 mg / L, and the content of COD was reduced from 966.4 mg / L to 267.4 mg / L. The removal rates of the contents of total nickel and COD were 99.99% and 72.33%, respectively. The removal effect of the content of total nickel was excellent, which ensured that the concentration of total nickel in the treated effluent of the wastewater containing nickel was below 0.1 mg / L, reaching the national first emission standard. In comparison, in comparative test example two, the ozone catalytic material was not used, and only ozone treatment was performed. The removal rates of the contents of total nickel and COD in the wastewater were 99.6% and 40.5%, respectively, which could not reach the content of total nickel below 0.1 mg / L.

[0098] Preparation of the special broken bond catalytic material in example 3

[0099] The specific formula components of the special broken bond catalytic material prepared in this example are shown in Table 5.

[0100] Table 5: Formula components of the special broken bond catalytic material

[0101] Ingredients Content Aluminum hydroxide powder / g 30.8 Iron oxide powder / g 2.6 Titanium dioxide / g 1.67 Nano cerium dioxide / g 0.046 Manganese oxide / g 0.24 Lanthanum oxide / g 0.164 Lan carbon / g 3.68 Borax / g 0.8

[0102] The special broken bond catalytic material was prepared according to the above-mentioned component formula. The specific preparation steps are as follows:

[0103] The main substrate (aluminum hydroxide powder, iron oxide powder), the catalytic active agent (titanium dioxide, nano cerium dioxide, manganese oxide, lanthanum oxide), and the auxiliary agent (semi-coke, borax) were fully mixed and uniformly placed in a mold, and then pressed into small balls with a diameter of 6 mm. After drying and dehydration, the small balls were sintered at 500°C for 5 h, and then cooled to obtain the special broken bond catalytic material.

[0104] Wastewater treatment process of the special broken bond catalytic material prepared in test example three and example 3

[0105] The special broken catalyst material prepared in Example 3 was used to treat wastewater. The high-concentration electroplating wastewater containing nickel from a factory in Huizhou was used as the treatment object. The quality of the raw water was as follows: total nickel 450 mg / L, total copper 40 mg / L, COD 572 mg / L, and pH 8.5.

[0106] The specific treatment steps were as follows:

[0107] S1, pretreatment

[0108] 100 mg / L of a coagulant (polyaluminum chloride) and 5 mg / L of a flocculant (polyacrylamide) were added to the wastewater for coagulation and sedimentation. After standing for 30 min, the supernatant of the wastewater was separated and used.

[0109] S2, broken catalyst treatment

[0110] The supernatant of the wastewater obtained in step S1 was fed into an ozone catalytic oxidation reactor containing the special broken catalyst material prepared in Example 3. The amount of the special broken catalyst material added was 1000 g / L. Then, 150 mg / L of an auxiliary agent, potassium ferrate, was added, and 100 mg / L of ozone was introduced into the ozone catalytic oxidation reactor for ozone reaction for 1 h. The pH of the wastewater after the ozone reaction was adjusted to 10.5 (using 30% sodium hydroxide). Then, 100 mg / L of a coagulant and 5 mg / L of a flocculant with the same composition as in step S1 were added for coagulation and sedimentation. After standing for 30 min, the supernatant was separated and used as the final effluent.

[0111] Comparative Test Three: Wastewater treatment without adding an auxiliary agent

[0112] In this test, the special broken catalyst material prepared in Example 3 was used to treat wastewater. No auxiliary agent, potassium ferrate, was added during the wastewater treatment process, and the other treatment steps were the same. The high-concentration electroplating wastewater containing nickel from a factory in Huizhou was used as the treatment object. The quality of the raw water was as follows: total nickel 450 mg / L, total copper 40 mg / L, COD 572 mg / L, and pH 8.5.

[0113] The specific treatment steps were as follows:

[0114] S1, pretreatment

[0115] 100 mg / L of a coagulant (polyaluminum chloride) and 5 mg / L of a flocculant (polyacrylamide) were added to the wastewater for coagulation and sedimentation. After standing for 30 min, the supernatant of the wastewater was separated and used.

[0116] S2, broken catalyst treatment

[0117] The supernatant of the wastewater obtained in step S1 is sent into an ozone catalytic oxidation reactor containing the special catalytic material for breaking complex, the special catalytic material for breaking complex is added in an amount of 1000 g / L, 100 mg / L ozone is introduced into the ozone catalytic oxidation reactor to perform ozone reaction for 1 h, the pH of the wastewater after ozone reaction is adjusted to 10.5 (adjustment is performed by using 30% sodium hydroxide), then 100 mg / L coagulant and 5 mg / L flocculant of the same composition as in step S1 are added to perform coagulation and precipitation, and the supernatant obtained after standing for 30 min is separated as the final effluent.

[0118] Determination and analysis of wastewater treatment effects of test example three and comparative test example three:

[0119] The average concentration and removal rate of total nickel, the average concentration and removal rate of total copper, and the COD content and removal rate in the final effluent of the wastewater treated by test example three and comparative test example three are determined, the specific determination method of COD is potassium dichromate method, the determination method of total nickel is flame atomic absorption spectrometry, and the determination method of total copper is atomic absorption spectrophotometry, and the results are shown in Table 6.

[0120] Table 6: Determination of the content of the final effluent of wastewater treatment of test example three and comparative test example three

[0121]

[0122] It can be known from the results in Table 6 that in the process of treating wastewater by using the special catalytic material for breaking complex prepared in comparative test example three, no auxiliary reagent is added, the COD concentration of the wastewater rises particularly obviously, and the treatment effects of total nickel and total copper also slightly decrease, which indicates that the special catalytic material for breaking complex and the auxiliary reagent are collectively treated to achieve a better wastewater treatment effect.

[0123] Preparation of the special catalytic materials for breaking complex in comparative examples 1-7

[0124] Comparative example 1: The difference between the special catalytic material for breaking complex in comparative example 1 and the special catalytic material for breaking complex in example 3 lies in that no aluminum hydroxide powder is added in the main substrate of the special catalytic material for breaking complex in comparative example 1, and iron oxide powder is used to make up.

[0125] Comparative example 2: The difference between the special catalytic material for breaking complex in comparative example 2 and the special catalytic material for breaking complex in example 3 lies in that the sintering temperature is 200 ℃ and the sintering time is 4 h during the preparation process.

[0126] Comparative example 3: The difference between the special catalytic material for breaking complex in comparative example 3 and the special catalytic material for breaking complex in example 3 lies in that titanium dioxide is replaced by copper oxide in the catalytic material in comparative example 3.

[0127] Comparative Example 4: The difference between the special broken bond catalytic material of Comparative Example 4 and the special broken bond catalytic material of Example 3 is that no titanium dioxide and nano cerium dioxide are added in the catalytic material of Comparative Example 4, the amount of manganese oxide added is 3.81 g, and the amount of lanthanum oxide added is 0.142 g.

[0128] Comparative Example 5: The difference between the special broken bond catalytic material of Comparative Example 5 and the special broken bond catalytic material of Example 3 is that no manganese oxide and lanthanum oxide are added in the catalytic material of Comparative Example 5, and the mass is supplemented with nano cerium dioxide.

[0129] Comparative Example 6: The difference between the special broken bond catalytic material of Comparative Example 6 and the special broken bond catalytic material of Example 3 is that sodium metasilicate is used instead of borax in the composition of the catalytic material of Comparative Example 6.

[0130] Comparative Example 7: The difference between the special broken bond catalytic material of Comparative Example 7 and the special broken bond catalytic material of Example 3 is that ordinary coal powder is used instead of semicoke in the composition of the catalytic material of Comparative Example 7.

[0131] The wastewater treatment effect of the special broken bond catalytic material prepared in Comparative Examples 1-7 is determined and analyzed.

[0132] The wastewater is treated by using the special broken bond catalytic material prepared in Comparative Examples 1-7, and the high-concentration electroplating nickel-containing wastewater of a certain factory in Huizhou is taken as the treatment object. The original water quality is as follows: total nickel is 450 mg / L, total copper is 40 mg / L, COD is 572 mg / L, and pH is 8.5.

[0133] The treatment method is the same as that of Test Example 3. The average concentration and removal rate of total nickel, the average concentration and removal rate of total copper, and the COD content and removal rate in the final effluent of the wastewater treated by the special broken bond catalytic material prepared in Comparative Examples 1-7 are determined. The specific determination method of COD is potassium dichromate method, the determination method of total nickel is flame atomic absorption spectrometry, and the determination method of total copper is atomic absorption spectrophotometry. The results are shown in Table 7.

[0134] Table 7: Determination of the final effluent content of wastewater treated by the special broken bond catalytic material prepared in Comparative Examples 1-7

[0135]

[0136] As can be seen from the comparison of Table 6 and Table 7, the effect of the special broken bond catalytic material prepared in Comparative Examples 1-7 on wastewater treatment is obviously lower than that of the special broken bond catalytic material prepared in Example 3, which indicates that the composition and preparation method of the special broken bond catalytic material of the present application have a great influence on the performance of the catalytic material.

[0137] Obviously, the above embodiments are merely example for clearly illustrating but not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments need not and can not be enumerated. The obvious changes or variations derived from the above description are still within the protection scope of the present application.

Claims

1. A special complex-breaking catalytic material, characterized in that, The special complex-breaking catalytic material comprises, by mass percentage, 65-90% main substrate, 2-10% catalytic activator, and 8-25% additives; The main substrate is aluminum hydroxide powder and iron oxide powder; by mass percentage, the main substrate contains 80-95% aluminum hydroxide powder and 5-20% iron oxide powder. The catalytic activator comprises titanium dioxide, nano-cerium oxide, manganese oxide, and lanthanum oxide; by mass percentage, the catalytic activator comprises 70-90% titanium dioxide, 1-10% nano-cerium oxide, 5-15% manganese oxide, and 0.5-10% lanthanum oxide. The additives comprise semi-coke and borax; by mass percentage, the additives comprise 45-85% semi-coke and 15-55% borax. The method for preparing semi-coke includes: High-volatile, low-ash, and low-sulfur coal is selected as raw material. The raw coal undergoes pyrolysis at 400–600℃ to produce semi-coke and volatile substances. Then, high-temperature steam or carbon dioxide gas reacts with the carbon atoms on the surface of the semi-coke to create a microporous structure, thereby increasing the specific surface area and adsorption capacity of the semi-coke. It also possesses an adhesive effect. It is made by grinding it into powder of 150-250 mesh after cooling.

2. A method for preparing the specific complex-breaking catalytic material according to claim 1, characterized in that, The preparation method includes: mixing the main substrate, catalytic activator and auxiliary agent evenly, forming small balls with a diameter of 4-6 mm, drying and dehydrating them, sintering them at 400-1200℃ for 4-6 h, and cooling them to obtain a special complex-breaking catalytic material.

3. The application of the special complex-breaking catalytic material according to claim 1 in the fields of wastewater treatment, sewage treatment, and heavy metal adsorption.

4. A highly efficient wastewater treatment method, characterized in that, The specific steps of the processing method include: S1, Preprocessing Under alkaline conditions, coagulants and flocculants are added to the wastewater to coagulate and settle it. After standing, the supernatant of the wastewater is separated and ready for use. S2, Collateral-breaking treatment Under alkaline conditions, the wastewater supernatant obtained in step S1 is fed into an ozone catalytic oxidation reactor containing the special complex-breaking catalytic material described in claim 1. Then, auxiliary agents are added, and ozone is introduced into the ozone catalytic oxidation reactor to react and adjust the pH of the wastewater. Then, coagulants and flocculants are added for coagulation and sedimentation. After standing, the supernatant is obtained by separation.

5. The efficient wastewater treatment method according to claim 4, characterized in that, In step S2, the pH is adjusted to 7.5–11.

0.

6. The efficient wastewater treatment method according to claim 4, characterized in that, The coagulant is selected from polyaluminum chloride, the flocculant is selected from polyacrylamide, and the auxiliary agent is selected from potassium ferrate.

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