A modified mineral-based water purifier for deep treatment of coking wastewater

Abstract

The present invention discloses a modified mineral-based water purifier for deep treatment of coking wastewater, which comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 25-50 parts of polyaluminium chloride and 10-28 parts of polyacrylamide. The modified mineral-based water purifier for deep treatment of coking wastewater provided by the present invention can improve the physical adsorption performance of pollutants in wastewater by functionally modifying attapulgite, and can also give it the function of chemical oxidation to remove organic matter, thereby greatly improving the deep treatment effect of attapulgite on coking wastewater; in the present invention, further by compounding functionalized modified attapulgite with inorganic polymer coagulant polyaluminium chloride and polyacrylamide as a water purifier, deep treatment of biochemical effluent in coking wastewater treatment can obtain satisfactory results.

Description

Technical Field

[0001] The invention relates to the field of wastewater treatment, and in particular to a modified mineral-based water purifier for deep treatment of coking wastewater. Background Art

[0002] Coking wastewater is high CODcr, high ammonia nitrogen, and high phenol industrial wastewater produced in the processes of coking, coal gas purification, and coking product recovery. It is highly toxic and needs to be treated before it can be discharged.

[0003] The biochemical method is a commonly used method for treating coking wastewater. It can effectively reduce phenols and cyanides in the wastewater, but the removal rate of difficult-to-degrade organic matter and ammonia nitrogen is relatively low. Therefore, further deep treatment is usually carried out after biochemical treatment, such as adding water purifiers with adsorption, flocculation and / or oxidation functions for re-purification.

[0004] Attapulgite is a natural mineral with rich pore structure and good stability. It is an adsorption material with good application potential and has been widely used in wastewater deep treatment. However, it has defects such as weak adsorption capacity for organic matter and insufficient adsorption capacity, which makes it difficult for natural attapulgite to meet the requirements in wastewater. Patent CN111646534A discloses a coking phenol-cyanide wastewater purifier and its preparation method and application. It uses a water purifier prepared from attapulgite, bentonite, fly ash, zeolite powder, silane coupling agent, dimethyldiallylammonium chloride, potassium persulfate, sodium carboxymethyl cellulose, polyferric sulfate, polyaluminum ferric silicate, ferrous sulfate, magnesium sulfate heptahydrate, trisodium phosphate, polyacrylamide, polyvinyl pyrrolidone and calcium hydroxide as raw materials to perform deep treatment of biochemical effluent in the coking wastewater treatment process. It makes full use of the adsorption performance of attapulgite and achieves good results, but its composition is complex, the interaction principle of each component is not clear, and the stability of its application needs to be considered. Patent CN110577254A discloses a water purifier used in coal chemical industry, coking industry and other chemical industries and its preparation method. It discloses a water purifier used to treat biochemical effluent, but its COD removal effect is average.

[0005] Therefore, it is necessary to improve the existing technology to provide a more reliable solution. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a modified mineral-based water purifier for deep treatment of coking wastewater in view of the deficiencies in the above-mentioned prior art.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: a modified mineral-based water purifier for deep treatment of coking wastewater, which comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 25-50 parts of polyaluminium chloride and 10-28 parts of polyacrylamide.

[0008] Preferably, the functionalized modified attapulgite is prepared by the following method:

[0009] 1) Preparation of modified attapulgite:

[0010] 1-1) crushing and sieving attapulgite, and then roasting;

[0011] 1-2) After cooling, adding the attapulgite into an acid solution, stirring, filtering, and washing with deionized water, wherein the acid solution is a mixture of hydrochloric acid and sulfuric acid;

[0012] 1-3) adding the attapulgite obtained in step 1-2) into a sodium citrate solution, shaking, centrifuging, washing, drying, and grinding to obtain modified attapulgite;

[0013] 2) Functional modification:

[0014] 2-1) adding the modified attapulgite into ethanol for soaking, filtering, washing, adding into deionized water, and ultrasonicating to obtain a modified attapulgite dispersion;

[0015] 2-2) FeCl 2 .4H 2 O is dissolved in deionized water, the obtained solution is added to the modified attapulgite dispersion and stirred, and then NaOH solution is added under stirring to obtain a mixture A;

[0016] 2-3) MnCl 2 The aqueous solution was added to KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0017] 2-4) Mix mixture A and mixture B and transfer them to a reactor, heat and react, dry after the reaction, and then calcine to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0018] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0019] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite is added into ethanol aqueous solution and dispersed by ultrasonic;

[0020] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added to a reaction kettle, reacted under heating, cooled to room temperature, filtered, washed with deionizer, vacuum dried, and ground to obtain functionalized modified attapulgite.

[0021] Preferably, the step 1) specifically includes:

[0022] 1-1) crush and sieve the attapulgite, and then roast at 350-550℃ for 4-12h;

[0023] 1-2) After cooling, adding attapulgite to an acid solution, stirring and reacting for 0.5-2 hours, filtering, and washing with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0024] 1-3) Add 2-10 mg of the attapulgite obtained in step 1-2) to 100 mL of a 0.1 mol / L sodium citrate solution, shake for 2-8 hours, centrifuge, wash, dry at 95-150° C., and grind to obtain modified attapulgite.

[0025] Preferably, the step 1) specifically includes:

[0026] 1-1) crush the attapulgite and pass it through a 200 mesh sieve, then roast it at 420°C for 6h;

[0027] 1-2) After cooling, adding attapulgite into an acid solution, stirring for 1 hour, filtering, and washing with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0028] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0029] Preferably, the step 2) specifically includes:

[0030] 2-1) adding the modified attapulgite into ethanol and soaking for 3-15 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 5-20 minutes to obtain a modified attapulgite dispersion;

[0031] 2-2) 0.01-0.05 mol FeCl 2 .4H 2O is dissolved in 100 mL of deionized water, and the obtained solution is added to the modified attapulgite dispersion, and stirred for 5-30 min under nitrogen, and then 5-30 mL of 2.0 M NaOH solution is added under stirring to obtain a mixture A;

[0032] 2-3) Add 40-100 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 60-150 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0033] 2-4) Mix mixture A and mixture B and transfer them to a reactor, react at 150-220°C for 2-8h, dry after the reaction, and then calcine at 350-480°C for 1-4h to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0034] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0035] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite is added into ethanol aqueous solution and ultrasonically dispersed for 15-45 minutes;

[0036] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added to a reaction kettle, reacted at 100-150° C. for 6-24 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 95-150° C., and ground to obtain functionalized modified attapulgite.

[0037] Preferably, the step 2) specifically includes:

[0038] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0039] 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0040] 2-3) Add 80 mL of 0.2 mol / L MnCl 2The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0041] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0042] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0043] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min;

[0044] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 h, cooled to room temperature, filtered, washed with deionizer, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite.

[0045] Preferably, in the step 2-2), the mass ratio of Fe: modified attapulgite is 3:1-0.8:1;

[0046] In the step 2-7), according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 0.5-2.5:100 added to the raw materials.

[0047] Preferably, in the step 2-2), the mass ratio of Fe: modified attapulgite is 1.5:1;

[0048] In the step 2-7), according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 1.8:100 added raw materials.

[0049] Preferably, the modified mineral-based water purifier for deep treatment of coking wastewater comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 30 parts of polyaluminium chloride and 22 parts of polyacrylamide.

[0050] Preferably, the modified mineral-based water purifier for deep treatment of coking wastewater is prepared by the following method: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 80-95°C for 1-4h, and then ground to obtain the modified mineral-based water purifier.

[0051] The beneficial effects of the present invention are:

[0052] The modified mineral-based water purifier for deep treatment of coking wastewater provided by the present invention can improve the physical adsorption performance of pollutants in wastewater by functional modification of attapulgite, and can also give it the function of chemical oxidation to remove organic matter, thereby greatly improving the deep treatment effect of attapulgite on coking wastewater;

[0053] The present invention first pre-treats the attapulgite to increase the pore volume and improve the electronegativity of the material, thereby being more conducive to improving the adsorption and removal effect of cations such as ammonia nitrogen; then in-situ grafting is performed on the attapulgite to form Fe 3 O 4 -MnO 2 Composite particles, with the help of the porous structure of attapulgite and the abundant silanol groups on the surface, can make Fe 3 O 4 -MnO 2 The composite particles are evenly loaded on the surface of attapulgite to reduce agglomeration, thus fully utilizing Fe 3 O 4 -MnO 2 The adsorption and catalytic effects of the composite particles; finally, Fe 3 O 4 -MnO 2 The modified attapulgite was modified with a strong oxidizing metal ruthenium, and finally Fe 3 O 4 -MnO 2 @Modified attapulgite-Ru structure system; Ruthenium is evenly and firmly connected to the surface of modified attapulgite through coordination with silanol. Metallic ruthenium can show strong oxidation performance and degrade high organic pollutants into CO 2 and H 2 O, or converted into low-toxic or non-toxic small molecular compounds that are easily biodegradable, while the Fe 3 O 4 -MnO 2 The composite particles can play a catalytic enhancement role in the process of ruthenium oxidation degradation of organic matter, so through Fe 3 O 4 -MnO 2 -Ru system can play a role in Fe 3 O 4 -MnO2 H 2 O 2 The conventional Fenton-like system formed has a stronger effect of oxidative degradation of organic matter, and can be supplemented by Fe by loading modified attapulgite. 3 O 4 -MnO 2 @The modified attapulgite-Ru structure system has better dispersibility and stability, making Fe 3 O 4 -MnO 2 -Ru system can give full play to its role of chemical oxidation to remove organic matter; and because Fe 3 O 4 Since it is magnetic, the water purifier can be easily recovered by applying an external magnetic field, thereby reducing costs. DETAILED DESCRIPTION

[0054] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0055] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0056] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are all commercially available unless otherwise specified. In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0057] The invention provides a modified mineral-based water purifier for deep treatment of coking wastewater, which comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 25-50 parts of polyaluminium chloride and 10-28 parts of polyacrylamide.

[0058] The preparation method of the modified mineral-based water purifier is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 80-95°C for 1-4h, and then ground to 200-300 meshes to obtain the modified mineral-based water purifier.

[0059] Among them, the functionalized modified attapulgite is prepared by the following method:

[0060] 1) Preparation of modified attapulgite:

[0061] 1-1) crush and sieve the attapulgite, and then roast at 350-550℃ for 4-12h;

[0062] 1-2) After cooling, the attapulgite is added to the acid solution, stirred to react for 0.5-2 hours, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0063] 1-3) Add 2-10 mg of the attapulgite obtained in step 1-2) to 100 mL of a 0.1 mol / L sodium citrate solution, shake for 2-8 hours, centrifuge, wash, dry at 95-150° C., and grind to obtain modified attapulgite.

[0064] 2) Functional modification:

[0065] 2-1) adding the modified attapulgite into ethanol and soaking for 3-15 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 5-20 minutes to obtain a modified attapulgite dispersion;

[0066] 2-2) 0.01-0.05 mol FeCl 2 .4H 2 O is dissolved in 100 mL of deionized water, and the obtained solution is added to the modified attapulgite dispersion, and stirred for 5-30 min under nitrogen, and then 5-30 mL of 2.0 M NaOH solution is added under stirring to obtain a mixture A;

[0067] Among them, the raw material FeCl is added according to the mass ratio of Fe: modified attapulgite of 3:1-0.8:1 2 .4H 2 O and modified attapulgite dispersion;

[0068] 2-3) Add 40-100 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 60-150 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0069] 2-4) Mix mixture A and mixture B and transfer them to a reactor, react at 150-220°C for 2-8h, dry after the reaction, and then calcine at 350-480°C for 1-4h to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0070] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0071] 2-6) The Fe-loaded 3 O 4 -MnO2 The modified attapulgite is added into ethanol aqueous solution and ultrasonically dispersed for 15-45 minutes;

[0072] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added to a reaction kettle, reacted at 100-150° C. for 6-24 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 95-150° C., and ground to obtain functionalized modified attapulgite;

[0073] Among them, according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 0.5-2.5:100 added to the raw materials.

[0074] Attapulgite is a natural mineral with rich pore structure and good stability. It is an adsorption material with good application potential and has been widely used in deep treatment of wastewater. However, it has defects such as weak adsorption capacity for organic matter and insufficient adsorption capacity, which makes it difficult for natural attapulgite to meet the requirements in wastewater. The present invention can overcome this defect by functional modification and give full play to its advantages, and can be well applied to deep treatment of coking wastewater; specifically:

[0075] In the pretreatment process of attapulgite: in the present invention, firstly, the bound water inside the pores of attapulgite can be removed by roasting, thereby opening up the internal channels, increasing the pore volume and specific surface area, and improving the adsorption capacity; then, the micropores can be further enlarged by acid leaching, and the Si-OH content on the surface of attapulgite can be increased, so that the surface properties of attapulgite are improved; finally, by soaking in sodium citrate, the divalent cations (Ca 2+) with larger particle size in the attapulgite are replaced by sodium ions with smaller particle size. 2+ Mg 2+ On the one hand, it can increase the pore volume, and on the other hand, it can improve the electronegativity of the material, thereby being more conducive to improving the adsorption and removal effect of cations such as ammonia nitrogen;

[0076] In the functionalization process: Fe is first grafted in situ on attapulgite 3 O 4 -MnO 2 Composite particles, with the help of the porous structure of attapulgite and the abundant silanol groups on the surface, can make Fe 3 O 4 -MnO 2 The composite particles are evenly loaded on the surface of attapulgite to reduce agglomeration, thus fully utilizing Fe 3 O 4 -MnO 2 Adsorption and catalytic effects of composite particles;

[0077] After that, Fe 3 O 4 -MnO 2 The modified attapulgite was modified with a strong oxidizing metal ruthenium, and finally Fe 3 O 4 -MnO 2 @Modified attapulgite-Ru structure system; ruthenium is evenly and firmly connected to the surface of modified attapulgite through coordination with silanol, the valence state of metal ruthenium is +8, and its oxidation potential is >3.35eV, which is stronger than conventional oxidants: hydroxyl radical (·OH), ozone, etc., as shown in Table 1 below:

[0078] Table 1

[0079]

[0080] The ruthenium metal on the surface of all modified attapulgite can show strong oxidation performance, which can degrade high organic pollutants into CO 2 and H 2 O, or converted into low-toxic or non-toxic small molecular compounds that are easily biodegradable, while the Fe 3 O 4 -MnO 2 The composite particles can play a catalytic enhancement role in the process of ruthenium oxidation degradation of organic matter, so through Fe 3 O 4 -MnO 2 -Ru system can play a role in Fe 3 O 4 -MnO 2 H 2 O 2 The conventional Fenton-like system formed has a stronger effect of oxidative degradation of organic matter, and can be supplemented by Fe by loading modified attapulgite. 3 O 4 -MnO 2 @The modified attapulgite-Ru structure system has better dispersibility and stability, making Fe 3 O 4 -MnO 2 -Ru system can give full play to its role of chemical oxidation in removing organic matter;

[0081] In the present invention, by functionalizing the attapulgite, it is possible to improve its physical adsorption performance for pollutants in wastewater and give it the function of chemical oxidation to remove organic matter, thereby greatly improving the deep treatment effect of the attapulgite on coking wastewater. 3 O 4Since it is magnetic, the water purifier can be easily recovered by applying an external magnetic field, thereby reducing costs.

[0082] In the present invention, functionalized modified attapulgite is further compounded with inorganic polymer coagulants such as polyaluminium chloride and polyacrylamide as water purifiers to achieve satisfactory results in deep treatment of biochemical effluent in coking wastewater treatment.

[0083] Example 1

[0084] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 30 parts of polyaluminium chloride and 22 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0085] In this embodiment, the functionalized modified attapulgite is prepared by the following method:

[0086] 1) Preparation of modified attapulgite:

[0087] 1-1) The attapulgite was crushed and passed through a 200-mesh sieve, and then calcined at 420°C for 6 hours;

[0088] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0089] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0090] 2) Functional modification:

[0091] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0092] 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0093] Among them, the mass ratio of Fe: modified attapulgite is 1.5:1;

[0094] 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0095] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0096] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0097] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min;

[0098] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite;

[0099] Among them, according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 1.8:100 added raw materials.

[0100] Example 2

[0101] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 28 parts of polyaluminium chloride and 17 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0102] Among them, the preparation method of functionalized modified attapulgite is the same as that in Example 1.

[0103] Example 3

[0104] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 25 parts of polyaluminium chloride and 15 parts of polyacrylamide; a preparation method thereof comprises: mixing the functionalized modified attapulgite, polyaluminium chloride and polyacrylamide in proportion, heating at 90°C for 2h, and then grinding to a size below 200 mesh with a proportion greater than 98%, thereby obtaining the modified mineral-based water purifier.

[0105] Among them, the preparation method of functionalized modified attapulgite is the same as that in Example 1.

[0106] Example 4

[0107] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 28 parts of polyaluminium chloride and 17 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0108] In this embodiment, the functionalized modified attapulgite is prepared by the following method:

[0109] 1) Preparation of modified attapulgite:

[0110] 1-1) crush the attapulgite and pass it through a 200 mesh sieve, then roast it at 420°C for 6h;

[0111] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0112] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0113] 2) Functional modification:

[0114] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0115] 2-2) 0.025 mol FeCl 2 .4H 2O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0116] Among them, the mass ratio of Fe: modified attapulgite is 2:1;

[0117] 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0118] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0119] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0120] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min;

[0121] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite;

[0122] Among them, according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 1.8:100 added raw materials.

[0123] Example 5

[0124] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 28 parts of polyaluminium chloride and 17 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0125] In this embodiment, the functionalized modified attapulgite is prepared by the following method:

[0126] 1) Preparation of modified attapulgite:

[0127] 1-1) The attapulgite was crushed and passed through a 200-mesh sieve, and then calcined at 420°C for 6 hours;

[0128] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0129] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0130] 2) Functional modification:

[0131] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0132] 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0133] Among them, the mass ratio of Fe: modified attapulgite is 2:1;

[0134] 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0135] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0136] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0137] 2-6) The Fe-loaded3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min;

[0138] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite;

[0139] Among them, according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 2:100 added raw materials.

[0140] Example 6

[0141] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 28 parts of polyaluminium chloride and 17 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0142] In this embodiment, the functionalized modified attapulgite is prepared by the following method:

[0143] 1) Preparation of modified attapulgite:

[0144] 1-1) The attapulgite was crushed and passed through a 200-mesh sieve, and then calcined at 420°C for 6 hours;

[0145] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0146] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0147] 2) Functional modification:

[0148] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0149] 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0150] Among them, the mass ratio of Fe: modified attapulgite is 2:1;

[0151] 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0152] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite;

[0153] 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0154] 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min;

[0155] 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite;

[0156] Among them, according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 2.2:100 added raw materials.

[0157] Comparative Example 1

[0158] A modified mineral-based water purifier for deep treatment of coking wastewater, comprising the following raw materials in parts by weight: 50 parts of modified attapulgite, 28 parts of polyaluminium chloride and 17 parts of polyacrylamide; a preparation method thereof is as follows: functionalized modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 90°C for 2h, and then ground to less than 200 meshes with a proportion greater than 98%, to obtain the modified mineral-based water purifier.

[0159] In this embodiment, the modified attapulgite is prepared by the following method:

[0160] 1) crush the attapulgite and pass it through a 200-mesh sieve, then calcine at 420°C for 6h;

[0161] 2) After cooling, adding the attapulgite into the acid solution, stirring for 1 hour, filtering, and washing with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0162] 3) 5 mg of the attapulgite obtained in step 2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0163] Comparative Example 2

[0164] This example is basically the same as Example 5, except that the preparation method of the functionalized modified attapulgite is different. Specifically, in this example, the functionalized modified attapulgite is prepared by the following method:

[0165] 1) Preparation of modified attapulgite:

[0166] 1-1) The attapulgite was crushed and passed through a 200-mesh sieve, and then calcined at 420°C for 6 hours;

[0167] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0168] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0169] 2) Functional modification:

[0170] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0171] 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A;

[0172] Among them, the mass ratio of Fe: modified attapulgite is 2:1;

[0173] 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B;

[0174] 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain functionalized Fe 3 O 4 -MnO 2 Modified attapulgite.

[0175] Comparative Example 3

[0176] This example is basically the same as Example 5, except that the preparation method of the functionalized modified attapulgite is different. Specifically, in this example, the functionalized modified attapulgite is prepared by the following method:

[0177] 1) Preparation of modified attapulgite:

[0178] 1-1) crush the attapulgite and pass it through a 200 mesh sieve, then roast it at 420°C for 6h;

[0179] 1-2) After cooling, the attapulgite is added to the acid solution, stirred for reaction for 1 hour, filtered, and washed with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1;

[0180] 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

[0181] 2) Functional modification:

[0182] 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion;

[0183] 2-2) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir;

[0184] 2-3) The solution obtained in step 2-2) and the modified attapulgite dispersion obtained in step 2-1) are mixed and added into a reaction kettle, reacted at 130° C. for 12 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite;

[0185] Among them, the raw materials are added in a mass ratio of triruthenium dodecacarbonyl: modified attapulgite = 2:100.

[0186] The following uses the biochemical effluent of a coking plant in Ordos, Inner Mongolia as an example to test the water purifiers prepared in the above embodiments and comparative examples. The main pollutant indicators of the biochemical effluent are shown in Table 2 below:

[0187] Table 2

[0188]

[0189] The test method is: add 0.4g of water purifier to 1L of biochemical effluent, stir at room temperature for 10min, then let it stand for 20min, take the supernatant to detect ammonia nitrogen concentration, CODcr concentration and chromaticity, calculate the ammonia nitrogen removal rate, CODcr removal rate and chromaticity removal rate, the measurement results are shown in Table 3 below:

[0190] Table 3

[0191]

[0192] It can be seen from the above results that the water purifiers of Examples 1-6 all have good wastewater treatment effects, while the results of Comparative Examples 1-3 are poor.

[0193] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A modified mineral-based water purifier for deep treatment of coking wastewater, It is characterized in that The method comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 25-50 parts of polyaluminium chloride and 10-28 parts of polyacrylamide; The functionalized modified attapulgite is prepared by the following method: 1) Preparation of modified attapulgite: 1-1) crushing and sieving attapulgite, and then roasting; 1-2) After cooling, adding the attapulgite into an acid solution, stirring, filtering, and washing with deionized water, wherein the acid solution is a mixture of hydrochloric acid and sulfuric acid; 1-3) adding the attapulgite obtained in step 1-2) into a sodium citrate solution, shaking, centrifuging, washing, drying, and grinding to obtain modified attapulgite; 2) Functional modification: 2-1) adding the modified attapulgite into ethanol for soaking, filtering, washing, adding into deionized water, and ultrasonicating to obtain a modified attapulgite dispersion; 2-2) FeCl 2 .4H 2 O is dissolved in deionized water, the obtained solution is added to the modified attapulgite dispersion and stirred, and then NaOH solution is added under stirring to obtain a mixture A; 2-3) MnCl 2 The aqueous solution was added to KMnO 4 The aqueous solution was stirred to obtain a mixture B; 2-4) Mix mixture A and mixture B and transfer them to a reactor, heat and react, dry after the reaction, and then calcine to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite; 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir; 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite is added into ethanol aqueous solution and dispersed by ultrasonic; 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added to a reaction kettle, reacted under heating, cooled to room temperature, filtered, washed with deionizer, vacuum dried, and ground to obtain functionalized modified attapulgite.

2. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 1, It is characterized in that The step 1) specifically includes: 1-1) crush and sieve the attapulgite, and then roast at 350-550℃ for 4-12h; 1-2) After cooling, adding attapulgite to an acid solution, stirring and reacting for 0.5-2 hours, filtering, and washing with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1; 1-3) Add 2-10 mg of the attapulgite obtained in step 1-2) to 100 mL of a 0.1 mol / L sodium citrate solution, shake for 2-8 hours, centrifuge, wash, dry at 95-150° C., and grind to obtain modified attapulgite.

3. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 2, It is characterized in that The step 1) specifically includes: 1-1) The attapulgite was crushed and passed through a 200-mesh sieve, and then calcined at 420°C for 6 hours; 1-2) After cooling, adding attapulgite into an acid solution, stirring for reaction for 1 hour, filtering, and washing with deionized water, wherein the acid solution is obtained by mixing 1 mol / L hydrochloric acid and 1 mol / L sulfuric acid in a volume ratio of 1:1; 1-3) 5 mg of the attapulgite obtained in step 1-2) was added to 100 mL of a 0.1 mol / L sodium citrate solution, shaken for 4 h, centrifuged, washed, dried at 110° C., and ground to obtain modified attapulgite.

4. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 2, It is characterized in that The step 2) specifically includes: 2-1) adding the modified attapulgite into ethanol and soaking for 3-15 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 5-20 minutes to obtain a modified attapulgite dispersion; 2-2) 0.01-0.05 mol FeCl 2 .4H 2 O is dissolved in 100 mL of deionized water, and the obtained solution is added to the modified attapulgite dispersion, and stirred for 5-30 min under nitrogen, and then 5-30 mL of 2.0 M NaOH solution is added under stirring to obtain a mixture A; 2-3) Add 40-100 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 60-150 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B; 2-4) Mix mixture A and mixture B and transfer them to a reactor, react at 150-220°C for 2-8h, dry after the reaction, and then calcine at 350-480°C for 1-4h to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite; 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir; 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite is added into ethanol aqueous solution and ultrasonically dispersed for 15-45 minutes; 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added to a reaction kettle, reacted at 100-150° C. for 6-24 hours, cooled to room temperature, filtered, washed with deionized water, vacuum dried at 95-150° C., and ground to obtain functionalized modified attapulgite.

5. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 4, It is characterized in that The step 2) specifically includes: 2-1) adding the modified attapulgite into ethanol and soaking for 5 minutes, filtering, washing, adding into deionized water, and ultrasonicating for 10 minutes to obtain a modified attapulgite dispersion; 2-2) 0.025 mol FeCl 2 .4H 2 O was dissolved in 100 mL of deionized water, and the obtained solution was added to the modified attapulgite dispersion, and stirred for 15 min under nitrogen, and then 15 mL of 2.0 M NaOH solution was added under stirring to obtain a mixture A; 2-3) Add 80 mL of 0.2 mol / L MnCl 2 The aqueous solution was added to 120 mL of 0.2 mol / L KMnO 4 The aqueous solution was stirred to obtain a mixture B; 2-4) Mixture A and mixture B were mixed and transferred to a reactor, reacted at 180°C for 4 hours, dried after the reaction, and then calcined at 400°C for 2 hours to obtain Fe-loaded 3 O 4 -MnO 2 Modified attapulgite; 2-5) Add triruthenium dodecacarbonyl into dimethyl sulfoxide and stir; 2-6) The Fe-loaded 3 O 4 -MnO 2 The modified attapulgite was added into ethanol aqueous solution and ultrasonically dispersed for 20 min; 2-7) The solution obtained in step 2-5) and the dispersion obtained in step 2-6) are mixed and added into a reaction kettle, reacted at 130° C. for 12 h, cooled to room temperature, filtered, washed with deionizer, vacuum dried at 105° C., and ground to obtain functionalized modified attapulgite.

6. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 5, It is characterized in that In the step 2-2), the mass ratio of Fe: modified attapulgite is 3:1-0.8:1; In the step 2-7), according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 0.5-2.5:100 added to the raw materials.

7. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 6, It is characterized in that In the step 2-2), the mass ratio of Fe: modified attapulgite is 1.5:1; In the step 2-7), according to the mass ratio, triruthenium dodecacarbonyl: loaded Fe 3 O 4 -MnO 2 Modified attapulgite = 1.8:100 added raw materials.

8. The modified mineral-based water purifier for deep treatment of coking wastewater according to claim 1, It is characterized in that The invention comprises the following raw materials in parts by weight: 50 parts of functionalized modified attapulgite, 30 parts of polyaluminium chloride and 22 parts of polyacrylamide.

9. The modified mineral-based water purifier for deep treatment of coking wastewater according to any one of claims 1 to 8, It is characterized in that The modified mineral-based water purifier is prepared by the following method: functional modified attapulgite, polyaluminium chloride and polyacrylamide are mixed in proportion, heated at 80-95°C for 1-4h, and then ground to obtain the modified mineral-based water purifier.

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