CN118005421A - Ceramic particles for organic wastewater treatment and preparation method thereof - Google Patents
Ceramic particles for organic wastewater treatment and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 92
- 239000002245 particle Substances 0.000 title claims abstract description 48
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 142
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 71
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 21
- WZEMSIKSCALWJZ-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO.CCO WZEMSIKSCALWJZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002261 Corn starch Polymers 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000008120 corn starch Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 238000005453 pelletization Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- -1 chloropropyl Chemical group 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 229940043237 diethanolamine Drugs 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- UPYVYJSWGZMBOU-UHFFFAOYSA-N 1-pentylimidazole Chemical compound CCCCCN1C=CN=C1 UPYVYJSWGZMBOU-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 22
- 230000015556 catabolic process Effects 0.000 abstract description 13
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 10
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- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention discloses ceramic particles for organic wastewater treatment and a preparation method thereof, and relates to the field of water treatment materials. When ceramic particles for treating organic wastewater are prepared, tetrabutyl titanate, absolute ethyl alcohol, deionized water, ammonia water and diethanol ammonia are mixed, dried, heated, calcined and crushed to prepare nitrogen-doped titanium dioxide powder; mixing the nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch, pelletizing, and performing heat treatment to obtain nitrogen-doped porous titanium dioxide ceramic; reacting imidazole with 1-hexene to obtain N-N-amyl imidazole; the nitrogen-doped porous titanium dioxide ceramic is reacted with (3-chloropropyl) trimethoxysilane and N-N-pentylimidazole in sequence to prepare ceramic particles for treating organic wastewater. The ceramic particles for treating organic wastewater prepared by the invention have high degradation rate and capability of absorbing anionic organic pollutants under natural light.
Description
Technical Field
The invention relates to the field of water treatment materials, in particular to ceramic particles for treating organic wastewater and a preparation method thereof.
Background
Organic pollutants are the main sources of environmental pollutants, and are mainly divided into natural organic pollutants and artificial synthetic organic pollutants according to different sources, wherein the natural organic pollutants are mainly generated by biological metabolism activities and other biochemical processes, the artificial synthetic organic pollutants are generated along with the rising of synthetic chemistry, most of the organic pollutants are easily oxidized and decomposed or are degraded through biological action, and part of the organic pollutants are difficult to degrade or have longer residual time, and the organic pollutants have low content, but can exist in the environment for a long time to generate persistent toxicity, can be absorbed by human bodies and gradually accumulated through food chains, and are extremely harmful to human beings.
Along with the development of modern society, the types and the quantity of organic pollutants discharged by human beings to natural environment are more and more, and the self-cleaning capability of the nature is exceeded, and most of the organic pollutants are teratogenic, oncogenic and mutagenic substances, and have the characteristics of low content, concealment, persistence, accumulation, toxicity and the like, so that the pollutants directly harm human health on one hand, and influence the survival, reproduction and sustainable development of human beings; the ceramic particles for treating organic wastewater have high degradation rate and capability of absorbing anionic organic pollutants under natural light.
Disclosure of Invention
In view of the above analysis, the present invention provides a ceramic particle for treating organic wastewater and a preparation method thereof, which are used for solving the problem of organic pollution existing in the existing water body.
In one aspect, the invention provides ceramic particles for organic wastewater treatment, which are prepared by sequentially reacting nitrogen-doped porous titanium dioxide ceramic with (3-chloropropyl) trimethoxysilane and N-N-pentylimidazole.
Further, the N-N-amyl imidazole is prepared by the reaction of imidazole and 1-hexene.
Further, the nitrogen-doped porous titanium dioxide ceramic is prepared by mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch, pelletizing and heat treatment.
Further, the nitrogen-doped titanium dioxide powder is prepared by mixing tetrabutyl titanate, absolute ethyl alcohol, deionized water, ammonia water and diethanol ammonia, drying, heating, calcining and crushing.
In another aspect, the present invention provides a method for preparing ceramic particles for organic wastewater treatment, which can be used at least for preparing the ceramic particles for organic wastewater treatment, the method comprising the steps of:
(1) Mixing deionized water, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1:1 (13-14), stirring for 3-5 min at a speed of 800-1000 r/min, adding titanium mixed solution with a mass of 13-15 times of that of diethanol amine and ammonia water with a mass of 9-11 times of that of diethanol amine at a constant speed of 8-10 min, continuously stirring for 50-70 min, standing for 6-8 d, drying for 1.5-2.5 h at 110-130 ℃, heating to 240-260 ℃, preserving heat for 50-70 min, continuously heating to 480-520 ℃ at a speed of 13-17 ℃/min, calcining for 1.5-2.5 h, and crushing to 100-300 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to the mass ratio of (90-94): (2-4): (4-6), preparing balls with the diameter of 6-8 cm, drying at 140-160 ℃ for 100-140 min, continuously heating to 480-520 ℃ at the heating rate of 4-6 ℃/min, preserving heat for 80-100 min, continuously heating to 1000-1200 ℃ and preserving heat for 80-100 min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to the mass ratio of 1:1 (18-22) (0.05-0.07), carrying out ultrasonic treatment for 25-35 min, heating to 100-120 ℃, reacting for 2-3 h under the irradiation of an ultraviolet lamp at 300-500 r/min, filtering, washing for 3-5 times with acetone, and drying for 8-10 h at 80-100 ℃ to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-pentylimidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to the mass ratio of (6-8) (4-6), immersing in N-methylpyrrolidone, reacting for 10-14 h at the temperature of 70-90 ℃ at the speed of 200-300 r/min, filtering, washing with N-methylpyrrolidone, 0.08-0.12 mol/L of hydrogen chloride solution and methanol for 3-5 times in sequence, and vacuum drying at the temperature of-10-0 ℃ for 22-24 h to obtain ceramic particles for treating organic wastewater.
Further, the titanium mixed solution in the step (1) is prepared by stirring tetrabutyl titanate for 3-5 min at 800-1000 r/min, adding absolute ethyl alcohol with the molar weight of 12-14 times of the tetrabutyl titanate at a constant speed within 10-20 min, and continuing stirring for 25-35 min.
Further, the N-N-amyl imidazole in the step (3) is prepared by mixing imidazole, methanol and 1-hexene according to a volume ratio of 1:1:1, heating to 50-60 ℃, reacting for 2-4 hours, and drying at 70-80 ℃ for 5-7 hours.
Further, the reaction process of the chloropropyl nitrogen-doped porous titanium dioxide ceramic in the step (3) is as follows:
。
Further, the reaction process of the N-N-pentylimidazole in the step (3) is as follows:
。
compared with the prior art, the invention has at least one of the following beneficial effects:
(1) When ceramic particles for treating organic wastewater are prepared, tetrabutyl titanate, absolute ethyl alcohol, deionized water, ammonia water and diethanol ammonia are mixed, dried, heated, calcined and crushed to prepare nitrogen-doped titanium dioxide powder; mixing the nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch, pelletizing, and performing heat treatment to obtain nitrogen-doped porous titanium dioxide ceramic; reacting imidazole with 1-hexene to obtain N-N-amyl imidazole; the nitrogen-doped porous titanium dioxide ceramic is sequentially reacted with (3-chloropropyl) trimethoxysilane and N-N-pentylimidazole to prepare ceramic particles for treating organic wastewater;
(2) Firstly, when ceramic particles for treating organic wastewater are prepared, tetrabutyl titanate, absolute ethyl alcohol, deionized water, ammonia water and diethanol ammonia are mixed, dried, heated, calcined and crushed to prepare nitrogen-doped titanium dioxide powder; mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch, pelletizing, and performing heat treatment to obtain nitrogen-doped porous titanium dioxide ceramic, wherein nitrogen element doping can replace a small amount of lattice oxygen atoms in titanium dioxide, and 2p orbitals of the oxygen atoms are hybridized with 2p orbitals of the nitrogen atoms, so that the band gap of the titanium dioxide is narrowed, the titanium dioxide has photoresponse under longer wavelength, and has certain photocatalytic activity under sunlight or visible light while the ultraviolet catalytic activity is not reduced; the ceramic particles for treating the organic wastewater are made into a porous structure, so that the contact area of the ceramic particles and the organic pollution wastewater can be increased, and the degradation rate of organic pollutants is increased;
(3) Secondly, imidazole and 1-hexene react to prepare N-N-amyl imidazole; the ceramic particles for treating organic wastewater are prepared by sequentially reacting nitrogen-doped porous titanium dioxide ceramic with (3-chloropropyl) trimethoxysilane and N-N-amyl imidazole, and imidazole ions are immobilized on the surface of the nitrogen-doped porous titanium dioxide ceramic, so that the imidazole ions are convenient to recycle and recycle, secondary pollution of the imidazole ions to the organic wastewater can be avoided, the imidazole ions have a better adsorption effect on anionic organic pollutants, and the organic pollutants can be gathered on the surface of the ceramic particles more quickly, so that the degradation rate of the organic pollutants is increased.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 3min at 800r/min, adding absolute ethyl alcohol with the molar weight of 12 times of that of the tetrabutyl titanate at a constant speed within 10min, and continuously stirring for 25min to obtain a titanium mixed solution; mixing deionized water, diethanol ammonia and absolute ethyl alcohol according to a molar ratio of 1:1:13, stirring for 3min at 800r/min, adding titanium mixed solution with the mass of 13 times of diethanol ammonia and ammonia water with the mass of 9 times of diethanol ammonia at a constant speed within 8min, continuously stirring for 50min, standing for 6d, drying at 110 ℃ for 1.5h, heating to 240 ℃, preserving heat for 50min, continuously heating to 480 ℃ at a speed of 13 ℃/min, calcining for 1.5h, and crushing to 100 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to a mass ratio of 90:2:4, preparing balls with diameters of 6cm, drying at 140 ℃ for 100min, continuously heating to 480 ℃ at a heating rate of 4 ℃/min, preserving heat for 80min, continuously heating to 1000 ℃ and preserving heat for 80min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing imidazole, methanol and 1-hexene according to the volume ratio of 1:1:1, heating to 50 ℃, reacting for 2 hours, and drying for 5 hours at 70 ℃ to prepare N-N-amyl imidazole; mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to a mass ratio of 1:1:18:0.05, carrying out ultrasonic treatment for 25min, heating to 100 ℃, reacting for 2h under the irradiation of an ultraviolet lamp at 300r/min, filtering, washing 3 times with acetone, and drying at 80 ℃ for 8h to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-amyl imidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to a mass ratio of 6:4, immersing the mixture in N-methyl pyrrolidone, reacting for 10 hours at 200r/min and 70 ℃, filtering, washing the mixture with N-methyl pyrrolidone, 0.08mol/L hydrogen chloride solution and methanol for 3 times in sequence, and vacuum drying the mixture at-10 ℃ for 22 hours to obtain ceramic particles for treating organic wastewater.
Example 2
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 4min at 900r/min, adding absolute ethyl alcohol with 13 times of the molar weight of the tetrabutyl titanate at a constant speed within 15min, and continuously stirring for 30min to obtain a titanium mixed solution; uniformly mixing deionized water, diethanol ammonia and absolute ethyl alcohol according to a molar ratio of 1:1:13.5, stirring for 4min at 900r/min, adding titanium mixed solution with the mass of 14 times of diethanol ammonia and ammonia water with the mass of 10 times of diethanol ammonia at a uniform speed within 9min, continuously stirring for 60min, standing for 7d, drying at 120 ℃ for 2h, heating to 250 ℃, preserving heat for 60min, continuously heating to 500 ℃ at a speed of 15 ℃/min, calcining for 2h, and crushing to 200 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to a mass ratio of 92:3:5, preparing balls with diameters of 7cm, drying at 150 ℃ for 120min, continuously heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 90min, continuously heating to 1100 ℃, and preserving heat for 90min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing imidazole, methanol and 1-hexene according to the volume ratio of 1:1:1, heating to 55 ℃, reacting for 3 hours, and drying at 75 ℃ for 6 hours to prepare N-N-amyl imidazole; mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to a mass ratio of 1:1:20:0.06, carrying out ultrasonic treatment for 30min, heating to 110 ℃, reacting for 2.5h under the irradiation of ultraviolet light at 400r/min, filtering, washing for 4 times with acetone, and drying for 9h at 90 ℃ to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-amyl imidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to the mass ratio of 7:5, immersing the ceramic in N-methyl pyrrolidone, reacting for 12 hours at the temperature of 250r/min and 80 ℃, filtering, washing for 4 times by using N-methyl pyrrolidone, 0.1mol/L hydrogen chloride solution and methanol in sequence, and vacuum drying for 23 hours at the temperature of minus 5 ℃ to prepare ceramic particles for treating organic wastewater.
Example 3
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 5min at 1000r/min, adding absolute ethyl alcohol with 14 times of the molar weight of the tetrabutyl titanate at a constant speed within 20min, and continuously stirring for 35min to obtain a titanium mixed solution; uniformly mixing deionized water, diethanol ammonia and absolute ethyl alcohol according to a molar ratio of 1:1:14, stirring for 5min at 1000r/min, adding titanium mixed solution with 15 times of diethanol ammonia mass and ammonia water with 11 times of diethanol ammonia mass at uniform speed within 10min, continuously stirring for 70min, standing for 8d, drying at 130 ℃ for 2.5h, heating to 260 ℃, preserving heat for 70min, continuously heating to 520 ℃ at a speed of 17 ℃/min, calcining for 2.5h, and crushing to 300 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to a mass ratio of 94:4:6, preparing balls with diameters of 8cm, drying at 160 ℃ for 140min, continuously heating to 520 ℃ at a heating rate of 6 ℃/min, preserving heat for 80min, continuously heating to 1200 ℃ and preserving heat for 100min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing imidazole, methanol and 1-hexene according to the volume ratio of 1:1:1, heating to 60 ℃, reacting for 4 hours, and drying at 80 ℃ for 7 hours to prepare N-N-amyl imidazole; mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to a mass ratio of 1:1:22:0.07, carrying out ultrasonic treatment for 35min, heating to 120 ℃, reacting for 3h under the irradiation of an ultraviolet lamp at 500r/min, filtering, washing for 5 times with acetone, and drying for 10h at 100 ℃ to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-amyl imidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to a mass ratio of 8:6, immersing the mixture in N-methyl pyrrolidone, reacting for 14 hours at 300r/min and 90 ℃, filtering, washing the mixture with N-methyl pyrrolidone, 0.12mol/L hydrogen chloride solution and methanol for 5 times in sequence, and vacuum drying the mixture at 0 ℃ for 24 hours to obtain ceramic particles for treating organic wastewater.
Comparative example 1
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 4min at 900r/min, adding absolute ethyl alcohol with 13 times of the molar weight of the tetrabutyl titanate at a constant speed within 15min, and continuously stirring for 30min to obtain a titanium mixed solution; uniformly mixing deionized water, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1:1:13.5, stirring for 4min at 900r/min, adding titanium mixed solution with the mass of 14 times of that of diethanol amine at a uniform speed within 9min, continuously stirring for 60min, standing for 7d, drying for 2h at 120 ℃, heating to 250 ℃, preserving heat for 60min, continuously heating to 500 ℃ at a speed of 15 ℃/min, calcining for 2h, and crushing to 200 meshes to obtain titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to a mass ratio of 92:3:5, preparing balls with diameters of 7cm, drying at 150 ℃ for 120min, continuously heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 90min, continuously heating to 1100 ℃, and preserving heat for 90min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing imidazole, methanol and 1-hexene according to the volume ratio of 1:1:1, heating to 55 ℃, reacting for 3 hours, and drying at 75 ℃ for 6 hours to prepare N-N-amyl imidazole; mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to a mass ratio of 1:1:20:0.06, carrying out ultrasonic treatment for 30min, heating to 110 ℃, reacting for 2.5h under the irradiation of ultraviolet light at 400r/min, filtering, washing for 4 times with acetone, and drying for 9h at 90 ℃ to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-amyl imidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to the mass ratio of 7:5, immersing the ceramic in N-methyl pyrrolidone, reacting for 12 hours at the temperature of 250r/min and 80 ℃, filtering, washing for 4 times by using N-methyl pyrrolidone, 0.1mol/L hydrogen chloride solution and methanol in sequence, and vacuum drying for 23 hours at the temperature of minus 5 ℃ to prepare ceramic particles for treating organic wastewater.
Comparative example 2
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 4min at 900r/min, adding absolute ethyl alcohol with 13 times of the molar weight of the tetrabutyl titanate at a constant speed within 15min, and continuously stirring for 30min to obtain a titanium mixed solution; uniformly mixing deionized water, diethanol ammonia and absolute ethyl alcohol according to a molar ratio of 1:1:13.5, stirring for 4min at 900r/min, adding titanium mixed solution with the mass of 14 times of diethanol ammonia and ammonia water with the mass of 10 times of diethanol ammonia at a uniform speed within 9min, continuously stirring for 60min, standing for 7d, drying at 120 ℃ for 2h, heating to 250 ℃, preserving heat for 60min, continuously heating to 500 ℃ at a speed of 15 ℃/min, and calcining for 2h to obtain the nitrogen-doped titanium dioxide ceramic;
(2) Mixing imidazole, methanol and 1-hexene according to the volume ratio of 1:1:1, heating to 55 ℃, reacting for 3 hours, and drying at 75 ℃ for 6 hours to prepare N-N-amyl imidazole; mixing nitrogen-doped titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to a mass ratio of 1:1:20:0.06, carrying out ultrasonic treatment for 30min, heating to 110 ℃, reacting for 2.5h under the irradiation of an ultraviolet lamp at 400r/min, filtering, washing for 4 times with acetone, and drying for 9h at 90 ℃ to obtain the chloropropyl nitrogen-doped titanium dioxide ceramic; mixing N-N-amyl imidazole and chloropropyl nitrogen-doped titanium dioxide ceramic according to the mass ratio of 7:5, immersing the mixture in N-methyl pyrrolidone, reacting for 12 hours at the temperature of 250r/min and the temperature of 80 ℃, filtering, washing the mixture with N-methyl pyrrolidone, 0.1mol/L hydrogen chloride solution and methanol for 4 times in sequence, and vacuum drying the mixture at the temperature of minus 5 ℃ for 23 hours to obtain ceramic particles for treating organic wastewater.
Comparative example 3
Ceramic particles for organic wastewater treatment and a preparation method thereof, comprising the following preparation steps:
(1) Stirring tetrabutyl titanate for 4min at 900r/min, adding absolute ethyl alcohol with 13 times of the molar weight of the tetrabutyl titanate at a constant speed within 15min, and continuously stirring for 30min to obtain a titanium mixed solution; uniformly mixing deionized water, diethanol ammonia and absolute ethyl alcohol according to a molar ratio of 1:1:13.5, stirring for 4min at 900r/min, adding titanium mixed solution with the mass of 14 times of diethanol ammonia and ammonia water with the mass of 10 times of diethanol ammonia at a uniform speed within 9min, continuously stirring for 60min, standing for 7d, drying at 120 ℃ for 2h, heating to 250 ℃, preserving heat for 60min, continuously heating to 500 ℃ at a speed of 15 ℃/min, calcining for 2h, and crushing to 200 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to the mass ratio of 92:3:5, preparing balls with the diameter of 7cm, drying at 150 ℃ for 120min, continuously heating to 500 ℃ at the heating rate of 5 ℃/min, preserving heat for 90min, continuously heating to 1100 ℃ and preserving heat for 90min, thus obtaining the ceramic particles for treating organic wastewater.
Test example 1
Organic pollutant degradation rate test
The testing method comprises the following steps: the measurement equipment was an Shimadzu UV-2700 ultraviolet spectrophotometer manufactured by Nippon electronics, inc., and the procedure was as follows: respectively preparing a Congo red solution and a2, 4-dinitrophenol solution with the concentration of 10mg/L, and adjusting the pH value to 7; placing the ceramic into a sandwich beaker, pouring a congo red solution, standing for 120min under natural light, and calculating the congo red and 2, 4-dinitrophenol degradation rate, wherein the congo red degradation rate= (congo red initial absorbance value-congo red absorbance value of 120 min)/congo red initial absorbance value is 100%, and the 2, 4-dinitrophenol is the same. The results are shown in Table 1.
TABLE 1
| Congo red solution | 2, 4-Dinitrophenol solution | |
| Example 1 | 92.3% | 91.8% |
| Example 2 | 92.8% | 92.5% |
| Example 3 | 91.9% | 92.1% |
| Comparative example 1 | 18.6% | 19.2% |
| Comparative example 2 | 72.3% | 71.9% |
| Comparative example 3 | 81.1% | 80.8% |
From comparison of experimental data of examples 1 to 3 and comparative examples 1 to 3 in Table 1, it can be found that the ceramic particles for organic wastewater treatment prepared by the invention have high degradation rate and capability of adsorbing anionic organic pollutants under natural light.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1 in table 1, it can be found that congo red and 2, 4-dinitrophenol of comparative example 1 of examples 1, 2 and 3 have high degradation rate, which indicates that nitrogen element can be doped to replace a small amount of lattice oxygen atoms in titanium dioxide, 2p orbitals of oxygen atoms will be hybridized with 2p orbitals of nitrogen atoms, so that the band gap of titanium dioxide is narrowed, the titanium dioxide has photoresponse under longer wavelength, and has certain photocatalytic activity under sunlight or visible light while the ultraviolet catalytic activity is not reduced;
From comparison of experimental data of examples 1,2 and 3 and comparative example 2, the examples 1,2 and 3 have high congo red and 2, 4-dinitrophenol degradation rates compared with the comparative example 2, which shows that the ceramic particles for treating organic wastewater are made into porous structures, so that the contact area between the ceramic particles and organic pollution wastewater can be increased, and the degradation rate of organic pollutants can be increased;
As can be found from the comparison of experimental data of examples 1,2 and 3 and comparative example 3, the congo red and 2, 4-dinitrophenol solutions of the comparative examples 1,2 and 3 have high degradation rates, which indicates that the prepared ceramic particles for treating organic wastewater are rich in imidazole ions, and the imidazole ions have better adsorption effect on anionic organic pollutants, so that the organic pollutants can be gathered on the surfaces of the ceramic particles more quickly, and the degradation rate of the organic pollutants is increased.
Claims (9)
1. The ceramic particles for treating the organic wastewater are characterized by being prepared by sequentially reacting nitrogen-doped porous titanium dioxide ceramic with (3-chloropropyl) trimethoxysilane and N-N-pentylimidazole.
2. The ceramic particle for organic wastewater treatment according to claim 1, wherein the N-pentylimidazole is prepared by reacting imidazole with 1-hexene.
3. The ceramic particles for organic wastewater treatment according to claim 1, wherein the nitrogen-doped porous titanium dioxide ceramic is prepared by mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch, pelletizing and heat treatment.
4. The ceramic particles for organic wastewater treatment according to claim 3, wherein the nitrogen-doped titanium dioxide powder is prepared by mixing tetrabutyl titanate, absolute ethyl alcohol, deionized water, aqueous ammonia and diethanol ammonia, drying, heating, calcining and pulverizing.
5. A method for producing ceramic particles for organic wastewater treatment, which can be used at least for producing ceramic particles for organic wastewater treatment according to any one of claims 1 to 4, comprising the following production steps:
(1) Mixing deionized water, diethanol amine and absolute ethyl alcohol according to a molar ratio of 1:1 (13-14), stirring for 3-5 min at a speed of 800-1000 r/min, adding titanium mixed solution with a mass of 13-15 times of that of diethanol amine and ammonia water with a mass of 9-11 times of that of diethanol amine at a constant speed of 8-10 min, continuously stirring for 50-70 min, standing for 6-8 d, drying for 1.5-2.5 h at 110-130 ℃, heating to 240-260 ℃, preserving heat for 50-70 min, continuously heating to 480-520 ℃ at a speed of 13-17 ℃/min, calcining for 1.5-2.5 h, and crushing to 100-300 meshes to obtain nitrogen-doped titanium dioxide powder;
(2) Uniformly mixing nitrogen-doped titanium dioxide powder, polyvinyl alcohol and corn starch according to the mass ratio of (90-94): (2-4): (4-6), preparing balls with the diameter of 6-8 cm, drying at 140-160 ℃ for 100-140 min, continuously heating to 480-520 ℃ at the heating rate of 4-6 ℃/min, preserving heat for 80-100 min, continuously heating to 1000-1200 ℃ and preserving heat for 80-100 min to obtain the nitrogen-doped porous titanium dioxide ceramic;
(3) Mixing nitrogen-doped porous titanium dioxide ceramic, (3-chloropropyl) trimethoxysilane, toluene and triethylamine according to the mass ratio of 1:1 (18-22) (0.05-0.07), carrying out ultrasonic treatment for 25-35 min, heating to 100-120 ℃, reacting for 2-3 h under the irradiation of an ultraviolet lamp at 300-500 r/min, filtering, washing for 3-5 times with acetone, and drying for 8-10 h at 80-100 ℃ to obtain the chloropropyl nitrogen-doped porous titanium dioxide ceramic; mixing N-N-pentylimidazole and chloropropyl nitrogen-doped porous titanium dioxide ceramic according to the mass ratio of (6-8) (4-6), immersing in N-methylpyrrolidone, reacting for 10-14 h at the temperature of 70-90 ℃ at the speed of 200-300 r/min, filtering, washing with N-methylpyrrolidone, 0.08-0.12 mol/L of hydrogen chloride solution and methanol for 3-5 times in sequence, and vacuum drying at the temperature of-10-0 ℃ for 22-24 h to obtain ceramic particles for treating organic wastewater.
6. The method for preparing ceramic particles for organic wastewater treatment according to claim 5, wherein the titanium mixed solution in the step (1) is prepared by stirring tetrabutyl titanate for 3-5 min at 800-1000 r/min, adding absolute ethyl alcohol with the molar quantity of tetrabutyl titanate being 12-14 times at a constant speed within 10-20 min, and continuing stirring for 25-35 min.
7. The method for preparing ceramic particles for organic wastewater treatment according to claim 5, wherein the N-N-pentylimidazole in the step (3) is prepared by mixing imidazole, methanol and 1-hexene according to a volume ratio of 1:1:1, heating to 50-60 ℃, reacting for 2-4 h, and drying at 70-80 ℃ for 5-7 h.
8. The method for preparing ceramic particles for organic wastewater treatment according to claim 5, wherein the reaction process of the chloropropyl nitrogen-doped porous titanium dioxide ceramic in the step (3) is as follows:
。
9. The method for preparing ceramic particles for organic wastewater treatment according to claim 5, wherein the reaction process of the N-pentylimidazole in the step (3) is as follows:
。
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