CN103111265A - Preparation method of adsorbent for removing antibiotics in water, prepared adsorbent and application thereof - Google Patents
Preparation method of adsorbent for removing antibiotics in water, prepared adsorbent and application thereof Download PDFInfo
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- CN103111265A CN103111265A CN2013100605955A CN201310060595A CN103111265A CN 103111265 A CN103111265 A CN 103111265A CN 2013100605955 A CN2013100605955 A CN 2013100605955A CN 201310060595 A CN201310060595 A CN 201310060595A CN 103111265 A CN103111265 A CN 103111265A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003242 anti bacterial agent Substances 0.000 title abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 230000003115 biocidal effect Effects 0.000 claims description 33
- 239000002250 absorbent Substances 0.000 claims description 11
- 230000002745 absorbent Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 5
- 241001553178 Arachis glabrata Species 0.000 claims description 5
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 5
- 235000018262 Arachis monticola Nutrition 0.000 claims description 5
- 235000020232 peanut Nutrition 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 12
- 230000003750 conditioning effect Effects 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 238000000855 fermentation Methods 0.000 abstract description 3
- 230000004151 fermentation Effects 0.000 abstract description 3
- 239000002657 fibrous material Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 235000015097 nutrients Nutrition 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 6
- 229930195503 Fortimicin Natural products 0.000 description 5
- BIDUPMYXGFNAEJ-APGVDKLISA-N astromicin Chemical compound O[C@@H]1[C@H](N(C)C(=O)CN)[C@@H](OC)[C@@H](O)[C@H](N)[C@H]1O[C@@H]1[C@H](N)CC[C@@H]([C@H](C)N)O1 BIDUPMYXGFNAEJ-APGVDKLISA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004098 Tetracycline Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940063650 terramycin Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a preparation method of an adsorbent for removing antibiotics in water, a prepared adsorbent and application thereof. The method comprises the steps of 1, drying, crushing and sieving a fiber material to obtain material powder; 2, adding conditioning fluid to the material powder to react for 1-5 hours at room temperature to obtain a reactant, wherein the conditioning fluid is aqueous alkali or alcoholic solution; and 3, washing and filtering the reactant, baking, crushing and sieving the solid to obtain an adsorbent product. The preparation method disclosed by the invention is low in cost, and simple in craft process, and has wide market prospect; industrialization can be carried out; the prepared adsorbent is stable in property, and good in absorption efficiency; and the adsorbent also can be used as fuel, a fermentation substrate adjuster, or a nutrient source of special microorganism after being used. Therefore, secondary pollution is avoided to a great extent, and regeneration does not need to be considered.
Description
Technical field
The present invention relates to a kind of antibiotic absorbent preparation method in removal water, make adsorbent and application, belong to technical field of waste water processing.
Background technology
In China, day by day serious by the environmental pollution that abuse of antibiotics causes.The multiple industries such as medical treatment, pharmacy, livestock and poultry and aquaculture all can produce and contain antibiotic waste water.Antibiotic existence detected at present in soil, surface water and groundwater.Containing hard-degraded substance in antibiotic waste water and have bio-toxicity, is the complicated organic wastewater than difficult degradation.These residual antibiotics not only cause harmful effect to ecological environment, also may jeopardize health by the transmission of food chain.
At present, be main to the processing of antibiotic waste water mainly with biodegradation technique, its investment and processing cost are higher, and waste water actual treatment rate is but very low, can not efficiently and economically remove the antibiotic in water.Application number is that 201110112108.6 Chinese invention patent application discloses a kind of active carbon of the KOH of utilization activation as the method for sorbent treatment antibiotic waste water.Although the method can effectively be processed antibiotic waste water, but have the following disadvantages: (1) is take commercial active carbon as raw material, need to use nitrogen, deionized water and the reaction temperature up to 850 ℃ in active carbon activation process, these have improved undoubtedly production cost and have increased energy consumption; (2) complicated process of preparation; (3) reclaim difficulty, regeneration cost is high, is difficult to sustainable use.Therefore, need to research and develop a kind of antibiotic adsorbent simple, with low cost for preparing.
Summary of the invention
Technical problem to be solved by this invention is: the problem for prior art exists, and a kind of antibiotic absorbent preparation method in removal water is provided, makes adsorbent and application, this adsorbent can be removed antibiotic in water.
The technology of the present invention design is as follows:
Contain abundant natural fiber material in the agricultural byproducts refuse, if can adopt simple processing method makes these natural fiber materials to antibiotic high-efficiency adsorbent, alternative traditional active carbon is used for containing antibiotic wastewater treatment, simplifies technique, reduces costs.Simultaneously, also can realize the secondary resource utilization to the agricultural byproducts refuse, both alleviate environmental pollution, can also improve resource utilization.
The technical scheme that the present invention solves its technical problem is as follows:
In a kind of removal water, antibiotic absorbent preparation method, is characterized in that, comprises the following steps:
The first step, fibrous raw material is dry, pulverize, sieve, get material powder;
Second step, add treatment fluid in material powder, reacted under room temperature 1～5 hour, get reactant; Described treatment fluid is aqueous slkali or alcoholic solution;
The 3rd goes on foot, reactant is washed, filters to get solid, and solid is dried, pulverizes, sieved, and namely gets the adsorbent finished product.
The technical scheme that the inventive method is further perfect is as follows:
Preferably, in the first step, described fibrous raw material is wood chip, peanut shell, pericarp, straw, straw, corncob, bagasse, bark or leaf.
Preferably, in the first step, described drying condition is: 55 ℃-65 ℃ of baking temperatures, dry to constant weight; The described condition of sieving was 20～100 mesh sieves.
Preferably, the aqueous slkali in second step is that mass concentration is NaOH solution or the KOH solution of 2-20%; Alcoholic solution is that mass concentration is the ethanolic solution of 76-95%.
Preferably, in second step, the w/v of described material powder and treatment fluid is 1:25-1:100.
Preferably, in the 3rd step, described wash conditions is: adopt the distilled water washing until the rear liquid of washing is neutral; Described drying condition is: 55 ℃-65 ℃ of bake out temperatures, dry to constant weight; The described condition of sieving was 20～100 mesh sieves.
The present invention also provides a kind of adsorbent that adopts above-mentioned preparation method to make.
In addition, the present invention also provides above-mentioned adsorbent to be used for removing the water Antibiotic use.
It is that raw material prepares adsorbent that the inventive method is used the agricultural byproducts refuse, with low cost, has realized simultaneously the secondary resource utilization to the agricultural byproducts refuse, alleviates environmental pollution.Absorbent preparation method of the present invention is carried out at normal temperatures, and technical process is simple, and is not high to equipment requirement, can implement industrialization, has wide market prospects.Adsorbent of the present invention can also be used as the nutrient source of fuel, fermentation substrate conditioning agent or extraordinary microorganism etc. after use, avoided to a great extent secondary pollution and need not to consider regeneration.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.But the invention is not restricted to given example.
Antibiotic adsorbent in water is removed in embodiment 1 preparation
The first step, fibrous raw material is dry, pulverize, sieve, get material powder;
Wherein, fibrous raw material is wood chip, peanut shell, pericarp, straw, straw, corncob, bagasse, bark or leaf; Drying condition is: 55 ℃-65 ℃ of baking temperatures, dry to constant weight (preferred 5～12 hours drying times); The condition of sieving was 20～100 mesh sieves.
Second step, add treatment fluid in material powder, reacted under room temperature 1～5 hour, get reactant; Described treatment fluid is aqueous slkali or alcoholic solution;
Wherein, aqueous slkali is that mass concentration is NaOH solution or the KOH solution of 2-20%; Alcoholic solution is that mass concentration is the ethanolic solution of 76-95%; The w/v of material powder and treatment fluid is 1:25-1:100.
The 3rd goes on foot, reactant is washed, filters to get solid, and solid is dried, pulverizes, sieved, and namely gets the adsorbent finished product.
Wherein, wash conditions is: adopt the distilled water washing until the rear liquid of washing is neutral (preferred washing times 5-10 time at least, each consumption 250～500ml); Drying condition is: 55 ℃-65 ℃ of bake out temperatures, dry to constant weight (preferred drying time 5～12 hours); The condition of sieving was 20～100 mesh sieves.
Concrete preparation case is for example shown in following each table:
Table 1 first step parameter
Table 2 second step parameter
The 3rd step of table 3 parameter
Embodiment 2 embodiment 1 make adsorbent and remove antibiotic Performance Detection in water
Preparation 100mL contains the simulated wastewater of terramycin, tetracycline, fortimicin, and wherein three kinds of antibiotic initial concentrations are 200mg/L, and pH is 7.Each drops into the 3g adsorbent, and under room temperature condition, the lucifuge oscillating reactions after 20 hours, detects antibiotic clearance in waste water.
It is as shown in the table that embodiment 1 each case is removed antibiotic result.
Table 4 is removed antibiotic result in water
In order to compare, get fibrous raw material---peanut shell, the wood chip processed without embodiment 1 method, directly adsorb antibiotic, adsorption conditions is as mentioned above.Experimental result is: peanut shell is respectively 19.70%, 31.71%, 67.31% to the clearance of terramycin, tetracycline, fortimicin, and wood chip is respectively 15.22%, 23.50%, 64.45% to the clearance of terramycin, tetracycline, fortimicin.
This shows, the adsorbent of embodiment 1 preparation is compared with undressed fibrous raw material, and antibiotic adsorption capacity is significantly improved.Embodiment 1 makes adsorbent can remove antibiotic in water, the highest to the clearance of fortimicin.It is pointed out that embodiment 1 makes adsorbent with low cost, can process waste water with higher input ratio as required in actual use, obtain the antibiotic removal effect that suits the requirements.
During actual the use, first pH value of waste water is adjusted to 5～7, every 100ml waste water drops into 0.5～3g adsorbent, and under room temperature condition, the lucifuge oscillating reactions got final product in 10～20 hours.
Compared with prior art, embodiment 1 makes adsorbent and has following advantage:
1, with low cost.The raw material of the present embodiment are wood chip, peanut shell etc., belong to the agricultural byproducts refuse, have wide material sources, the advantage such as cheap, renewable.
2, preparation process is simple, all carries out at normal temperatures, and energy consumption is low, and is not high to equipment requirement, can implement industrialization, has wide market prospects.
3, only add conventional alkali or alcohol in preparation process, can not work the mischief to environment; Do not have a large amount of organic pigment strippings after processing waste water and make the water variable color, need not the subsequent treatment link; Can also act as a fuel after adsorbent uses, the nutrient source of fermentation substrate conditioning agent or extraordinary microorganism etc., avoided to a great extent secondary pollution and need not to consider regeneration.
4, the large and stable performance of adsorption capacity, applied widely.Multiple Classes of Antibiotics in adsorbable water is affected by the factors such as adsorption temp, pH less, and under certain condition, the clearance of tetracycline and fortimicin can reach 80 ~ 90%.
5, has good economy and environment benefit.Raw material of the present invention derive from the agricultural byproducts refuse, are used for substituting the adsorbent of traditional costliness as a kind of high-efficiency adsorbent of cheapness, not only can alleviate environmental pollution, can also improve resource utilization simultaneously.
Claims (8)
1. remove antibiotic absorbent preparation method in water for one kind, it is characterized in that, comprise the following steps:
The first step, fibrous raw material is dry, pulverize, sieve, get material powder;
Second step, add treatment fluid in material powder, reacted under room temperature 1～5 hour, get reactant; Described treatment fluid is aqueous slkali or alcoholic solution;
The 3rd goes on foot, reactant is washed, filters to get solid, and solid is dried, pulverizes, sieved, and namely gets the adsorbent finished product.
2. remove according to claim 1 antibiotic absorbent preparation method in water, it is characterized in that, in the first step, described fibrous raw material is wood chip, peanut shell, pericarp, straw, straw, corncob, bagasse, bark or leaf.
3. remove according to claim 2 antibiotic absorbent preparation method in water, it is characterized in that, in the first step, described drying condition is: 55 ℃-65 ℃ of baking temperatures, dry to constant weight; The described condition of sieving was 20～100 mesh sieves.
4. remove according to claim 3 antibiotic absorbent preparation method in water, it is characterized in that, the aqueous slkali in second step is that mass concentration is NaOH solution or the KOH solution of 2-20%; Alcoholic solution is that mass concentration is the ethanolic solution of 76-95%.
5. remove according to claim 4 antibiotic absorbent preparation method in water, it is characterized in that, in second step, the w/v of described material powder and treatment fluid is 1:25-1:100.
6. remove according to claim 5 antibiotic absorbent preparation method in water, it is characterized in that, in the 3rd step, described wash conditions is: adopt the distilled water washing until the rear liquid of washing is neutral; Described drying condition is: 55 ℃-65 ℃ of bake out temperatures, dry to constant weight; The described condition of sieving was 20～100 mesh sieves.
7. adsorbent that adopts the described preparation method of claim 1 to 6 any one to make.
8. the described adsorbent of claim 7 is used for removing the water Antibiotic use.
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| CN201310060595.5A CN103111265B (en) | 2013-02-27 | 2013-02-27 | Preparation method of adsorbent for removing antibiotics in water, prepared adsorbent and application thereof |
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| CN201310060595.5A CN103111265B (en) | 2013-02-27 | 2013-02-27 | Preparation method of adsorbent for removing antibiotics in water, prepared adsorbent and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709498A (en) * | 2016-02-29 | 2016-06-29 | 徐州深蓝新材料科技有限公司 | Graphene carbon filtering material and preparation method thereof |
| CN106925232A (en) * | 2017-05-11 | 2017-07-07 | 北京益净环保设备科技有限公司 | For the modified pine branch adsorbent of Adsorption polymyxins |
| CN106955673A (en) * | 2017-05-11 | 2017-07-18 | 北京益净环保设备科技有限公司 | Modified peanut adsorbent for Adsorption clindamycin |
| CN106975460A (en) * | 2017-05-11 | 2017-07-25 | 北京益净环保设备科技有限公司 | Modified corn core adsorbent for Adsorption kanamycins |
| CN106975459A (en) * | 2017-05-11 | 2017-07-25 | 北京益净环保设备科技有限公司 | Modification cotton stem adsorbent for Adsorption pyrazinamide |
| CN107008234A (en) * | 2017-05-11 | 2017-08-04 | 北京益净环保设备科技有限公司 | Modification walnut shell adsorbent for Adsorption mafenide |
| CN108160052A (en) * | 2018-01-22 | 2018-06-15 | 桐源（上海）网络技术有限公司 | A kind of preparation method of highly effective air sorbing material |
| CN109292885A (en) * | 2018-10-30 | 2019-02-01 | 四川施邦威生物科技发展有限公司 | A kind of poultry farming waste water treating agent |
| CN110560007A (en) * | 2019-08-27 | 2019-12-13 | 湖南君悦达科技有限公司 | Preparation process of chloramphenicol adsorbent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709498A (en) * | 2016-02-29 | 2016-06-29 | 徐州深蓝新材料科技有限公司 | Graphene carbon filtering material and preparation method thereof |
| CN106925232A (en) * | 2017-05-11 | 2017-07-07 | 北京益净环保设备科技有限公司 | For the modified pine branch adsorbent of Adsorption polymyxins |
| CN106955673A (en) * | 2017-05-11 | 2017-07-18 | 北京益净环保设备科技有限公司 | Modified peanut adsorbent for Adsorption clindamycin |
| CN106975460A (en) * | 2017-05-11 | 2017-07-25 | 北京益净环保设备科技有限公司 | Modified corn core adsorbent for Adsorption kanamycins |
| CN106975459A (en) * | 2017-05-11 | 2017-07-25 | 北京益净环保设备科技有限公司 | Modification cotton stem adsorbent for Adsorption pyrazinamide |
| CN107008234A (en) * | 2017-05-11 | 2017-08-04 | 北京益净环保设备科技有限公司 | Modification walnut shell adsorbent for Adsorption mafenide |
| CN108160052A (en) * | 2018-01-22 | 2018-06-15 | 桐源（上海）网络技术有限公司 | A kind of preparation method of highly effective air sorbing material |
| CN108160052B (en) * | 2018-01-22 | 2020-10-30 | 桐源（上海）网络技术有限公司 | Preparation method of efficient air adsorption material |
| CN109292885A (en) * | 2018-10-30 | 2019-02-01 | 四川施邦威生物科技发展有限公司 | A kind of poultry farming waste water treating agent |
| CN110560007A (en) * | 2019-08-27 | 2019-12-13 | 湖南君悦达科技有限公司 | Preparation process of chloramphenicol adsorbent |
| CN110560007B (en) * | 2019-08-27 | 2020-10-09 | 湖南君悦达科技有限公司 | Preparation process of chloramphenicol adsorbent |
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