技术领域technical field
本发明涉及一种生态吸附柱的制备方法。The invention relates to a preparation method of an ecological adsorption column.
背景技术Background technique
随着养殖业由传统的小规模生产向集约化、规模化的生产模式转变，伴随而来的是富含碳氮磷的粪便和冲栏废水的过度集中，也给环境造成极大的压力，在许多地区，畜禽养殖带来的污染已经或正在成为当地主要污染源，因此针对这些问题，近年来国家出台了一系列政策大力加强规模化畜禽养殖场大中型沼气工程的建设。大中型沼气工程在处理畜禽废弃物、生产沼气的同时，也会大量的副产物一沼液。因为经过厌氧发酵，原水中易降解和慢降解COD逐渐被利用，含量逐渐减少，而氮、磷与有机物去除不同步，导致沼液出水中污染物之间的比例变化，造成了氮、磷的累积，且C/N失调，可生化性差，NH/-N/TN高，不利于直接使生物处理。目前，废水的深度处理方法主要有物理法、化学法、生物法。物理法主要包括膜分离、活性炭吸附等。膜分离法具有去除效果好、出水水质稳定等优点，但其工程投资一般较大、运行费用亦较高，且膜易堵塞、老化，需定期更换，一般仅适用于处理高浓度有机工业废水；活性炭吸附法处理效果亦较好，但活性炭价格较高(目前市场售价4000-8000元/吨)，吸附容量有限，容易吸附饱和，对其进行再生的费用也较大。化学法主要有臭氧氧化法、芬顿试剂法、电化学氧化法等，这样方法虽然有一定的去除效果，但同样因试剂成本高或电耗高，难以应用于大水量养殖废水的深度处理。With the transformation of the aquaculture industry from traditional small-scale production to intensive and large-scale production, it is accompanied by excessive concentration of carbon, nitrogen, and phosphorus-rich manure and fence waste water, which also puts great pressure on the environment. In many areas, the pollution caused by livestock and poultry breeding has become or is becoming the main local pollution source. Therefore, in response to these problems, the state has issued a series of policies in recent years to vigorously strengthen the construction of large and medium-sized biogas projects for large-scale livestock and poultry farms. When large and medium-sized biogas projects process livestock and poultry waste and produce biogas, a large amount of by-product, biogas slurry, will also be produced. Because after anaerobic fermentation, the easily degradable and slowly degradable COD in the raw water is gradually utilized, and the content gradually decreases, while the removal of nitrogen, phosphorus and organic matter is not synchronized, resulting in a change in the ratio of pollutants in the biogas slurry effluent, resulting in nitrogen, phosphorus Accumulation, and C/N imbalance, poor biodegradability, high NH/-N/TN, which is not conducive to direct biological treatment. At present, the advanced treatment methods of wastewater mainly include physical, chemical and biological methods. Physical methods mainly include membrane separation and activated carbon adsorption. Membrane separation method has the advantages of good removal effect and stable effluent quality, but its engineering investment is generally large and operating costs are also high, and the membrane is easy to clog and aging, and needs to be replaced regularly. Generally, it is only suitable for treating high-concentration organic industrial wastewater; The treatment effect of activated carbon adsorption method is also better, but the price of activated carbon is relatively high (the current market price is 4000-8000 yuan/ton), the adsorption capacity is limited, it is easy to absorb saturation, and the cost of its regeneration is also relatively high. Chemical methods mainly include ozone oxidation, Fenton’s reagent method, electrochemical oxidation, etc. Although this method has a certain removal effect, it is also difficult to apply to the advanced treatment of large-scale aquaculture wastewater due to the high cost of reagents or high power consumption.
目前国内外利用生物质材料如秸秆材料、稻壳、木屑等开发功能吸附质材料的研究报道较多，利用生物质材料制备吸附剂可极大的降低吸附剂的成本，沸石具有吸附性、离子交换性、催化和耐酸耐热等性能，且价格低廉，因此被广泛用作吸附剂，此外沸石施入土壤后，能改善土壤的物理性况，有保肥保水性能。因此本发明的生态吸附柱的填充材料，吸附沼液废水中的N、P等营养物质后，无需再生，可直接作为土壤改良剂出售或使用。At present, there are many research reports on the development of functional adsorbent materials using biomass materials such as straw materials, rice husks, and wood chips at home and abroad. The use of biomass materials to prepare adsorbents can greatly reduce the cost of adsorbents. Zeolite has adsorptive, ion- Exchangeability, catalysis, acid and heat resistance, and low price, so it is widely used as an adsorbent. In addition, after zeolite is applied to the soil, it can improve the physical properties of the soil, and has the ability to retain fertilizer and water. Therefore, the filling material of the ecological adsorption column of the present invention can be directly sold or used as a soil improver without regeneration after absorbing nutrients such as N and P in biogas slurry wastewater.
发明内容Contents of the invention
本发明的目的是要解决现有处理奶牛养殖废水的方法存在运行成本高，处理效果不佳，不合适用于深度处理奶牛养殖废水的问题，而提供一种处理奶牛养殖废水专用的生态吸附柱的制备方法。The purpose of the present invention is to solve the problems of high operating cost, poor treatment effect and unsuitability for advanced treatment of dairy wastewater in the existing method for treating dairy wastewater, and to provide a special ecological adsorption column for treating dairy wastewater Preparation.
一种处理奶牛养殖废水专用的生态吸附柱的制备方法，具体是按以下步骤制备的：A preparation method of an ecological adsorption column specially used for treating dairy farming wastewater, specifically prepared according to the following steps:
一、切割：去除玉米秸秆的枝叶和玉米秸秆芯，再将玉米秸秆进行切割，得到长度为2cm～4cm的玉米秸秆；使用蒸馏水对长度为2cm～4cm的玉米秸秆进行洗涤5次～8次，再在温度为45℃～55℃下干燥8h～12h，得到干燥的长度为2cm～4cm的玉米秸秆；1. Cutting: remove the branches and leaves of the corn stalks and the core of the corn stalks, and then cut the corn stalks to obtain corn stalks with a length of 2cm to 4cm; use distilled water to wash the corn stalks with a length of 2cm to 4cm for 5 to 8 times, Then drying at a temperature of 45° C. to 55° C. for 8 hours to 12 hours to obtain dry corn stalks with a length of 2 cm to 4 cm;
二、浸泡：将干燥的长度为2cm～4cm的玉米秸秆浸泡在质量分数为8％～15％的硫酸溶液中15min～20min，得到硫酸溶液浸泡后的玉米秸秆；将硫酸溶液浸泡后的玉米秸秆浸泡在质量分数为30％～50％的磷酸钾溶液中40min～50min，得到磷酸钾溶液浸泡后的玉米秸秆；将磷酸钾溶液浸泡后的玉米秸秆置于温度为105℃的烘箱中干燥3h～4h，再置于马弗炉中，再将马弗炉从室温以升温速率为10℃/min，并在温度为400℃～450℃活化30min～60min；再将温度为400℃～450℃马弗炉以升温速率为10℃/min升温至600℃，温度为600℃下活化10min～30min，再自然冷却至室温，再以蒸馏水为清洗剂进行洗涤3次～5次，再在温度为45℃～50℃下干燥8h～12h，再过5目～10目筛，得到粒径为2mm～4mm的颗粒活性炭；2. Soaking: Soak dry corn stalks with a length of 2cm to 4cm in a sulfuric acid solution with a mass fraction of 8% to 15% for 15min to 20min to obtain corn stalks soaked in sulfuric acid solution; soak corn stalks in sulfuric acid solution Soak in a potassium phosphate solution with a mass fraction of 30% to 50% for 40 to 50 minutes to obtain corn stalks soaked in the potassium phosphate solution; place the corn stalks soaked in the potassium phosphate solution in an oven at a temperature of 105°C to dry for 3 hours to 4h, then placed in the muffle furnace, and then the muffle furnace was activated from room temperature at a heating rate of 10°C/min, and activated at a temperature of 400°C to 450°C for 30min to 60min; Furnace is heated up to 600°C at a heating rate of 10°C/min, activated at 600°C for 10min to 30min, then cooled to room temperature naturally, then washed 3 to 5 times with distilled water as a cleaning agent, and then cleaned at a temperature of 45 Dry at ℃～50℃ for 8h～12h, and then pass through a 5-10 mesh sieve to obtain granular activated carbon with a particle size of 2mm-4mm;
三、制备吸附纤维素分解酶的活性炭：将粒径为2mm～4mm的颗粒活性炭加入到温度为20℃～60℃的纤维素分解酶酶液中，再利用震荡器震荡5h～8h，再静置12h～13h，再在离心速度为5000r/min～5500r/min下离心处理10min～15min，弃去上清液，得到吸附纤维素分解酶的活性炭；3. Preparation of activated carbon for adsorbing cellulolytic enzymes: Add granular activated carbon with a particle size of 2mm to 4mm into the cellulolytic enzyme solution at a temperature of 20°C to 60°C, then use an oscillator to shake for 5h to 8h, and then statically Set it aside for 12h to 13h, then centrifuge at a centrifugal speed of 5000r/min to 5500r/min for 10min to 15min, discard the supernatant, and obtain activated carbon that adsorbs cellulolytic enzymes;
步骤三中所述的纤维素分解酶酶液的pH值为4.3～6.5；所述的纤维素分解酶酶液中纤维素分解酶的酶活度为5unit/mL～10unit/mL；The pH value of the cellulolytic enzyme liquid described in step 3 is 4.3-6.5; the enzyme activity of the cellulolytic enzyme in the cellulolytic enzyme liquid is 5 unit/mL-10 unit/mL;
步骤三中所述的粒径为2mm～4mm的颗粒活性炭的质量与纤维素分解酶酶液的体积比为(1g～1.5g):5mL；The volume ratio of the mass of granular activated carbon with a particle diameter of 2 mm to 4 mm and the cellulolytic enzyme liquid described in step 3 is (1 g to 1.5 g): 5 mL;
四、将吸附纤维素分解酶的活性炭加入到质量分数为2％的海藻酸钠溶液中，在搅拌速度为120r/min～150r/min的条件下搅拌60min～80min，再在搅拌速度为10r/min和10滴/min～15滴/min的滴加速度下滴加质量分数为1％的氯化钙溶液至得到直径为3mm～5mm凝胶珠，停止搅拌和滴加质量分数为1％的氯化钙溶液；再将得到的直径为3mm～5mm的凝胶珠在温度为4℃～5℃下静置12h～13h，再使用蒸馏水进行洗涤3次～4次，再进行滤干，得到固定了混合酶的活性炭；4. Add activated carbon that absorbs cellulolytic enzymes into a sodium alginate solution with a mass fraction of 2%, stir for 60min to 80min at a stirring speed of 120r/min to 150r/min, and then stir at a stirring speed of 10r/min Min and 10 drops/min to 15 drops/min dropwise add calcium chloride solution with a mass fraction of 1% to obtain gel beads with a diameter of 3 mm to 5 mm, stop stirring and dropwise add a mass fraction of 1% chlorine Calcium solution; then the obtained gel beads with a diameter of 3 mm to 5 mm were left to stand at a temperature of 4°C to 5°C for 12h to 13h, then washed with distilled water for 3 to 4 times, and then filtered to dry to obtain a fixed Activated carbon with mixed enzymes;
步骤四中所述的吸附纤维素分解酶的活性炭的质量与质量分数为2％的海藻酸钠溶液的体积比为100g:500mL；The mass fraction of the activated carbon for adsorbing cellulolytic enzymes described in step 4 is 100g:500mL with a mass fraction of 2% sodium alginate solution;
五、将天然沸石进行粉碎和筛分，得到粒径小于1.5cm的沸石；再使用质量分数为2％的硝酸对粒径小于1.5cm的沸石洗涤3次～5次，再将清洗后的粒径小于1.5cm的沸石浸泡在质量分数为2％的硝酸中20min～30min，得到硝酸浸泡后的沸石；再使用蒸馏水对硝酸浸泡后的沸石进行清洗，至清洗液的pH值为6.5～7.5，再在温度为90℃～95℃下干燥3h～4h；得到处理后的沸石；5. Grinding and screening the natural zeolite to obtain zeolite with a particle size of less than 1.5 cm; then use nitric acid with a mass fraction of 2% to wash the zeolite with a particle size of less than 1.5 cm for 3 to 5 times, and then wash the zeolite with a particle size of less than 1.5 cm. The zeolite whose diameter is less than 1.5cm is soaked in nitric acid with a mass fraction of 2% for 20min to 30min to obtain the zeolite soaked in nitric acid; then use distilled water to clean the zeolite soaked in nitric acid until the pH value of the cleaning solution is 6.5 to 7.5, Then dry at a temperature of 90°C to 95°C for 3h to 4h; obtain the treated zeolite;
六、装柱：首先将透水垫片放入到吸附柱中，再加入处理后的沸石，至吸附柱高度的25％～40％处；再加入固定了混合酶的活性炭，至吸附柱高度的60％～70％；再加入处理后的沸石至吸附柱高度的90％～100％，得到处理奶牛养殖废水专用的生态吸附柱。6. Column packing: first put the water-permeable gasket into the adsorption column, then add the treated zeolite to 25% to 40% of the height of the adsorption column; then add activated carbon with fixed mixed enzymes to the height of the adsorption column 60% to 70%; then add treated zeolite to 90% to 100% of the height of the adsorption column to obtain an ecological adsorption column dedicated to treating dairy cow breeding wastewater.
本发明的优点：Advantages of the present invention:
一、本发明利用玉米秸秆制备活性炭作为复合酶体系固定的载体以及天然沸石作为填料制备奶牛养殖废水专用的生态吸附柱；本发明利用活性炭及沸石的表面多孔性和表面官能团的存在对养殖废水厌氧发酵后产生的沼液中溶解性有机物、氮、磷进行有效吸附，同时利用固定化酶对废水中的纤维素及有机污染物进行降解；本发明制备的生态吸附柱达到饱和吸附状态后，可用于退化土壤，如盐碱土的改良。1. The present invention uses corn stalks to prepare activated carbon as a fixed carrier for the composite enzyme system and natural zeolite as a filler to prepare a dedicated ecological adsorption column for dairy farming wastewater; The dissolved organic matter, nitrogen, and phosphorus in the biogas slurry produced after oxygen fermentation are effectively adsorbed, and the cellulose and organic pollutants in the wastewater are degraded by using immobilized enzymes; after the ecological adsorption column prepared by the present invention reaches a saturated adsorption state, It can be used for the improvement of degraded soil, such as saline-alkali soil.
本发明制备的生态吸附柱适用于处理奶牛养殖废水。The ecological adsorption column prepared by the invention is suitable for treating dairy cow breeding wastewater.
附图说明Description of drawings
图1为不同材质对氨氮的吸附曲线；图1中1为沸石，2为秸秆炭，3为瓜子炭，4为花生炭；Figure 1 shows the adsorption curves of different materials for ammonia nitrogen; in Figure 1, 1 is zeolite, 2 is straw charcoal, 3 is melon seed charcoal, and 4 is peanut charcoal;
图2为试验一制备的得到处理奶牛养殖废水专用的生态吸附柱对氨氮的去除效果图。Figure 2 is a diagram showing the removal effect of ammonia nitrogen by the eco-adsorption column specially prepared for the treatment of dairy cow breeding wastewater prepared in Experiment 1.
具体实施方式Detailed ways
具体实施方式一：本实施方式是一种处理奶牛养殖废水专用的生态吸附柱的制备方法具体是按以下步骤制备的：Embodiment 1: This embodiment is a method for preparing an eco-adsorption column dedicated to treating dairy cow breeding wastewater, which is specifically prepared according to the following steps:
一、切割：去除玉米秸秆的枝叶和玉米秸秆芯，再将玉米秸秆进行切割，得到长度为2cm～4cm的玉米秸秆；使用蒸馏水对长度为2cm～4cm的玉米秸秆进行洗涤5次～8次，再在温度为45℃～55℃下干燥8h～12h，得到干燥的长度为2cm～4cm的玉米秸秆；1. Cutting: remove the branches and leaves of the corn stalks and the core of the corn stalks, and then cut the corn stalks to obtain corn stalks with a length of 2cm to 4cm; use distilled water to wash the corn stalks with a length of 2cm to 4cm for 5 to 8 times, Then drying at a temperature of 45° C. to 55° C. for 8 hours to 12 hours to obtain dry corn stalks with a length of 2 cm to 4 cm;
二、浸泡：将干燥的长度为2cm～4cm的玉米秸秆浸泡在质量分数为8％～15％的硫酸溶液中15min～20min，得到硫酸溶液浸泡后的玉米秸秆；将硫酸溶液浸泡后的玉米秸秆浸泡在质量分数为30％～50％的磷酸钾溶液中40min～50min，得到磷酸钾溶液浸泡后的玉米秸秆；将磷酸钾溶液浸泡后的玉米秸秆置于温度为105℃的烘箱中干燥3h～4h，再置于马弗炉中，再将马弗炉从室温以升温速率为10℃/min，并在温度为400℃～450℃活化30min～60min；再将温度为400℃～450℃马弗炉以升温速率为10℃/min升温至600℃，温度为600℃下活化10min～30min，再自然冷却至室温，再以蒸馏水为清洗剂进行洗涤3次～5次，再在温度为45℃～50℃下干燥8h～12h，再过5目～10目筛，得到粒径为2mm～4mm的颗粒活性炭；2. Soaking: Soak dry corn stalks with a length of 2cm to 4cm in a sulfuric acid solution with a mass fraction of 8% to 15% for 15min to 20min to obtain corn stalks soaked in sulfuric acid solution; soak corn stalks in sulfuric acid solution Soak in a potassium phosphate solution with a mass fraction of 30% to 50% for 40 to 50 minutes to obtain corn stalks soaked in the potassium phosphate solution; place the corn stalks soaked in the potassium phosphate solution in an oven at a temperature of 105°C to dry for 3 hours to 4h, then placed in the muffle furnace, and then the muffle furnace was activated from room temperature at a heating rate of 10°C/min, and activated at a temperature of 400°C to 450°C for 30min to 60min; Furnace is heated up to 600°C at a heating rate of 10°C/min, activated at 600°C for 10min to 30min, then cooled to room temperature naturally, then washed 3 to 5 times with distilled water as a cleaning agent, and then cleaned at a temperature of 45 Dry at ℃～50℃ for 8h～12h, and then pass through a 5-10 mesh sieve to obtain granular activated carbon with a particle size of 2mm-4mm;
三、制备吸附纤维素分解酶的活性炭：将粒径为2mm～4mm的颗粒活性炭加入到温度为20℃～60℃的纤维素分解酶酶液中，再利用震荡器震荡5h～8h，再静置12h～13h，再在离心速度为5000r/min～5500r/min下离心处理10min～15min，弃去上清液，得到吸附纤维素分解酶的活性炭；3. Preparation of activated carbon for adsorbing cellulolytic enzymes: Add granular activated carbon with a particle size of 2mm to 4mm into the cellulolytic enzyme solution at a temperature of 20°C to 60°C, then use an oscillator to shake for 5h to 8h, and then statically Set it aside for 12h to 13h, then centrifuge at a centrifugal speed of 5000r/min to 5500r/min for 10min to 15min, discard the supernatant, and obtain activated carbon that adsorbs cellulolytic enzymes;
步骤三中所述的纤维素分解酶酶液的pH值为4.3～6.5；所述的纤维素分解酶酶液中纤维素分解酶的酶活度为5unit/mL～10unit/mL；The pH value of the cellulolytic enzyme liquid described in step 3 is 4.3-6.5; the enzyme activity of the cellulolytic enzyme in the cellulolytic enzyme liquid is 5 unit/mL-10 unit/mL;
步骤三中所述的粒径为2mm～4mm的颗粒活性炭的质量与纤维素分解酶酶液的体积比为(1g～1.5g):5mL；The volume ratio of the mass of granular activated carbon with a particle diameter of 2 mm to 4 mm and the cellulolytic enzyme liquid described in step 3 is (1 g to 1.5 g): 5 mL;
四、将吸附纤维素分解酶的活性炭加入到质量分数为2％的海藻酸钠溶液中，在搅拌速度为120r/min～150r/min的条件下搅拌60min～80min，再在搅拌速度为10r/min和10滴/min～15滴/min的滴加速度下滴加质量分数为1％的氯化钙溶液至得到直径为3mm～5mm凝胶珠，停止搅拌和滴加质量分数为1％的氯化钙溶液；再将得到的直径为3mm～5mm的凝胶珠在温度为4℃～5℃下静置12h～13h，再使用蒸馏水进行洗涤3次～4次，再进行滤干，得到固定了混合酶的活性炭；4. Add activated carbon that absorbs cellulolytic enzymes into a sodium alginate solution with a mass fraction of 2%, stir for 60min to 80min at a stirring speed of 120r/min to 150r/min, and then stir at a stirring speed of 10r/min Min and 10 drops/min to 15 drops/min dropwise add calcium chloride solution with a mass fraction of 1% to obtain gel beads with a diameter of 3 mm to 5 mm, stop stirring and dropwise add a mass fraction of 1% chlorine Calcium solution; then the obtained gel beads with a diameter of 3 mm to 5 mm were left to stand at a temperature of 4°C to 5°C for 12h to 13h, then washed with distilled water for 3 to 4 times, and then filtered to dry to obtain a fixed Activated carbon with mixed enzymes;
步骤四中所述的吸附纤维素分解酶的活性炭的质量与质量分数为2％的海藻酸钠溶液的体积比为100g:500mL；The mass fraction of the activated carbon for adsorbing cellulolytic enzymes described in step 4 is 100g:500mL with a mass fraction of 2% sodium alginate solution;
五、将天然沸石进行粉碎和筛分，得到粒径小于1.5cm的沸石；再使用质量分数为2％的硝酸对粒径小于1.5cm的沸石洗涤3次～5次，再将清洗后的粒径小于1.5cm的沸石浸泡在质量分数为2％的硝酸中20min～30min，得到硝酸浸泡后的沸石；再使用蒸馏水对硝酸浸泡后的沸石进行清洗，至清洗液的pH值为6.5～7.5，再在温度为90℃～95℃下干燥3h～4h；得到处理后的沸石；5. Grinding and screening the natural zeolite to obtain zeolite with a particle size of less than 1.5 cm; then use nitric acid with a mass fraction of 2% to wash the zeolite with a particle size of less than 1.5 cm for 3 to 5 times, and then wash the zeolite with a particle size of less than 1.5 cm. The zeolite whose diameter is less than 1.5cm is soaked in nitric acid with a mass fraction of 2% for 20min to 30min to obtain the zeolite soaked in nitric acid; then use distilled water to clean the zeolite soaked in nitric acid until the pH value of the cleaning solution is 6.5 to 7.5, Then dry at a temperature of 90°C to 95°C for 3h to 4h; obtain the treated zeolite;
六、装柱：首先将透水垫片放入到吸附柱中，再加入处理后的沸石，至吸附柱高度的25％～40％处；再加入固定了混合酶的活性炭，至吸附柱高度的60％～70％；再加入处理后的沸石至吸附柱高度的90％～100％，得到处理奶牛养殖废水专用的生态吸附柱。6. Column packing: first put the water-permeable gasket into the adsorption column, then add the treated zeolite to 25% to 40% of the height of the adsorption column; then add activated carbon with fixed mixed enzymes to the height of the adsorption column 60% to 70%; then add treated zeolite to 90% to 100% of the height of the adsorption column to obtain an ecological adsorption column dedicated to treating dairy cow breeding wastewater.
本实施方式点：The points of this implementation mode:
一、本实施方式利用玉米秸秆制备活性炭作为复合酶体系固定的载体以及天然沸石作为填料制备奶牛养殖废水专用的生态吸附柱；本实施方式利用活性炭及沸石的表面多孔性和表面官能团的存在对养殖废水厌氧发酵后产生的沼液中溶解性有机物、氮、磷进行有效吸附，同时利用固定化酶对废水中的纤维素及有机污染物进行降解；本实施方式制备的生态吸附柱达到饱和吸附状态后，可用于退化土壤，如盐碱土的改良。1. This embodiment uses corn stalks to prepare activated carbon as the carrier for the composite enzyme system and natural zeolite as a filler to prepare an ecological adsorption column dedicated to dairy farming wastewater; this embodiment utilizes the surface porosity and surface functional groups of activated carbon and zeolite. The biogas slurry produced after anaerobic fermentation of wastewater can effectively adsorb dissolved organic matter, nitrogen, and phosphorus, and at the same time use immobilized enzymes to degrade cellulose and organic pollutants in wastewater; the ecological adsorption column prepared in this embodiment can achieve saturated adsorption After the state, it can be used for the improvement of degraded soil, such as saline-alkali soil.
本实施方式制备的生态吸附柱适用于处理奶牛养殖废水。The ecological adsorption column prepared in this embodiment is suitable for treating wastewater from dairy farming.
具体实施方式二：本实施方式与具体实施方式一不同点是：步骤六中所述的吸附柱的材料为有机玻璃。其他步骤与具体实施方式一相同。Embodiment 2: The difference between this embodiment and Embodiment 1 is that the material of the adsorption column described in step 6 is organic glass. Other steps are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二之一不同点是：步骤一种去除玉米秸秆的枝叶和玉米秸秆芯，再将玉米秸秆进行切割，得到长度为2cm的玉米秸秆；使用蒸馏水对长度为2cm的玉米秸秆进行洗涤5次～6次，再在温度为45℃～50℃下干燥10h～12h，得到干燥的长度为2cm～4cm的玉米秸秆。其他步骤与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is: step 1 removes the branches and leaves of corn stalks and the core of corn stalks, and then cuts the corn stalks to obtain corn stalks with a length of 2 cm; The corn stalks with a length of 2 cm are washed with distilled water for 5 to 6 times, and then dried at a temperature of 45° C. to 50° C. for 10 h to 12 h to obtain dry corn stalks with a length of 2 cm to 4 cm. Other steps are the same as those in Embodiment 1 or 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同点是：步骤二中将干燥的长度为2cm的玉米秸秆浸泡在质量分数为8％～10％的硫酸溶液中20min，得到硫酸溶液浸泡后的玉米秸秆；将硫酸溶液浸泡后的玉米秸秆浸泡在质量分数为45％～50％的磷酸钾溶液中40min，得到磷酸钾溶液浸泡后的玉米秸秆。其他步骤与具体实施方式一至三相同。Specific embodiment four: the difference between this embodiment and specific embodiment one to three is that in step 2, the corn stalks with a dry length of 2 cm are soaked in a sulfuric acid solution with a mass fraction of 8% to 10% for 20min to obtain sulfuric acid Corn stalks soaked in the solution; soaking the corn stalks soaked in the sulfuric acid solution in a potassium phosphate solution with a mass fraction of 45% to 50% for 40 minutes to obtain the corn stalks soaked in the potassium phosphate solution. Other steps are the same as those in Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同点是：步骤二中将磷酸钾溶液浸泡后的玉米秸秆置于温度为105℃的烘箱中干燥3h～4h，再置于马弗炉中，再将马弗炉从室温以升温速率为10℃/min，并在温度为400℃活化30min～40min；再将温度为400℃马弗炉以升温速率为10℃/min升温至600℃，温度为600℃下活化20min～30min，再自然冷却至室温，再以蒸馏水为清洗剂进行洗涤3次～5次，再在温度为45℃下干燥10h～12h，再过5目～10目筛，得到粒径为2mm的颗粒活性炭。其他步骤与具体实施方式一至四相同。Embodiment 5: The difference between this embodiment and Embodiments 1 to 4 is that in step 2, the corn stalks soaked in the potassium phosphate solution are placed in an oven with a temperature of 105° C. for 3 hours to 4 hours, and then placed in a horse In the Furnace, the muffle furnace is activated from room temperature at a heating rate of 10°C/min, and activated at a temperature of 400°C for 30 to 40 minutes; then the temperature of the muffle furnace at 400°C is raised to 600°C, activated at 600°C for 20-30 minutes, then cooled naturally to room temperature, then washed 3-5 times with distilled water as a cleaning agent, then dried at 45°C for 10-12 hours, and passed through 5-mesh 10 mesh sieves to obtain granular activated carbon with a particle size of 2mm. Other steps are the same as those in Embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同点是：步骤三中将粒径为2mm的颗粒活性炭加入到温度为20℃～30℃的纤维素分解酶酶液中，再利用震荡器震荡6h，再静置12h，再在离心速度为5000r/min下离心处理10min，弃去上清液，得到吸附纤维素分解酶的活性炭。其他步骤与具体实施方式一至五相同。Specific embodiment six: the difference between this embodiment and one of specific embodiments one to five is that in step three, granular activated carbon with a particle diameter of 2mm is added to the cellulolytic enzyme liquid at a temperature of 20°C to 30°C, and then Vibrate for 6 hours with a vibrator, then let stand for 12 hours, then centrifuge at a centrifugal speed of 5000r/min for 10 minutes, discard the supernatant, and obtain activated carbon that adsorbs cellulolytic enzymes. Other steps are the same as those in Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同点是：步骤三中所述的纤维素分解酶酶液的pH值为5～6.5；所述的纤维素分解酶酶液中纤维素分解酶的酶活度为5unit/mL～7unit/mL。其他步骤与具体实施方式一至六相同。Embodiment 7: The difference between this embodiment and Embodiment 1 to Embodiment 6 is: the pH value of the cellulolytic enzyme liquid described in step 3 is 5-6.5; The enzyme activity of the cellulolytic enzyme is 5 unit/mL-7 unit/mL. Other steps are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同点是：步骤四中将吸附纤维素分解酶的活性炭加入到质量分数为2％的海藻酸钠溶液中，在搅拌速度为150r/min的条件下搅拌60min～70min，再以10滴/min的滴加速度滴加质量分数为1％的氯化钙溶液，得到直径为3mm～5mm的固定化凝胶珠；再将直径为3mm～4mm的固定化凝胶珠在温度为4℃下静置12h～13h，再使用蒸馏水进行洗涤3次～4次，再进行滤干，得到固定了混合酶的活性炭。其他步骤与具体实施方式一至七相同。Embodiment 8: The difference between this embodiment and Embodiments 1 to 7 is that in step 4, the activated carbon that adsorbs cellulolytic enzymes is added to the sodium alginate solution with a mass fraction of 2%, and the stirring speed is 150r Stir for 60min to 70min under the condition of 10 drops/min, then dropwise add calcium chloride solution with a mass fraction of 1% at a rate of 10 drops/min to obtain immobilized gel beads with a diameter of 3mm to 5mm; The ~4 mm immobilized gel beads were left standing at 4° C. for 12 h to 13 h, washed with distilled water for 3 to 4 times, and then filtered to obtain activated carbon immobilized with mixed enzymes. Other steps are the same as those in Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同点是：步骤五中将天然沸石进行粉碎和筛分，得到粒径小于1.5cm的沸石；再使用质量分数为2％的硝酸对粒径小于1.5cm的沸石洗涤3次～5次，再将清洗后的粒径小于1.5cm的沸石浸泡在质量分数为2％的硝酸中20min，得到硝酸浸泡后的沸石；再使用蒸馏水对硝酸浸泡后的沸石进行清洗，至清洗液的pH值为6.5～7.5，再在温度为90℃下干燥4h；得到处理后的沸石。其他步骤与具体实施方式一至八相同。Specific embodiment nine: the difference between this embodiment and specific embodiment one to eight is: in step five, the natural zeolite is crushed and sieved to obtain a zeolite with a particle size less than 1.5 cm; then use the nitric acid with a mass fraction of 2% Wash the zeolite with a particle size less than 1.5cm for 3 to 5 times, then soak the zeolite with a particle size of less than 1.5cm in nitric acid with a mass fraction of 2% for 20min to obtain the zeolite soaked in nitric acid; The zeolite soaked in nitric acid is cleaned until the pH value of the cleaning solution is 6.5-7.5, and then dried at 90° C. for 4 hours to obtain the treated zeolite. Other steps are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同点是：步骤六中首先将透水垫片放入到吸附柱中，再加入处理后的沸石，至吸附柱高度的30％处；再加入固定了混合酶的活性炭，至吸附柱高度的70％；再加入处理后的沸石至吸附柱高度的100％，得到处理奶牛养殖废水专用的生态吸附柱。其他步骤与具体实施方式一至九相同。Embodiment 10: The difference between this embodiment and Embodiment 1 to Embodiment 9 is that in step 6, the water-permeable gasket is first put into the adsorption column, and then the treated zeolite is added to reach 30% of the height of the adsorption column adding activated carbon fixed with mixed enzymes to 70% of the height of the adsorption column; adding treated zeolite to 100% of the height of the adsorption column to obtain an ecological adsorption column dedicated to treating dairy cow breeding wastewater. Other steps are the same as those in Embodiments 1 to 9.
采用以下试验验证本发明的有益效果：Adopt following test to verify beneficial effect of the present invention:
试验一：一种处理奶牛养殖废水专用的生态吸附柱的制备方法，具体是按以下步骤制备的：Test 1: A method for preparing an eco-adsorption column dedicated to treating dairy wastewater, specifically prepared according to the following steps:
一、切割：去除玉米秸秆的枝叶和玉米秸秆芯，再将玉米秸秆进行切割，得到长度为2cm的玉米秸秆；使用蒸馏水对长度为2cm的玉米秸秆进行洗涤5次，再在温度为45℃下干燥12h，得到干燥的长度为2cm的玉米秸秆；1. Cutting: Remove the branches and leaves of the corn stalks and the core of the corn stalks, and then cut the corn stalks to obtain corn stalks with a length of 2 cm; use distilled water to wash the corn stalks with a length of 2 cm 5 times, and then dry them at a temperature of 45 ° C. Dry for 12 hours to obtain dry corn stalks with a length of 2 cm;
二、浸泡：将干燥的长度为2cm的玉米秸秆浸泡在质量分数为10％的硫酸溶液中20min，得到硫酸溶液浸泡后的玉米秸秆；将硫酸溶液浸泡后的玉米秸秆浸泡在质量分数为45％的磷酸钾溶液中40min，得到磷酸钾溶液浸泡后的玉米秸秆；将磷酸钾溶液浸泡后的玉米秸秆置于温度为105℃的烘箱中干燥3h，再置于马弗炉中，再将马弗炉从室温以升温速率为10℃/min，并在温度为400℃活化30min；再将温度为400℃马弗炉以升温速率为10℃/min升温至600℃，温度为600℃下活化20min，再自然冷却至室温，再以蒸馏水为清洗剂进行洗涤3次～5次，再在温度为45℃下干燥12h，再过10目筛，得到粒径为2mm的颗粒活性炭；2. Soaking: Soak the dry corn stalks with a length of 2 cm in a sulfuric acid solution with a mass fraction of 10% for 20 minutes to obtain corn stalks soaked in sulfuric acid solution; soak the corn stalks soaked in sulfuric acid solution in 45% The potassium phosphate solution was soaked in the potassium phosphate solution for 40 minutes to obtain the corn stalks soaked in the potassium phosphate solution; the corn stalks soaked in the potassium phosphate solution were dried in an oven at a temperature of 105°C for 3 hours, and then placed in a muffle furnace. The furnace was activated from room temperature at a heating rate of 10°C/min, and activated at a temperature of 400°C for 30 minutes; then the temperature of the muffle furnace at a temperature of 400°C was raised to 600°C at a heating rate of 10°C/min, and activated at a temperature of 600°C for 20 minutes , then naturally cooled to room temperature, then washed 3 to 5 times with distilled water as a cleaning agent, then dried at 45°C for 12 hours, and passed through a 10-mesh sieve to obtain granular activated carbon with a particle size of 2mm;
三、制备吸附纤维素分解酶的活性炭：将粒径为2mm的颗粒活性炭加入到温度为30℃的纤维素分解酶酶液中，再利用震荡器震荡8h，再静置12h，再在离心速度为5000r/min下离心处理10min，弃去上清液，得到吸附纤维素分解酶的活性炭；3. Preparation of activated carbon for adsorbing cellulolytic enzymes: Add granular activated carbon with a particle size of 2mm to the cellulolytic enzyme solution at a temperature of 30°C, then use an oscillator to shake for 8 hours, then let it stand for 12 hours, and then increase the temperature at a centrifuge speed. Centrifuge at 5000r/min for 10min, discard the supernatant to obtain activated carbon that adsorbs cellulolytic enzymes;
步骤三中所述的纤维素分解酶酶液的pH值为5.1；所述的纤维素分解酶酶液中纤维素分解酶的酶活度为6.5unit/mL；The pH value of the cellulolytic enzyme liquid described in step 3 is 5.1; the enzyme activity of the cellulolytic enzyme in the cellulolytic enzyme liquid is 6.5 unit/mL;
步骤三中所述的粒径为2mm的颗粒活性炭的质量与纤维素分解酶酶液的体积比为1g:5mL；The particle diameter described in step 3 is that the mass of the granular activated carbon of 2mm and the volume ratio of cellulolytic enzyme enzyme liquid are 1g:5mL;
四、将吸附纤维素分解酶的活性炭加入到质量分数为2％的海藻酸钠溶液中，在搅拌速度为150r/min的条件下搅拌60min，再在搅拌速度为10r/min和10滴/min的滴加速度下滴加质量分数为1％的氯化钙溶液至得到直径为3mm～4mm凝胶珠，停止搅拌和滴加质量分数为1％的氯化钙溶液；再将得到的直径为3mm～4mm的凝胶珠在温度为4℃下静置12h，再使用蒸馏水进行洗涤3次，再进行滤干，得到固定了混合酶的活性炭；4. Add activated carbon that absorbs cellulolytic enzymes into a sodium alginate solution with a mass fraction of 2%, stir for 60 minutes at a stirring speed of 150r/min, and then stir at a stirring speed of 10r/min and 10 drops/min Dropping the calcium chloride solution that the mass fraction is 1% to obtain the diameter is 3mm～4mm gel beads under the dropping speed of 1%, stop stirring and dropwise add the calcium chloride solution that the mass fraction is 1%; ~4mm gel beads were left to stand at 4°C for 12 hours, then washed 3 times with distilled water, and then filtered to dry to obtain activated carbon immobilized with mixed enzymes;
步骤四中所述的吸附纤维素分解酶的活性炭的质量与质量分数为2％的海藻酸钠溶液的体积比为100g:500mL；The mass fraction of the activated carbon for adsorbing cellulolytic enzymes described in step 4 is 100g:500mL with a mass fraction of 2% sodium alginate solution;
五、将天然沸石进行粉碎和筛分，得到粒径小于1.5cm的沸石；再使用质量分数为2％的硝酸对粒径小于1.5cm的沸石洗涤3次，再将清洗后的粒径小于1.5cm的沸石浸泡在质量分数为2％的硝酸中20min，得到硝酸浸泡后的沸石；再使用蒸馏水对硝酸浸泡后的沸石进行清洗，至清洗液的pH值为6.5，再在温度为90℃下干燥4h；得到处理后的沸石；5. Grinding and screening the natural zeolite to obtain a zeolite with a particle size of less than 1.5 cm; then use 2% nitric acid to wash the zeolite with a particle size of less than 1.5 cm for 3 times, and then wash the particle size of the zeolite with a particle size of less than 1.5 cm cm of zeolite soaked in nitric acid with a mass fraction of 2% for 20 minutes to obtain the zeolite soaked in nitric acid; then use distilled water to clean the zeolite soaked in nitric acid until the pH of the cleaning solution is 6.5, and then wash the zeolite at a temperature of 90°C Dry 4h; Obtain the treated zeolite;
六、装柱：首先将透水垫片放入到吸附柱中，再加入处理后的沸石，至吸附柱高度的27％处；再加入固定了混合酶的活性炭，至吸附柱高度的63％；再加入处理后的沸石至吸附柱高度的90％，得到处理奶牛养殖废水专用的生态吸附柱；6. Column packing: first put the water-permeable gasket into the adsorption column, then add the treated zeolite to 27% of the height of the adsorption column; then add activated carbon immobilized with mixed enzymes to 63% of the height of the adsorption column; Then add the treated zeolite to 90% of the height of the adsorption column to obtain an ecological adsorption column dedicated to treating dairy wastewater;
步骤六中所述的吸附柱的材料为有机玻璃；The material of the adsorption column described in step 6 is plexiglass;
步骤六中所述的吸附柱的直径为5cm，高度为30cm。The adsorption column described in step 6 has a diameter of 5 cm and a height of 30 cm.
将浓度为50mg/L的NH4Cl溶液分别加入到标号为1#、2#、3#、4#、5#、6#、7#和8#的500mL的三角瓶中，得到分别装有500mLNH4Cl溶液的1#、2#、3#、4#、5#、6#、7#和8#三角瓶；分别调节1#、2#、3#、4#、5#、6#、7#和8#中的NH4Cl溶液的pH值为7.0，再分别向1#、2#、3#、4#、5#、6#、7#和8#三角瓶中滴加2滴氯仿，再分别将2.5g沸石加入到1#和2#三角瓶中；分别将0.5g秸秆炭加入到3#和4#三角瓶中；分别将0.5g瓜子炭加入到5#和6#三角瓶中；分别将0.5g花生炭加入到7#和8#三角瓶中；分别于0min，20min，40min，1h，2h，4h，8h，12h，24h，48h向1#、2#、3#、4#、5#、6#、7#和8#三角瓶中取样2mL，过0.45um滤膜，进行氨氮浓度的测定；将1#和2#得到的数据取平均值；将3#和4#得到的数据取平均值；将5#和6#得到的数据取平均值；将7#和8#得到的数据取平均值进行绘图；如图1所示；图1为不同材质对氨氮的吸附曲线，图1中1为沸石，2为秸秆炭，3为瓜子炭，4为花生炭；Add the NH4 Cl solution with a concentration of 50mg/L into 500mL conical flasks labeled 1#, 2#, 3#, 4#, 5#, 6#, 7# and 8# respectively to obtain 1#, 2#, 3#, 4#, 5#, 6#, 7# and 8# triangular flasks of 500mL NH4 Cl solution; adjust 1#, 2#, 3#, 4#, 5#, 6# respectively The pH value of the NH4 Cl solution in , 7# and 8# is 7.0, and then drop 2 Drop chloroform, then add 2.5g zeolite into 1# and 2# triangular flasks respectively; add 0.5g straw charcoal into 3# and 4# triangular flasks respectively; add 0.5g melon seed charcoal into 5# and 6# In the triangular flask; add 0.5g peanut charcoal into 7# and 8# triangular flasks respectively; #, 4#, 5#, 6#, 7# and 8# take a sample of 2mL in the triangular flask, pass through a 0.45um filter membrane, and measure the concentration of ammonia nitrogen; take the average value of the data obtained by 1# and 2#; The data obtained with 4# are averaged; the data obtained with 5# and 6# are averaged; the data obtained with 7# and 8# are averaged and drawn; as shown in Figure 1; Figure 1 is a pair of different materials The adsorption curve of ammonia nitrogen, in Figure 1, 1 is zeolite, 2 is straw charcoal, 3 is melon seed charcoal, and 4 is peanut charcoal;
从图1可知不同吸附材质达到吸附平衡时的吸附量及在此吸附时间内的吸附速率。从图1中可以看出沸石对氨氮的吸附量为8.28mg/g；秸秆炭对氨氮的吸附性能最好，吸附量为16.35mg/g。在2h内吸附速率最高，随着吸附时间的延长吸附速率逐渐下降。最终在24h达到吸附平衡。From Figure 1, we can know the adsorption capacity of different adsorption materials when they reach adsorption equilibrium and the adsorption rate within this adsorption time. It can be seen from Figure 1 that the adsorption capacity of zeolite to ammonia nitrogen is 8.28 mg/g; the adsorption performance of straw charcoal on ammonia nitrogen is the best, and the adsorption capacity is 16.35 mg/g. The adsorption rate was the highest within 2h, and the adsorption rate gradually decreased with the extension of the adsorption time. The adsorption equilibrium was finally reached within 24 h.
利用上述两种吸附性能最好的沸石和玉米秸秆炭作为填料考察该吸附柱对氨氮的动态吸附能力。这两种材质按照上述比例制成的吸附柱，即试验一得到的处理奶牛养殖废水专用的生态吸附柱。The above two kinds of zeolite and corn stalk charcoal with the best adsorption performance were used as fillers to investigate the dynamic adsorption capacity of the adsorption column for ammonia nitrogen. The adsorption column made of these two materials according to the above ratio is the special ecological adsorption column obtained in Experiment 1 for treating dairy cow breeding wastewater.
以蠕动泵持续将100mg/L氯化铵溶液以1mL/min的速度泵入试验一得到的处理奶牛养殖废水专用的生态吸附柱中，试验一得到的处理奶牛养殖废水专用的生态吸附柱对氨氮的去除效果如图2所示；图2为试验一制备的得到处理奶牛养殖废水专用的生态吸附柱对氨氮的去除效果图；《畜禽养殖废水排放标准》奶牛养殖废水氨氮的排放标准是废水中氨氮的含量为80mg/L，因此按氨氮出水80mg/L计算试验一得到的处理奶牛养殖废水专用的生态吸附柱能处理的水量为5L，有效吸附量为6.67mg/g。Use a peristaltic pump to continuously pump 100mg/L ammonium chloride solution at a speed of 1mL/min into the eco-adsorption column specially used for the treatment of dairy farming wastewater obtained in the first test. The removal effect is shown in Figure 2; Figure 2 is the removal effect figure of ammonia nitrogen by the special ecological adsorption column for the treatment of dairy cow breeding wastewater prepared in the first test; The content of ammonia nitrogen in the medium is 80mg/L. Therefore, the amount of water that can be treated by the ecological adsorption column dedicated to the treatment of dairy farming wastewater obtained in Experiment 1 is 5L, and the effective adsorption capacity is 6.67mg/g.
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