技术领域technical field
本发明属于固体废弃物处理处置，尤其是抗生素菌渣的处理处置，具体涉及一种用“碱/高压破壁预处理+蛋白质回收+剩余残渣厌氧消化”联合处理土霉素菌渣的方法。The invention belongs to the treatment and disposal of solid waste, especially the treatment and disposal of antibiotic slag, and specifically relates to a method for jointly treating oxytetracycline slag with "alkali/high pressure wall breaking pretreatment + protein recovery + anaerobic digestion of remaining residue" .
背景技术Background technique
我国是世界上最大的抗生素原料药生产国与出口国，据统计，2013年抗生素产量达12.12万t，包括青霉素工业盐、头孢菌素、土霉素和链霉素等。即使按生产1t的抗生素产生菌渣8t计（实际可能超过此值），我国抗生素菌渣年产生也达到100万t以上。抗生素菌渣为生产抗生素提纯后剩余的发酵残渣，被列入2008年实施的《国家危险废物名录》；2016年新修订实施的《国家危险废物名录》中，抗生素菌渣依然被列入危险废物。针对抗生素菌渣产量高、处理处置难度大等困境，抗生素菌渣的减量化、资源化和安全化处理处置问题成为目前环保领域研究的难点之一。my country is the world's largest producer and exporter of antibiotic raw materials. According to statistics, the output of antibiotics in 2013 reached 121,200 tons, including penicillin industrial salt, cephalosporins, oxytetracycline and streptomycin. Even if 1 ton of antibiotics produces 8 tons of bacteria residues (actually it may exceed this value), the annual production of antibiotics bacteria residues in my country will reach more than 1 million tons. Antibiotic residues are the remaining fermentation residues after the purification of antibiotics, and were included in the "National List of Hazardous Wastes" implemented in 2008; in the newly revised "National List of Hazardous Wastes" implemented in 2016, antibiotic residues are still included in hazardous wastes . In view of the difficulties of high yield and difficult disposal of antibiotic residues, the reduction, recycling and safe disposal of antibiotic residues have become one of the difficulties in the field of environmental protection research.
土霉素菌渣主要由菌丝体、剩余培养基、发酵代谢产物组成，其中含有大量的残留抗生素、多糖、蛋白质和多种氨基酸及微量元素，具有极大的可生化处理的潜能。但由于菌渣细胞中刚性细胞壁的保护作用，导致胞内大分子有机物难以释放出来，从而难以与水解酸化菌直接接触和降解利用。The oxytetracycline residue is mainly composed of mycelia, remaining medium, and fermentation metabolites, which contain a large amount of residual antibiotics, polysaccharides, proteins, various amino acids and trace elements, and have great potential for biochemical treatment. However, due to the protective effect of the rigid cell wall in the bacteria residue cells, it is difficult to release the macromolecular organic matter in the cells, so it is difficult to directly contact and degrade and utilize the hydrolytic acidification bacteria.
因此，寻找一种即可使菌渣减量、又可提高抗生素菌渣中胞内有机质的溶出率、改善菌渣厌氧消化特性的方法，从而提高土霉素菌渣的资源化利用率和厌氧产沼气效率，最终实现土霉素菌渣的减量化和资源化利用，并降低抗生菌渣中抗生素残留浓度，这对节约资源、防止环境污染、发展循环经济具有重要的意义。Therefore, look for a method that can reduce the amount of bacteria residues, increase the dissolution rate of intracellular organic matter in the antibiotic residues, and improve the anaerobic digestion characteristics of bacteria residues, thereby improving the resource utilization and utilization of oxytetracycline residues. The efficiency of anaerobic biogas production can finally realize the reduction and resource utilization of oxytetracycline residues, and reduce the concentration of antibiotic residues in antibiotic residues, which is of great significance for saving resources, preventing environmental pollution, and developing circular economy.
发明内容Contents of the invention
本发明的目的是在对土霉素菌渣的破胞预处理的基础上，提取菌渣中的蛋白质，从而进一步提高土霉素菌渣的厌氧消化特性。本发明采用碱/高压破壁技术对土霉素菌渣进行溶破胞预处理，提取回收菌渣中的蛋白质，实现菌渣的高效厌氧消化产沼气能力，最终达到菌渣减量化和资源化利用的目的。The purpose of the present invention is to extract the protein in the oxytetracycline slag on the basis of cell-breaking pretreatment of the oxytetracycline slag, thereby further improving the anaerobic digestion characteristics of the oxytetracycline slag. The present invention adopts the alkali/high pressure wall-breaking technology to pretreat the oxytetracycline slag, extract and recover the protein in the slag, realize the high-efficiency anaerobic digestion of the slag to produce biogas, and finally achieve the reduction of the slag and the The purpose of resource utilization.
本发明采用如下技术方案：The present invention adopts following technical scheme:
一种土霉素菌渣处理及利用方法，其包括如下步骤：A kind of oxytetracycline slag treatment and utilization method, it comprises the steps:
（1）土霉素菌渣含水率的调节：调整土霉素菌渣含水率为95%~99%；(1) Adjustment of moisture content of oxytetracycline residue: adjust the moisture content of oxytetracycline residue to 95%~99%;
（2）调pH：向步骤（1）处理得到的菌渣中加碱，调整其pH为11~13.5；(2) pH adjustment: add alkali to the bacterial residue obtained in step (1) to adjust the pH to 11~13.5;
（3）高压破壁溶胞：将经步骤（2）处理得到的菌渣送入高压破壁机内，破壁次数为1~5次；(3) High-pressure wall-breaking and lysis: send the bacteria residue obtained through step (2) into the high-pressure wall-breaking machine, and the number of wall-breaking is 1 to 5 times;
（4）蛋白质溶出液分离：将经步骤（3）处理得到的菌渣在离心机内进行固液分离，得到蛋白质提取液和残渣；(4) Separation of protein eluate: Separating the bacterial residue obtained through step (3) into solid and liquid in a centrifuge to obtain protein extract and residue;
（5）蛋白质沉淀分离与回收：调节步骤（4）得到的蛋白质提取液的pH对蛋白质进行等电点沉淀，静置1~5min，离心分离到蛋白质和提取液残液；蛋白质干燥后回收利用；(5) Protein precipitation separation and recovery: adjust the pH of the protein extract obtained in step (4) to conduct isoelectric precipitation on the protein, let it stand for 1-5 minutes, and centrifuge to separate the protein and extract residue; recycle the protein after drying ;
（6）剩余残渣混合液厌氧消化处理：将步骤（4）得到的残渣与步骤（5）得到的提取液残液混合，得到剩余残渣混合液；向所述剩余残渣混合液中加碱调节pH为6.8~7.5后进入UASB厌氧反应器中处理，厌氧反应产生的沼气通过碱吸收和水封后进入沼气收集装置；(6) Anaerobic digestion treatment of the residual residue mixture: mix the residue obtained in step (4) with the extract liquid residue obtained in step (5) to obtain the residual residue mixture; add alkali to the remaining residue mixture to adjust After the pH is 6.8~7.5, it enters the UASB anaerobic reactor for treatment, and the biogas generated by the anaerobic reaction enters the biogas collection device after being absorbed by alkali and sealed with water;
（7）沼渣浓缩处理：经步骤（6）处理得到的沼渣经浓缩后进行填埋或肥料化利用。(7) Biogas residue concentration treatment: the biogas residue obtained after the treatment in step (6) is concentrated and used for landfill or fertilizer use.
进一步的，所述步骤（1）中，向土霉素原菌渣中加入水，搅拌均匀后待用，调整土霉素菌渣的含水率为95%~99%（质量百分含量）。优选的，调整土霉素菌渣含水率为98%。Further, in the step (1), water is added to the original oxytetracycline slag, stirred evenly before use, and the moisture content of the oxytetracycline slag is adjusted to 95%-99% (mass percentage). Preferably, the moisture content of oxytetracycline slag is adjusted to 98%.
进一步的，所述步骤（2）中，调整菌渣溶液pH为11~13.5，优选的，pH值为13。Further, in the step (2), the pH of the bacterial residue solution is adjusted to 11-13.5, preferably, the pH value is 13.
进一步的，所述步骤（3）中，破壁压力为50~100MPa，优选的，破壁压力为80MPa。Further, in the step (3), the breaking pressure is 50-100 MPa, preferably, the breaking pressure is 80 MPa.
进一步的，所述步骤（4）和步骤（5）中，离心转速为3500r/min~4500r/min，离心时间为10~30min。优选的，离心转速为3800r/min，离心时间为15min。Further, in the step (4) and step (5), the centrifugal speed is 3500r/min~4500r/min, and the centrifugation time is 10~30min. Preferably, the centrifugal speed is 3800r/min, and the centrifugal time is 15min.
进一步的，所述步骤（5）的等电点pH为2~5。优选的，等电点pH为5。Further, the isoelectric point pH of the step (5) is 2-5. Preferably, the isoelectric point pH is 5.
进一步的，所述步骤（6）的UASB厌氧反应器中，污泥接种比为0.3~0.6，容积负荷为1.0~5.5gVS/(L•d)，反应温度为35~40℃。优选的容积负荷为5.0 gVS/(L•d)。Further, in the UASB anaerobic reactor in the step (6), the sludge inoculum ratio is 0.3-0.6, the volume load is 1.0-5.5 gVS/(L·d), and the reaction temperature is 35-40°C. The preferred volume load is 5.0 gVS/(L•d).
进一步的，所述步骤（7）中，所述沼渣排入沼渣浓缩池中进行浓缩，停留时间为29~33d。Further, in the step (7), the biogas residue is discharged into a biogas residue concentration tank for concentration, and the residence time is 29-33 days.
进一步的，所述酸为盐酸，所述碱为氢氧化钠。Further, the acid is hydrochloric acid, and the alkali is sodium hydroxide.
本发明的有益效果在于：The beneficial effects of the present invention are:
1、实现了土霉素菌渣的减量化处理，充分降低了菌渣中悬浮物的浓度，菌渣中SS的消减率最高可达63.84%。1. Realized the reduction treatment of oxytetracycline bacteria residue, fully reduced the concentration of suspended solids in the bacteria residue, and the reduction rate of SS in the bacteria residue can reach up to 63.84%.
2、实现了土霉素菌渣蛋白质的分离与回收，在最优运行条件下，菌渣中蛋白质的溶出率为73.11%，蛋白质的沉淀回收效率达到98.35%，回收的固体蛋白质纯度达到83.00%，实现了土地霉素菌渣中资源的回收。2. Realized the separation and recovery of protein from oxytetracycline bacteria residue. Under the optimal operating conditions, the dissolution rate of protein in bacteria residue was 73.11%, the precipitation recovery efficiency of protein reached 98.35%, and the purity of recovered solid protein reached 83.00%. , to realize the recovery of resources in the terramycin residue.
3、土霉素菌渣经碱/高压破壁预处理后，有效降低了残渣中土霉素残留，土霉素的含量由原来的633mg/L降低到了150mg/L以下，降低了抗生素对厌氧微生物的毒害作用，为后续的厌氧生物处理提供了良好条件。3. After the oxytetracycline slag is pretreated by alkali/high pressure wall breaking, the oxytetracycline residue in the residue is effectively reduced, and the content of oxytetracycline is reduced from the original 633mg/L to below 150mg/L, which reduces the resistance to antibiotics. The toxic effect of aerobic microorganisms provides good conditions for subsequent anaerobic biological treatment.
4、本系统可以恒定多种运行参数，可以考察单一运行条件对土霉素菌渣无害化、资源化处理的影响，经处理后的废渣可作为有机肥的原料回收利用。4. This system can keep multiple operating parameters constant, and can investigate the impact of a single operating condition on the harmless and resourceful treatment of oxytetracycline residues. The treated waste residues can be recycled as raw materials for organic fertilizers.
5、本发明首次开发出一种土霉素菌渣“碱/高压破壁预处理+蛋白质回收+剩余残渣厌氧消化”的处理技术与方法，产生的沼气回收利用做清洁燃料，沼渣经鉴别为无害可作为制作有机肥的原料。5. For the first time, the present invention has developed a treatment technology and method of oxytetracycline bacteria residue "alkali/high pressure wall-breaking pretreatment + protein recovery + anaerobic digestion of remaining residue". It is identified as harmless and can be used as raw material for making organic fertilizer.
6、与本课题组申请的“一种从土霉菌渣中提取蛋白质的方法”（申请号CN201710120823.1）相比，本专利不仅仅在菌渣的破壁方法上提出了改进，同时在提高蛋白质回收率的基础上，更进一步的明确了“碱/高压破壁”技术对菌渣其它主要污染指标（COD、SS和土霉素残留等）的影响，并更进一步的提供了土霉素菌渣的全过程处理技术，为土霉素菌渣的减量化、资源化和无害化提供了更全面的技术支持。6. Compared with the "A Method for Extracting Protein from Earth Mold Residue" (application number CN201710120823.1) applied by our research group, this patent not only improves the method of breaking the wall of the fungus residue, but also improves the On the basis of the protein recovery rate, the impact of the "alkali/high-pressure wall breaking" technology on other major pollution indicators (COD, SS and oxytetracycline residues, etc.) The whole-process treatment technology of oxytetracycline slag provides more comprehensive technical support for the reduction, recycling and harmlessness of oxytetracycline slag.
7、本发明所用到“碱/高压破壁预处理+蛋白质回收+剩余残渣厌氧消化”的处理工艺设备能源消耗少，操作简单，为土霉素菌渣的减量化、资源化和无害化处理提供了合理的可操作的工艺路线，也为其它抗生素菌渣的处理提供了理论基础与技术支持。7. The treatment process equipment of "alkali/high-pressure wall-breaking pretreatment + protein recovery + anaerobic digestion of remaining residue" used in the present invention has less energy consumption and simple operation, which is the reduction, resource utilization and non-toxicity of oxytetracycline bacteria residue. Harmful treatment provides a reasonable and operable process route, and also provides a theoretical basis and technical support for the treatment of other antibiotic residues.
附图说明Description of drawings
图1为本发明的技术流程示意图。Fig. 1 is a schematic diagram of the technical process of the present invention.
图2为含水率对土霉素菌渣中蛋白质溶出率的影响示意图。Figure 2 is a schematic diagram of the effect of water content on the dissolution rate of protein in oxytetracycline bacteria residue.
图3为破壁压力对土霉素菌渣中蛋白质溶出率的影响示意图。Fig. 3 is a schematic diagram showing the effect of wall breaking pressure on the dissolution rate of protein in oxytetracycline bacteria residue.
图4为pH对土霉素菌渣中蛋白质溶出率的影响示意图。Fig. 4 is a schematic diagram showing the effect of pH on the dissolution rate of protein in oxytetracycline residue.
图5为破壁次数对土霉素菌渣中蛋白质溶出率的影响示意图。Fig. 5 is a schematic diagram showing the effect of the number of wall breaking on the dissolution rate of protein in oxytetracycline residue.
图6为pH对蛋白质沉淀率的影响示意图。Figure 6 is a schematic diagram of the effect of pH on the protein precipitation rate.
图7为剩余残渣厌氧消化的沼气累集产率结果示意图。Fig. 7 is a schematic diagram of the biogas accumulation yield results of anaerobic digestion of residual residues.
具体实施方式Detailed ways
实施例1Example 1
如图1所示。As shown in Figure 1.
第一步，调节菌渣含水率为95～99%。The first step is to adjust the moisture content of the bacteria residue to 95-99%.
第二步，加碱调节菌渣溶液pH为11～13.5。In the second step, alkali is added to adjust the pH of the bacteria residue solution to 11-13.5.
第三步，将试验用菌渣送入高压破壁机进行处理，控制破壁参数为压力50～100MPa和破壁次数1~5次；在这个过程中，菌渣细胞在碱/高压破壁双重协同作用下进行破溶胞，使得胞内物质释放并破解，菌渣溶液中的溶解性蛋白质含量和SCOD浓度均大幅提高，同时菌渣溶液中的SS浓度大幅降低。In the third step, the bacteria residues used in the test are sent to the high-pressure wall breaking machine for processing, and the parameters of the wall breaking are controlled at a pressure of 50-100 MPa and the number of times of wall breaking is 1-5 times; Under the double synergistic effect, the cells were broken and lysed, so that the intracellular substances were released and cracked, the soluble protein content and SCOD concentration in the bacteria residue solution were greatly increased, and the SS concentration in the bacteria residue solution was greatly reduced.
第四步，破壁后的菌渣溶液进行离心分离，控制离心条件为转速3500r/min～4500r/min、时间10～30min，离心分离后得到蛋白质提取液和剩余残渣；得到的溶解性蛋白质提取液进行蛋白质沉淀回收，剩余残渣进入后续的厌氧消化处理系统。The fourth step is to centrifuge the broken bacterial residue solution. The centrifugation conditions are controlled at a speed of 3500r/min to 4500r/min and the time is 10 to 30min. After centrifugation, the protein extract and the remaining residue are obtained; the obtained soluble protein is extracted The liquid is recovered by protein precipitation, and the remaining residue enters the subsequent anaerobic digestion treatment system.
第五步，用1mol/L盐酸调整蛋白质提取液pH值后进行等电点法蛋白质沉淀，pH值范围为2～5，蛋白质随着pH的逐渐降低而沉淀，然后采用离心分离蛋白质溶液，控制离心条件为转速3500r/min～4500 r/min、时间10～30min，得到固体蛋白质和剩余残液。The fifth step is to adjust the pH value of the protein extract with 1mol/L hydrochloric acid and then carry out the protein precipitation by isoelectric point method. The centrifugation conditions are 3500r/min-4500r/min, and 10-30min, to obtain solid protein and remaining raffinate.
第六步，固体蛋白质自然晾干后回收再利用。In the sixth step, the solid protein is recycled and reused after drying naturally.
第七步，将第五步剩余残液和第四步剩余残渣混合后得到剩余残渣混合液，然后送入厌氧消化系统进行处理，厌氧条件控制为：混合液pH为6.8~7.5，厌氧颗粒污泥接种比为0.3～0.6，反应温度35℃～40℃，容积负荷设定1.0～5.5gVS/(L·d)；厌氧搅拌为连续搅拌，厌氧反应产生的沼气通过碱吸收和水封后进入沼气收集装置，然后将沼气净化燃烧用来加热产生蒸汽用来加热厌氧反应器。The seventh step is to mix the remaining residue of the fifth step with the residue of the fourth step to obtain the remaining residue mixture, and then send it to the anaerobic digestion system for treatment. The anaerobic conditions are controlled as follows: the pH of the mixture is 6.8~7.5, The oxygen granular sludge inoculation ratio is 0.3-0.6, the reaction temperature is 35°C-40°C, and the volume load is set at 1.0-5.5gVS/(L d); the anaerobic stirring is continuous stirring, and the biogas generated by the anaerobic reaction is absorbed by alkali After being sealed with water, it enters the biogas collection device, and then the biogas is purified and burned for heating to generate steam for heating the anaerobic reactor.
第八步，厌氧消化处理后的剩余沼渣排入沼渣浓缩池，沼渣停留时间设定为29~33d。经浓缩后的沼渣经安全检测后进行填埋或肥料化利用；对上清液进行检测，检测指标符合后排入市政管网或厂区污水处理设施进行进一步处理。In the eighth step, the residual biogas residue after anaerobic digestion treatment is discharged into the biogas residue concentration tank, and the residence time of the biogas residue is set to 29~33d. The concentrated biogas residue is landfilled or fertilized after safety inspection; the supernatant is tested and discharged into the municipal pipe network or factory sewage treatment facilities for further treatment after the detection indicators meet the requirements.
实施例2Example 2
碱/高压破壁协同预处理土霉素菌渣。正交试验设计与步骤：Synergistic pretreatment of oxytetracycline slag by alkali/high pressure wall breaking. Orthogonal experiment design and steps:
（1）正交试验设计：以菌渣含水率、反应pH、破壁压力和破壁次数为四因素，每个因素控制三水平，设计L9（43）正交试验，试验设计见表1。(1) Orthogonal test design: take the moisture content of bacteria residue, reaction pH, wall breaking pressure and breaking times as four factors, each factor controls three levels, and designs L9 (43 ) orthogonal test, the test design is shown in Table 1 .
（2）正交试验步骤：称取一定量土霉素菌渣至烧杯内，加入蒸馏水调整菌渣含水率至一定含水率，充分搅拌均匀，通过4 mol/L NaOH溶液调节菌渣溶液pH值，然后将菌渣倒入高压破壁机内进行高压破壁处理。高压破壁完成后，对菌渣混合液在3800 r/min条件下离心15 min，弃去残渣后得到蛋白质提取液。预处理完成后，对菌渣混合液的SS、COD和蛋白质浓度进行测定和分析，溶解性蛋白质浓度采用考马斯亮蓝法进行溶液中蛋白质浓度测定。试验结果见表1。(2) Orthogonal test procedure: Weigh a certain amount of oxytetracycline bacteria residue into a beaker, add distilled water to adjust the moisture content of the bacteria residue to a certain moisture content, stir well, and adjust the pH value of the bacteria residue solution through 4 mol/L NaOH solution , and then pour the bacteria residue into the high-pressure wall breaking machine for high-pressure wall breaking treatment. After the high-pressure wall breaking was completed, the mixture of bacteria residue was centrifuged at 3800 r/min for 15 min, and the protein extract was obtained after discarding the residue. After the pretreatment, the SS, COD and protein concentration of the fungus residue mixture were measured and analyzed, and the soluble protein concentration was measured by the Coomassie brilliant blue method. The test results are shown in Table 1.
表1 正交试验结果分析表Table 1 Orthogonal test results analysis table
。 .
由表1可知，含水率、破壁压力、破壁次数和溶液pH值对土霉素菌渣的破溶胞效果均有一定的影响，而对于菌渣细胞内的蛋白质溶出效果也非常明显。按蛋白质溶出率计算正交试验的均值与方差，结果表明含水率是影响土霉素菌渣中蛋白质溶出率的主要因素，其次为均质压力、pH与均质次数。通过极差分析可得最佳工艺条件为A3B2C1D3，即含水率98%、破壁压力70 MPa、破壁次数1次和pH=13。It can be seen from Table 1 that the moisture content, wall-breaking pressure, number of wall-breaking times and solution pH all have certain influences on the cell-breaking and lysing effect of oxytetracycline slag, and the protein dissolution effect in the slag cell is also very obvious. The mean and variance of the orthogonal test were calculated according to the protein dissolution rate, and the results showed that the water content was the main factor affecting the protein dissolution rate in oxytetracycline residue, followed by homogenization pressure, pH and homogenization times. Through the range analysis, the optimal process conditions can be obtained as A3B2C1D3, that is, the water content is 98%, the wall breaking pressure is 70 MPa, the number of wall breaking is 1 time, and pH=13.
实施例3Example 3
单因素水平实验（以蛋白质溶出率为主要参考指标）。Single factor level experiment (with protein dissolution rate as the main reference index).
（1）含水率对土霉素菌渣中蛋白质溶出率的影响(1) Effect of water content on protein dissolution rate in oxytetracycline residue
选取含水率为95%、96%、97%、98%和99%，其他条件为：pH=13、破壁次数1次、破壁压力70MPa。试验结果如图2。结果表明，含水率的变化对菌渣中蛋白质溶出率影响显著。含水率低于98%时，蛋白质溶出效果呈上升趋势。当含水率超出98%时，蛋白质溶出效率反而降低，这说明土霉素菌渣中蛋白质的溶解浓度在本试验条件下可达到饱和。The selected water content is 95%, 96%, 97%, 98% and 99%, and the other conditions are: pH=13, the number of wall breaking times is 1, and the wall breaking pressure is 70MPa. The test results are shown in Figure 2. The results showed that the change of water content had a significant effect on the dissolution rate of protein in the bacteria residue. When the water content is lower than 98%, the protein dissolution effect tends to increase. When the water content exceeds 98%, the protein dissolution efficiency decreases instead, which shows that the dissolved concentration of protein in oxytetracycline slag can reach saturation under the test conditions.
（2）破壁压力对土霉素菌渣中蛋白质溶出率的影响(2) Effect of wall-breaking pressure on protein dissolution rate from oxytetracycline residue
选取破壁压力为50 MPa、60 MPa、70 MPa、80 MPa、90 MPa，其他条件为：含水率98 %、pH=13、破壁次数1次。试验结果如图3。结果表明蛋白质溶出率随着破壁压力的增大呈先升高后降低的趋势。破壁压力的增大可加剧细胞壁的破碎并利于碱解反应，这是蛋白质质溶出率增大的原因；但进一步增大压力易造成蛋白质的破碎和裂解。因此，优选最佳破壁压力为压力80 MPa。The wall-breaking pressure was selected as 50 MPa, 60 MPa, 70 MPa, 80 MPa, and 90 MPa, and other conditions were: moisture content 98%, pH=13, and wall-breaking times once. The test results are shown in Figure 3. The results showed that the protein dissolution rate first increased and then decreased with the increase of the breaking pressure. The increase of breaking pressure can intensify the breakage of cell wall and facilitate the alkaline hydrolysis reaction, which is the reason for the increase of protein dissolution rate; but further increase of pressure can easily cause protein breakage and cracking. Therefore, the optimum wall breaking pressure is preferably 80 MPa.
（3）pH对土霉菌渣中蛋白质溶出率的影响(3) Effect of pH on the dissolution rate of protein in soil mold residue
选择pH为11.5、12.0、12.5、13.0、13.5，其他条件为：含水率97%、声能密度8 W·mL-1、反应时间30 min。试验结果如图4。pH代表了参与碱解反应的碱的浓度，pH越高，参与碱解反应的NaOH就越多，对于菌渣细胞的影响也越大。结果表明，当pH<13.0时，蛋白质溶出率随着pH的增大而增大；当pH>13.0时，蛋白质溶出率随pH的增大而降低。反应体系中碱含量过高，溶液中过多的羟基自由基，不仅对菌体细胞壁造成了破坏，还会对溶出的蛋白质进行破坏，这导致了蛋白质溶出率随pH的变化而变化。Select pH as 11.5, 12.0, 12.5, 13.0, 13.5, other conditions are: water content 97%, sound energy density 8 W·mL-1 , reaction time 30 min. The test results are shown in Figure 4. pH represents the concentration of alkali involved in the alkaline hydrolysis reaction, the higher the pH, the more NaOH involved in the alkaline hydrolysis reaction, and the greater the impact on the slag cells. The results showed that when the pH<13.0, the protein dissolution rate increased with the increase of pH; when the pH>13.0, the protein dissolution rate decreased with the increase of pH. The alkali content in the reaction system is too high, and the excessive hydroxyl radicals in the solution not only damage the cell wall of the bacteria, but also destroy the dissolved protein, which leads to the change of the protein dissolution rate with the change of pH.
（4）破壁次数对土霉素菌渣中蛋白质溶出率的影响(4) Effect of breaking times on protein dissolution rate in oxytetracycline residue
选取破壁次数为1次、2次、3次、4次、5次，其他条件为：含水率98%、破壁压力80 MPa、pH=13。试验结果见图5。结果表明，蛋白质溶出率随着均质次数的增大而持续降低。随着均质次数的增多，均质过程中产生大量的剪切破坏、高频振动与热量。大量的剪切破坏与高频振动将会作用于溶出的蛋白质，使蛋白质发生水解。同时，由于蛋白质具有热不稳定性，温度的上升也可能导致溶出的蛋白质发生变性而沉淀于残渣内。另外，均质次数的增加，意味着能量消耗的增大，不利于实际生产所产生的良好效益。因此，选取均质1次为最佳处理条件。The number of broken walls was selected as 1 time, 2 times, 3 times, 4 times, and 5 times, and other conditions were: moisture content 98%, wall breaking pressure 80 MPa, pH=13. The test results are shown in Figure 5. The results showed that the protein dissolution rate continued to decrease with the increase of homogenization times. As the number of homogenization increases, a large amount of shear damage, high-frequency vibration and heat are generated during the homogenization process. A large amount of shear damage and high-frequency vibration will act on the dissolved protein to hydrolyze the protein. At the same time, due to the thermal instability of the protein, the rise in temperature may also cause the denaturation of the eluted protein and precipitate in the residue. In addition, the increase of homogenization times means the increase of energy consumption, which is not conducive to the good benefits generated by actual production. Therefore, homogenization once was selected as the best treatment condition.
实施例4Example 4
采用等电点法对蛋白质提取溶液中的蛋白质进行沉淀回收。The protein in the protein extraction solution was precipitated and recovered by the isoelectric point method.
将蛋白质提取液移至离心管内，以1 mol/L盐酸溶液调整蛋白质提取液pH值，然后对蛋白质沉淀进行离心分离，最终回收蛋白质沉淀。离心机控制条件：3800 r/min的转速，15 min离心时间。采用考马斯亮蓝法测定上清液蛋白质浓度。试验结果见图6。结果表明，蛋白质沉淀效率在酸性条件下要明显优于碱性条件。蛋白质为两性电解质，提取液的酸碱度直接影响蛋白质分子的电解状态与解离程度。通过调节提取液的pH值，可以改变提取液中蛋白质分子的带电量与电荷性质。因此用等电点沉淀法提取蛋白的最佳条件为pH=5.0，此时蛋白沉淀效率可达到98.35%。Transfer the protein extract to a centrifuge tube, adjust the pH of the protein extract with 1 mol/L hydrochloric acid solution, then centrifuge the protein precipitate, and finally recover the protein precipitate. Centrifuge control conditions: 3800 r/min speed, 15 min centrifugation time. The protein concentration of the supernatant was determined by the Coomassie brilliant blue method. The test results are shown in Figure 6. The results showed that the protein precipitation efficiency was significantly better under acidic conditions than under alkaline conditions. Protein is an ampholyte, and the pH of the extract directly affects the electrolysis state and dissociation degree of protein molecules. By adjusting the pH value of the extract, the charged amount and charge properties of protein molecules in the extract can be changed. Therefore, the optimal condition for protein extraction by isoelectric point precipitation is pH=5.0, and the protein precipitation efficiency can reach 98.35%.
实施例5Example 5
蛋白质提取后剩余残渣混合液性质与原菌渣性质的对比。Comparison of the properties of the remaining residue mixture after protein extraction with the properties of the original bacteria residue.
试验条件：调节菌渣含水率为98%、pH值为13后，将试验用菌渣送入高压破壁机进行处理，控制破壁压力为80MPa、破壁次数为一次；破壁后的菌渣溶液进行离心分离，控制离心条件为转速3800 r/min、时间15 min，得到蛋白质提取液和剩余残渣；用1 mol/L盐酸调整蛋白质提取液pH值后进行等电点法蛋白质沉淀，采用3800 r/min的转速进行15 min离心分离，得到固体蛋白质和剩剩余残液；固体蛋白质回收再利用；剩余残液和第二步剩余残渣混合后得到剩余残渣混合液，然后送入厌氧消化系统进行处理。剩余残渣混合液与原菌渣的蛋白质对比结果见表2。Test conditions: After adjusting the moisture content of the bacteria residue to 98% and the pH value to 13, the bacteria residue used in the test was sent to a high-pressure wall breaking machine for processing, and the wall breaking pressure was controlled to be 80MPa, and the number of wall breaking times was one time; the bacteria after breaking the wall Centrifuge the slag solution, control the centrifugation speed at 3800 r/min for 15 min, and obtain the protein extract and the remaining residue; adjust the pH value of the protein extract with 1 mol/L hydrochloric acid and carry out protein precipitation by the isoelectric point method. Centrifuge at a speed of 3800 r/min for 15 minutes to obtain solid protein and remaining residue; solid protein is recovered and reused; the remaining residue is mixed with the residue from the second step to obtain a mixture of residue, which is then sent to anaerobic digestion system to process. The protein comparison results of the remaining residue mixture and the original bacterial residue are shown in Table 2.
表2 土霉素菌渣中蛋白质提取后剩余残渣混合液性质Table 2 Properties of the residual residue mixture after protein extraction from oxytetracycline bacteria residue
。 .
实施例6Example 6
剩余残渣混合液厌氧消化特性分析。Analysis of anaerobic digestion characteristics of residual residue mixture.
剩余残渣混合液进行厌氧消化特性分析，厌氧条件控制为：调节混合液pH到6.8~7.5，厌氧颗粒污泥接种比为0.3～0.6，反应温度35℃，记录沼气累集产率。试验结果如图7。由图7可见，预处理后菌渣在5.05gVS/(L•d)负荷时，达到产气高峰，在5.75gVS/(L•d)负荷时迅速下降，直至不产气；而未处理菌渣在3.98gVS/(L•d)时，到达产气高峰。预处理后菌渣的厌氧消化运行负荷提高了27%，同时，平均沼气产量也提高了10%以上。这一结果表明预处理“碱/高压破壁+蛋白质回收”预处理措施能够促进菌渣的厌氧消化，这不仅体现在菌渣厌氧沼气的产量上，而且对菌渣厌氧消化的运行负荷的提高也有很大的促进作用。Analyze the anaerobic digestion characteristics of the remaining residue mixture. The anaerobic conditions are controlled as follows: adjust the pH of the mixture to 6.8-7.5, the inoculum ratio of anaerobic granular sludge is 0.3-0.6, and the reaction temperature is 35°C. Record the biogas accumulation yield. The test results are shown in Figure 7. It can be seen from Figure 7 that the pretreated bacteria residue reached the peak of gas production at a load of 5.05gVS/(L·d), and dropped rapidly at a load of 5.75gVS/(L·d) until no gas was produced; while the untreated bacteria When the slag is at 3.98gVS/(L•d), it reaches the peak of gas production. After the pretreatment, the anaerobic digestion operation load of the bacteria residue increased by 27%, and at the same time, the average biogas production also increased by more than 10%. This result shows that the pretreatment measures of "alkali/high-pressure wall breaking + protein recovery" can promote the anaerobic digestion of the fungal residue, which is not only reflected in the anaerobic biogas production of the fungal residue, but also affects the operation of the anaerobic digestion of the fungal residue. The increase in load also has a big boost.
以上所述的实施例仅仅是对本发明的优选实施方式进行描述，但并不限于此，本领域的技术人员很容易根据上述实施例领会本发明的精神，并作出不同的引申和变化，但只要不脱离本发明的精神，都在本发明的保护范围之内。The above-mentioned embodiments only describe the preferred implementation of the present invention, but are not limited thereto. Those skilled in the art can easily understand the spirit of the present invention based on the above-mentioned embodiments, and make different extensions and changes, but as long as All are within the protection scope of the present invention without departing from the spirit of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399445.1ACN108101956B (en) | 2017-12-22 | 2017-12-22 | Method for treating and utilizing oxytetracycline bacterial residues |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399445.1ACN108101956B (en) | 2017-12-22 | 2017-12-22 | Method for treating and utilizing oxytetracycline bacterial residues |
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| CN108101956B CN108101956B (en) | 2021-09-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711399445.1AActiveCN108101956B (en) | 2017-12-22 | 2017-12-22 | Method for treating and utilizing oxytetracycline bacterial residues |
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