Technology And Mechanism Of Berberine Pharmaceutical Wastewater By Physico-chemical Pretreatment

In recent years,the frequent appearances of antibiotic substances and heavy metals in the environment have got the focus of the public.Heavy metals in the waste water,which emitted to the water body,will become part of the sedimentation.They will move and be released and enriched among aquatic organisms.Heavy metals will not only harm the aquatic plants,but also damage human body through the food chain.Moreover,this characteristic of heavy metals also harms the microorganisms used in waste water treatment,which further jeopardizes the running effects of waste water processing facilities.Antibiotic substances are highly biologically active and lipophilic,so they are severe threats to the water and aquatic environment and human health.Whats more,large amount of antibiotics in water will also induce and spread resistant bacteria and gene.Pharmaceutical antibiotic waste water is an important source of heavy metals and antibiotic wastes in water environment.It has the characteristics of high concentration of CODCr,high toxicity of microorganisms,great complexity of treatment processes,and high costs of treatments,which has become the focus and nodus of pharmaceutical waste water treatment.The research targets of this proposal are Berberine Wastewater Containing Copper and berberine wastewater.They are two typical types,which are emitted from the berberine production,of pharmaceutical antibiotic waste water.Because these two types of waste water have the characteristics of low biodegradability,high concentration of copper ions,and high contents of organic contaminants,this research would employ crystalline precipitation and resin adsorption process as the main process to remove and recycle copper ions and berberine.This process utilizes the resources in pharmaceutical waste water,and create favorable conditions for further biochemical discharges.Firstly copper ions are recycled in the form of Cu?OH?Cl crystallization from the waste water.Then the left copper ions are removed from the waste water by Ion exchange resin.Finally berberine is selectively adsorpted from waste water by using amino-modified polymeric adsorbent,and recycled through desorption.The goal of the above steps is to change the concept that pharmaceutical waste water is just industrial waste.However,the copper ions and berberine in the waste water are more of rich mineral resources in the city,than just the products of environmental protection.By extending the production line of berberine and producing the by-products of Cu?OH?Cl,we not only realize cleaner berberine production,but also raise the economic benefits of enterprises.A combination of crystalline precipitation and resin adsorption process was adopted for the recovery of copper contained in berberine production industrial wastewater.Optimized conditions were studied by batch experiments.The crystal structure of produced precipitate as tribasic copper chloride?TBCC?was evaluated by XRD analysis.The results showed that under the condition of p H value 7.0-9.0,over 99.9% copper was recovered by crystalline precipitation process.The composition of basic copper chloride precipitation would meet with national standards?GB/T21696-2008?of feed-grade after water washing.After a following ion exchange treatment the effluent met the compliance discharge.On the basis of the bench-scale test,a pilot scale test was carried out.The results of pilot scale test certified the effect of this combined process.This process recovered the copper resource from pharmaceutical industrial wastewater.At the same time,the pH value improved from lower than 1.0 to higher than 7.0,would be beneficial to the comprehensive treatment of pharmaceutical wastewater and the meeting discharge standard.Ion exchange resin?D152,D113,D401?were applied for treatment of pharmaceutical wastewater containing copper ions and berberine.The D401 was selected as optimal polymeric adsorbent based on the comparison of copper and berberine adsorption removal rates.In addition,the adsorption kinetics and thermodynamics was analyzed,and the Cu²⁺ removal efficiency of competitive adsorption process within berberine-copper system was investigated.Flowing experiments were carried out at 1 bv/h,2 bv/h and 5 bv/h flow velocity.The results showed that adsorption ratio increased with temperature rising and declined with increasing resin dosage.The D401 resin exhibited distinct selectivity of Cu²⁺ from berberine-copper system in a broad range pH value.The best adsorption condition achieved 39.86 mg/g at pH value of 5.0.The adsorption process could be described by Langmuir model and pseudo-second-order kinetic model.Flowing experiments showed that the 1 bv/h was the best condition.The removal of Cu²⁺ obtained better results under this flow velocity and the adsorption of berberine were not obviously at three flow velocities.Cu²⁺ contained by berberine pharmaceutical wastewater could be effectively removed after crystallize precipitation and ion exchange processes,however high concentration of berberine within mother Liquor and wastewater remained to be recycled.In order to improve the performance of macroporous resin on adsorbing berberine,amino-modified H-AM resin was prepared on the basis of H103 resin and the changes of functional groups,specific surface and pore size were detected.The results showed that,compared with H103 resin,both specific surface and pore size of H-AM resin were apparently increased.In addition,the berberine absorption ration improved by 8.1mg/g,which is due to amino group on H-AM resin was apt to form hydrogen bonds with ether group of berberine.Based on the investigation of berberine adsorbing performance using H-AM resin under different conditions,the optimum conditions would be initial pH value of 8 and reaction temperature of 25?.Moreover,the adsorption dynamics and thermodynamics were analyzed,which indicated the adsorption process fitted the Freundlich-type isotherm adsorption equation and pseudo-second-order kinetics equation.On the basis of single component adsorption experiment,the study of competitive adsorption characteristics of two-component system that consisted of berberine and 3,4-methylenedioxy-phenethylamin using amino-modified H-AM resin under different conditions was conducted.The selective adsorption ability and adsorption thermodynamics,as well as the interactions between the solute and adsorbent were researched and compared with single component adsorption.The actual treatment process for wastewater containing high concentration of berberine and low proportion of 3,4-methylenedioxy-phenethylamin applying H-AM resin was further evaluated.The results demonstrated that,3,4-methylenedioxy-phenethylamin would barely affect adsorption of berberine.In contrast,the presence of berberine in wastewater would significantly reduce the adsorption capacity of 3,4-methylenedioxy-phenethylamin.The reason would be that,the adsorption was favor for the stronger static electricity generated between berberine and resin.The adsorption isotherms of two-component system under different conditions were in accordance with the Freundlich-type isotherm adsorption equation.The pilot scale test was carried out within the pharmaceutical enterprise,which verified the results of bench-scale experiments and further proved feasibility of crystallize precipitation-resin adsorption process.This treatment process could achieve recycling of berberine and copper from wastewater while adjusting pH value from acidic to neutral?from less than 1.0 to higher than 7.0?,thus contributed to following biochemical treatment and discharging with standard level.Lastly,the modification of existing production facility for tribasic copper chloride?TBCC?and a month-long trial production were carried out in the workshop.The trial production achieved efficient performance and gained recognition of the enterprise.Compared with the previous ferric-carbon process,TBCC process had advantages in several aspects: 1)more secure.The potential safety risks would be greatly reduced due to the fact that it would not generate hydrogen.2)more environmentally friendly.After treatment,effluent could be directly discharged into sewer,which may reduce the operation cost of wastewater treatment plant in enterprise.3)easy to operate.No heating required for this process,thus it may prolong the service life of filter press and reduce the impact of manual operation on production quality.4)shorter production period.It would decrease 1-1.5 hours reaction time for each batch compared with ferric-carbon process.5)high economic benefit.It may increase the economic benefit of 120,000 yuan a month.Additionally,it only required a storage tank and automatic dosing equipment for modifying original process.The equipment for berberine recycling try-production was in planning as well.