Fermentation production of propionic acid（PA）and vitamin B₁₂(VB₁₂)is greatly inhibited by propionic acid that is product of fermentation.By the removal of propionate acid,high concentration of propionic acid and VB₁₂ was obtained.In this thesis,PA has been separated by adsorption.Adsorption behaviors and the selectivity were studied by using static methods including the static equilibrium adsorption,the adsorption thermo dynamics properties and the kinetics of adsorption.The good operation conditions including adsorption,washing,desorption and regeneration,have been confirmed by dynamic adsorption methods.Then PA has been separated from the fermentation broth.PA was separated by expanded bed was preliminary studied.The adsorbent ZGA330 was selected to separate PA from the residual solution of fermentation.The adsorbent selectivity is good,which the selectivity coefficient（K）of PA with amino acids and glucose in turn equaled to 0.025 g·L^-1and 22.9 g·L^-1.The dynamic adsorption experiments indicated that the best flow rate was 3BV·h-^-1;the fitting washing condition:at first wash out 2.0 BV at 3BV·h^-1;the good desorption condition:flow rate of desorption was 3BV·h^-1,the concentration of NaOH solution was 1.0mol·L^-1,the volume of desorption solution was 2.5BV.Based on study of fixed bed,that PA was separated by expanded bed was preliminary studied.The dynamic adsorption experiments indicated that the best expanded volume was 2BV;the fitting washing condition:at first wash out 5.0 BV with 2BV of expanded volume;the good desorption condition: flow rate of desorption was 3BV·h^-1,the concentration of NaOH solution was 1.0mol·L^-1,the volume ofdesorption solution was 2.5BVBy the secondary removal of PA with fixed bed of ZGA330,high concentration of VB₁₂was obtained comparing to the batch fermentation. VB₁₂concentration was 0.55 fold of those in the batch fermentation respectively.By the once removal of PA with expanded bed of ZGA330,high concentration of VB₁₂was obtained comparing to the batch fermentation. VB₁₂concentration was 0.51 fold of those in the batch fermentation respectively.

The matrix used in this study was the natural bentonite produced in Neimeng. The study determined the natural calcium-base bentonite’s basic physicochemical properties first. The result showed that its multiple of expansion and gluey valence are 8.4mL/g and 10.2mL/g, the content of Montmorillonite is 43.79%.The study adopt three modified methods, Na-modified, roasting-modified and organic-modified.The result showed that the best preparation condition of Na-modified bentonite is: the proportion of calcium-base bentonite and 4% Na2CO3 solution is 1:10, pH 9.0, 60℃,stir time 1.0 h, its multiple of expansion and gluey valence are 82.6L/g and 88.8mL/g.The best reaction temperature of roasting-modified bentonite is 450℃and the reaction time is 2h .The best preparation condition of organic-modified bentonite is: the proportion of Na-base bentonite and 5% CTMAB solution is 1:10, pH 4.0, 60℃,stir time 2.0 h.Study on the effect of the Cr (VI)-containing wastewater by using the three kinds of modified bentonite, it can be find that the adsorption rate was affected by pH, adsorption time, dosage of adsorbents and adsorption temperature. Under the best conditions of experiment, the adsorption rate of the Cr (VI) of Na-modified bentonite, roasting-modified bentonite and organic-modified bentonite are 86.1%、81.2% and 97.5%. After modifying, the nature bentonite can improve its adsorption ability greatly.By the end , the correlative mechanism also be discussed , the experiment result show that the Na-activated modification bentonite’absorption on the Cr (VI)-containing wastewater conforms to the Freundlich absorption isothermal equation more suitable, accordingly the Na-activated modification bentonite’absorption on the Cr (VI)-containing wastewater conforms to the Langmuir absorption isothermal equation more suitable.

With the more demand for energy and the less fossil fuel,to find a new continuable energy is to be an urgency mission for us in near future.Biomass energy as a renewable energy has been paid more attention in the countries all over the world,and how to study, exploit and utilize it has become an important task,too.Biomass pyrolysis/catalytic pyrolysis is one of the promising technologies converting biomass to bioenergy.Pyrolysis and Catalytic pyrolysis experiments,using micron pine sawdust as test materials,were performed in a fixed-bed with nickel-based catalysts prepared by ourselves, and the products and its components were analyzed.The influences of parameters such as catalysts,temperature and steam on experiment were also discussed.The results showed that the catalytic pyrolysis with nickel-based catalyst,which is superior to dolomite, promoted significantly the cracking of tar in gas and improved effectively the quality and yield of product gas.The yields of tar and char decreased while that of gas increased markedly,and content of CO and H₂ in gas also enhanced as the increasing temperature, which is helpful for producing more combustible gas.At the same time,the contents of tar and coke lessened while that of H₂ and the quantity of gas enhanced prominently with vopour in catalyst pyrolysis.Meanwhile,this dissertation studied on characteristic of residual carbon after steam activation derived from biomass pyrolysis and its adsorption performance on copper ion in waste water.The effect of adsorption time,particle size and solution pH on adsorption of copper ion were discussed.The results indicated that the optimal adsorption condition was as follows:particle size 0.3-0.45mm,adsorption time 120min,pH6.2.The corresponding adsorption efficiency was above 85%.

Nitrogen and phosphate are essential elements for animals and plants. But with the rapid development of industry and agriculture, there are thousands of tons phosphate and nitrogen releasing into surface water system. Because it enhances the growth of organisms in most ecosystems such as rivers, lakes, result in eutrophication and deterioration of water quality. Many techniques have been carried out for the removal of phosphorus and nitrogen from wastewater, for examplephysical chemistry method, biologic method, and membrane technique and constructing wetland to remove phosphate. Because of high cost and secondary pollution, they are largely limited to be applied. The application of iron sludge used as a sorbent to construct wetland is low cost and easily available. So it becomes a research hotspot and an important task. It has a large potential value to utilize iron sludge from waterworks to pure wastewater.After a detailed research, the iron sludge from waterworks is first used to remove phosphorus for its strong adsorption properties in this study. It can be applied for the deep deck of wetland soil landfill, not only can play a solid phosphorus supply to wetlands Plants, can also manage the water plant sludge reasonable consumed. A series of experiment have been carried out for the adsorption capacity to remove phosphorus, then the results showed that the pH around 5 was the best condition for phosphate adsorption.Batch adsorption studies on dried iron sludge were conducted to optimize various equilibrating conditions like the effect of contact time, initial concentration, pH, mass of sorbent, coexisting ion and so on. The results show that strong acid and strong base went against the adsorption of phosphate; while the optimal pH was around 5 and the maximal adsorption reach 24mg/g. The adsorption capacity decreased with the increase of adsorbent doze and ion strength. Simple ions had no obvious effects on adsorption. Iron sludge had good selectivity for adsorption of phosphate. Longmuir and Freundlich adsorption isotherm constants and correlation coefficients were calculated and compared. It was concluded that the adsorption data of phosphate onto iron sludge fitted to the Langmuir model more than Freundlich model.XRD, SEM, TEM, FT-IR and TG were used for the characterization of the sorbent. It is concluded that the coordination mechanism of ligand ion exchange outer surface and electrostatic adsorption were dominant. In addition, the column of iron sludge was experimnented at different column length , flux, initial concentration. The conclution suggested that the iron sluge can be used in the wetland for it chemical characteristic.

Esters as volatile organic compounds are harmful for human being, which are emitted in many industrial activities. In particular, methyl acrylate （MA） and ethyl acetate （EA） are widely used in industry. Therefore, the investigation for removal of them from the exhaust gas and further for the recovery of them from the exhaust gas is of great importance in terms of economic and social benefic meaning.In this thesis, adsorption of MA and EA on activated carbons was investigated in dynamic adsorption method in the MA/N₂ and EA/N₂ system, respectively. For the investigation, two kinds of activated carbons, AC and Y₂, made from coconut shells, and one kind of activated carbon, C5, made from coal were used. On the activated carbons, the adsorption influenced by the concentration of esters in gas mixtures, adsorption temperature and relative humidity of the gas mixtures was discussed in detail.It indicated that the adsorption isotherm could be described well by the Langmuir-Freundlich model and that the saturated adsorption amount of MA on the AC at 40℃was always the largest among those obtained on the three activated carbons when the volume percentage of MA (ρ_MA) in the gas mixture was ranged from 0.015 % to 0.34 %. Nevertheless, whenρ_MA was lower than 0.015 %, Y₂ gave the largest adsorption amount in equilibrium. The results indicated that pore structure of activated carbons had much effect on their adsorption capacities. The above adsorption performence of AC and Y₂ in different conditions can be interpreted by the abundant micropores and mesopores in AC and the smaller average pores in Y₂, respectively. Similar to the case of MA, larger saturated adsorption amount of EA was obsverved on activated carbons AC and Y₂ compared to that on C5 at 40℃when the volume concentration of EA (ρ_EA) in the gas mixture falls in the range of 0.10～0.30 %. In the gas mixture of EA/N₂ with a concentration of 0.15 % in volume percentage, the adsorption amount of EA on the activated carbons AC and Y₂ were 0.28 g·g^-1 and 0.27 g·g^-1, respectively. On the other hand, no significant change in the saturated adsorption amount of EA was observered for the activated carbons with modified surface chemistry properties compared to those unmodified activated carbons. These results indicated that the adsorption capacity of activated carbons for EA was mainly determined by the micropore less than 1.70 nm （in diameter） but not surface chemistry of the adsorbents. The influence of temperature on adsorption for MA and EA on AC was studied. The saturated adsorption amount of MA on AC at 40, 30, 20 and 10℃were 0.29, 0.33, 0.35 and 0.37 g·g^-1. In the case of EA, the saturation adsorption amount on the activated carbon were 0.27,0.30 and 0.31 g·g^-1 at 40, 30 and 20℃in the gas mixture of EA/N₂ with a concentration of 0.15 % in volume percentage. As temperature had little effect on the esters adsorption on the activated carbon, it is suggested that the adsorption technique using the activated carbon as adsorbent can be put to use for remove the esters from exhaust at room temperature.Saturated adsorption amount of MA and EA on AC that is as high as 90 % of that achieved in dry conditions was still obtained when an adsorption experiment was conducted under a relative humidity of 40 %.The regeneration of activated carbon and the recovery of EA and MA could be effectively performed by heating the absorbent after adsorption. The adsorption （40℃）-desorption （300℃） recycle was conducted for six times in experiment, and the result has revealed that the adsorption property of activated carbon was unchanged, indicating that the activated carbon AC can be well used repeatedly as an adsorbent for esters adsorption.

A new route for the economic and efficient treatment of azo dye pollutants is reported, in which mesoporous silica （MS） and surface-modified organic-inorganic hybrid mesoporous silica spheres were chosen as microreactors for the accumulation and subsequent photodegradation of pollutants in defined regions. The MS was synthesized according to Stober method from sodium silicate. The surface-modified silica materials were prepared by anchoring the polycationic species such as poly（allylamine hydrochloride） （PAH） on MS spheres via a simple wet impregnation method. The as-synthesized MS and PAH-modified MS （PAH-MS） spheres with well-defined porous structures exhibited a very efficient accumulating capacity for different kinds of the target pollutant. According to the new method, the pollutants were completely degradated in the Fenton system under the visible light efficientlyComparative photodegradation study on homogeneous dye solution and heterogeneous dye-accumulated suspension in Fenton reagent, together with kinetics patterns in recycling degradation show that the MS and the PAH-MS spheres may be utilized as environment-friendly microcarriers for the remediation of dye wastewater.It was also examined that Fe-anchored mesoporous SiO₂ as microcarrier accumulated dyes, and the dyes-accumlated on the SiO₂ was degradated in Fenton system under the visible light. It was found that the degradation efficiency of dyes on the Fe-anchored mesoporous SiO₂ had been improved greatly.

With the development of crude oil industry and oil carrying trade, seabed oil reconnaissance、exploitation and oil tanker building, more and more crude oil have been the most dangerous contamination, ocean spilled oil accident was a important environment contamination, complicated physical、chemical and biological reaction happen when crude oil influxes seawater, including the sorption of crude oil by suspended particulate matter.Heavy fuel oil ,one of the crude oil , contain more impurity and substance, Studying on sorption of heavy fuel oil by suspended particulate matter, researching this sorption rule is helpful for the transform and vanish, even for self- purification of the ocean, it will provide effective measures to improve environment quality.Zhoushan is the important fishery of our country, also the main port, zhoushan is the distributing center of national crude oil, suffer the influence of spilled oil. At the same time, this place locates alluvial area of Changjiang River, contains high suspended particulate matter, study this adsorption theory in order to provide foundation of controlling pollution.This paper simulates the process of the sorption of heavy fuel oil by suspended particulate matter; discuss the influence factor to the sorption, provide reliable theoretic support to repair spilled oil environment.According to this paper, we can conclude that: the process of the sorption between suspended particulate matter and heavy fuel oil is effected by following factors: temperature、particle size、salinity、pH, averagely, the process reaches the equilibrium within 40 minutes, temperature is the main factor, at low temperature , sorption tend to happen following the elevatory temperature. High temperature does go against the adsorption, sorption amount descend at high temperature .more sorption happens when the particle is smaller and higher salinity, acidic and alkalescent environment promote the sorption, sorption process could describe as Freundlich isotherm.

These decades, oil spill occurs often on the sea, the oil contaminant has heavily effect on the marine ecosystem. One of the most important final fate of the oil contamination is entering into the sediments by the adsorption and sedimentation, it exists the adsorption and desorption of oil on sediments in the same time, which is a homeostasis, the desorption of oil contamination brings the secondary pollution to the marine ecosystem, thus studying on the adsorption between the sediments and the oil is benefit for understanding of the equilibrium adsorption quantity, adsorption equilibrium time and the adsorption disciplinary, which could provide some information about the investigation and governing of the environment contamination.The paper accords to the current status of oil contamination, especially when it was 2006, the container ship is driving into the ship yard dock of Zhoushan city of Zhejiang province, which was collide into another ship, the fuel oil tank was despair, the heavy fuel oil spilled, according the above, we study on adsorption of heavy fuel oil on the sediments.The paper simulated the process of adsorption of heavy fuel oil on the Yellow River Estuary sediments and the Zhoushan maritime area sediments, we study on the time and the quality of adsorption equilibrium in the dynamic and static circumstance, then we measured the petroleum content with Ultraviolet Spectrophotometer. It comes to the following conclusions:When it is in the dynamic condition, the time of adsorption equilibrium on the Yellow River Estuary and the Zhoushan maritime area sediments is about 3h and 2h; And the quality of adsorption equilibrium on the Yellow River Estuary and the Zhoushan maritime area sediments is about 1072.9μg/g and 1224.7μg/g in the dynamic condition.When it is in the static condition, the time of adsorption equilibrium on the Yellow River Estuary and the Zhoushan maritime area sediments is about 36h and 24h; And the quality of adsorption equilibrium on the Yellow River Estuary and the Zhoushan maritime area sediments is about 444.99μg/g and 919.26μg/g; The adsorption quality of heavy fuel oil on the the Yellow River Estuary and the Zhoushan maritime area sediments decreases with the increasing temperature, increases with the increasing salty, and decreases first, then increases with the increasing pH. decreases with the increasing particle size.When it is in the static condition, the adsorption of heavy fuel oil on the Yellow River Estuary is fit for the Langmuir adsorption isotherms, and the adsorption of heavy fuel oil on the Zhoushan maritime area sediments is fit for the Freundlich adsorption isotherms.

Cadmium is a non-essential nutrient element for plant. Due to the high biotoxicity, strong bioavailability and mobility, the presence of Cadmium in the rhizosphere can inhibit the plant growth, cause alterations in morphological and physiological disorders in plant, affect several plant metabolic processes such as photosynthesis. With the development of economy, more and more cadmium goes into the natural environment. Cadmium contamination is characterized by hidden and accumulation and it is closely related to man’s living, in this case, this problem has been the key point in the research of environmental science.In this article, we analized the changes of the cadmium desorption along with the time passing under different cadmium content; the effect of the cadmium on the morphological and physiological of the vegetable; the relationship between the configuration of the internal structure in the plant and the content of the cadmium, in order to study the stability and the plant effect of the cadmium in the soil. The results showed as following:(1) Via column test, we analyzed the changes of the cadmium desorption along with the time passing under the different cadmium content, we also add active carbon-calcium hydroxide into the soil, and the result showed that when the amount of the active carbon-calcium hydroxide reached 5g/kg, the cadmium was greatly restrained. At the same time, the stability of the other heavy metal ion affected by cadmium was studied too.(2) On the basis of the potted plant experiment of lettuce、spinach、cabbage, we analyzed the morphological and physiological of those vegetable at different growth period, and also at different cadmium content, we found that the lettuce was the best vegetable to monitor the changes of the cadmium in the soil.(3) We used the OCT to analyze the leaf samples, the OCT parameters such as light intensity, light intensity×thickness, light intensity/variance are significant changed as the content of cadmium and growth period of the vegetable increased. At last we found the relationship between the configuration of the internal structure of the plant and the content of the cadmium.(4) As the content of cadmium in the soil increased, the content in the roots, stems and leaves were increased too, while the zinc was greatly inhibited. The ratio of the content in the plant and soil was reduced, it showed that the ability of the plant to absorbed the heavy metal was keep consistent with the content of the heavy metal.

The molecule of chitosan contains high contents of amino groups, which can be protonated by integrating H+ in solution. So it has favorable adsorbability to some inorganic acid, organic acid, acor compound. Chitosan can be dissolved in acid solution. It limits its application as absorbent.The references about the chitosan structure characteristics, properties and modification research actualities and its practical application had been investigated sufficiently. On the basis of this, using glutaradehyde as the cross-linker, magnetic chitosan microspheres (MCTS) were prepared by the suspension cross-linking technique.The experiments had been carried out to study the adsorption behavior of MCTS for three kinds of phytohormone. In the medium of isopropanol, using perchloric acid as catalyst, hydroxypropyl chloride magnetic chitosan microspheres (ECH-MCTS) were prepared. Furthermore, aminated magnetic chitosan microspheres (EN-MCTS) were prepared by grafting ethylenediamine on the microsphere surface. The adsorption efficiency of aminated magnetic chitosan microspheres were investigated in removal of anoinic dyes acid rhodamine B(AR)、fuchsin acid (FA) and reactive brilliant blue X-BR (RBB) compared with MCTS and ECH-MCTS. The adsorption thermodynamics, kinetics and mechanism were discussed. Chitosan powder had been prepared to be magnetic resin. To the contribution of magnetic field, the chitosan and the resin can be easily isolated. This expanded the application of chitosan consumedly. The major study works and results were as follows:1. The preparation and characterization of magnetic chitosan microspheres.The effects of the dosage of crosslinker glutaraldehyde on microspheres morphology and yield had been observed intensively. The modality observed by optical microscope show that, the yield of microsphere increased, but the aggregation of the microspheres became more serious as the quantity of crosslinker increasing and the adsorption values to abscisic acid decreased correspondingly. The reason was that the amino groups on the surface of the microspheres had been occupied by overmany crosslinker. Therefore, when the crosslinker concentration was 7% and the qantity of the chitosan was 0.5 g, the magnetic microspheres with good dispersion property and uniformity the particle size diffusion were obtained.Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to investigate the morphology and size of the microspheres. The results indicated that the microspheres had well shaped spherical form with smooth surface and the particle size was 3~5μm. The fourier transfor IR (FT-IR) spectrameter , X-ray diffraction (XRD) , differential scanning calorimetry (DSC) and thermogravinetry (TG) were used to analyze the molecular structure and the alteration of the microspheres’thermal character. The results showed that Fe3O4 nanoparticles remained its spinel structure, which packed in the microspheres to form core-shell structure, and the weight percentage of Fe3O4 nanoparticles was estimated to be about 10.9 wt%. The thermal stability of MCTS was lower than chitosan, but was as high as chitosan before 225℃, and also can be easily separated from aqueous solution under the magnetic field.2. The studies of adsorption behaviour and mechanism for acidic phytohormone onto magnetic chitosan mocrospheresMCTS was utilized to adsorb abscisic acid (ABA), gibberellin (GA3) ,3-indoleacetic acid (IAA) by static adsorption. The effects of adsorbent dosage, contact time, pH and the original concentration of ABA, GA3, IAA on the adsorption rate were investigated and optimized. In order to explore the adsorption mechanism of the modified microspheres, the experimental data were fitting by dynamics model including pseudo-second-order equation and pseudo-first-order equation, and isotherms Langmuir and Freundlich isotherms. The results showed that the adsorbent dosage was appropriated at 1.25 g L-1. In 20 minutes ,the adsorption rate to ABA(c0 = 32.28mg L-1),IAA(c0 = 43.80mg L-1),GA3(c0 = 200.0mg L-1)raised up to maximum, and the one step adsorption rate was 89%,93% and 81% respectively. Furthermore, the adsorption efficiencies were greatly influenced by the acidity and ionic strength of solution. A possible explanation for pH effect on adsorption may be related to the surface charge of magnetic microspheres and phytohormone. Amino groups on the surface of microspheres played a major role in adsorption proces. It could be protoned in low pH, combining with acid radical ion dissociated by ABA, IAA or GA3 to complete the adsorption process. So when the pH is too low, amino group couldn’t be protonated easily, but the high acidity impeded the dissociation of ABA, IAA and GA3. And aslo as the increase of ionic strength, high concentrations of NaCl ions could cover the particle surface and form an ion shield, which can decrease the diffusivity of phytohormone and enlarge the absorbed molecules, and therefore reduce the adsorption rate.The results for the experimental data applying pseudo-first-order equation and pseudo-second-order equation showed that the adsorption for phytohormone conformed to the pseudo-second-order equation. It confirmed that the adsorption rate was controlled by chemical sorption. The isotherms model of ABA and GA3 of the modified microspheres indicated that Langmuir isotherm equation gave better fit than the Freundlich isotherm. It confirmed that the adsorption on microspheres was in a monolayer form. The regeneration of the adsorbents could be implemented by 0.1 mol L-1 sodium chloride , only the 5% decrease of adsorption rate could be obtained after regenerating absorbents for five times. These results indicated that the magnetic chitosan microspheres can be recycled.3. The preparation and characterization of modified magnetic chitosan microspheres.The adsorption efficiency of chitosan closely related to its alkalinity. Cross-linking reaction weakened the alkalinity of absorbent and reduced the adsorption efficiency of absorbent. Thus, two kinds of modified microspheres were prepared in order to increase the adsorption efficiency.①Preparation of hydroxypropyl chloride magnetic chitosan microspheres (ECH-MCTS) by using epichlorohydrin modified magnetic chitosan microspheres②Preparation of a new adsobent aminated magnetic chitosan microspheres (EN-MCTS) by using ethylenediamine grafted on the surface of microspheres.The content of amino groups on microspheres were determined by titrimetric method. IR , XRD ,DSC and TG were used to analyze the alteration of ECH-MCTS and EN-MCTS’molecular structure and characte. The results showed that the amino group content of ECH-MCTS decreased obviously. It indicated that both amino groups and hydroxy groups participated in the reaction with ethylenediamine. However, the amino group content of EN-MCTS was twice than that of MCTS. So the alkalinity of EN-MCTS had been strengthened and the adsorbability had been enhanced .4. The studies on adsorption behaviour and mechanism for anionic dye onto MCTS, ECH-MCTS and EN-MCTSThe adsorption behaviour for the three anionic dyes acid rhodamine B, fuchsin acid and reactive brilliant blue X-BR were studied, the experimental factors contact time, pH and temperature had also been explored and optimized. The results showed that within 60 minutes, the adsorption rate for AR and FA on EN-MCTS can reach to 95%, when the original concentrations of AR were chosen at 0.50 mmol L-1, FA were at 0.80 mmol L-1, and the adsorbent dosage was at 0.5 g L-1 and 0.8 g L-1 respectively. However, within 4 hours, the adsorption rate for RBB can reach to 98% on EN-MCTS when the original concentrations were chosen at 0.30 mmol L-1 and the adsorbent dosage was at 0.8 g L-1. The adsorption capability could be enhanced as the concentration of dyes increasing, while the adsorption rate decreased as the acidity increasing on the three magnetic microspheres. But the adsorption on MCTS was affected greatly by the solution acidity compared with ECH-MCTS and EN-MCTS. The results indicated that the adsorption for anionic dyes were affected by the structure of dyes and the steric hindrance of amino groups on microspheres .The results for the experimental data applying dynamics equations and isotherm equations showed that the adsorption for anionic dyes conformed to the pseudo-second-order equation and Langmuir isotherm equation. It confirmed that the adsorption process was in monolayer controlled by chemical sorption. The regeneration of the adsorbents could be implemented by 0.5 mol L-1 NaOH + 2 mol L-1NaCl (V/V=1:1) , the second-regenerated ratios were all > 95%.