CN101234335A - Method and use for preparing natural adsorption agent by zymolysis - Google Patents
Method and use for preparing natural adsorption agent by zymolysis Download PDFInfo
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Abstract
The invention discloses a method and usage of preparing natural absorbent with enzymatic hydrolysis. Adding abandoned biomass and degrading enzyme solution into a fermentation reactor, and the pH value of the enzymolysis buffer solution is 3 to 6 under a enzymolysis temperature of 30-50 DEG C, and the natural absorbent is prepared through washing, filtering, drying and grinding after 1 to 10 days of stirring enzymolysis in 20 to 200r/min; the degradation enzyme is cellulose of 0.5 to 8mg/L, pectinase of 0.5 to 8mg/L or the mixing solution of the cellulose and the pectinase with a proportion of 1 to 1; 10 to 100mL degradation enzymes are added into every gram of abandoned biomass raw materials, which enables 2 to 20IU of active enzymes to be added into every gram of biomass raw material. The prepared natural absorbent are used for removing a micro amount of persistent organic pollutants in wastewater or drinking raw water and absorbing liquid organic pollutants leaked in accidents. The method and usage of preparing natural absorbent with enzymatic hydrolysis has the advantages of simple preparation method, low cost and environmental protection; the absorbent has strong absorption power, large capacity without toxicity or harm.
Description
Technical field
The present invention relates to the preparation and the application in polluting control thereof of environmental friendliness sorbing material, relate in particular to a kind of method and purposes of preparing natural adsorption agent by zymolysis.
Background technology
Persistence organic pollutant (persistent organic pollutants, POPs) great majority have carcinogenic, teratogenesis, mutagenicity, and high biological accumulation and refractory organics extensively are present in the environment.Calendar year 2001, more than 100 countries and regions representative signed famous " Convention of Stockholm " jointly in the Stockholm of Sweden, require each signatory to adopt various measures, strengthen international cooperation, production, use, trade and the processing of common specification and management POPs are disposed.In the waste water of industries such as coking, medication chemistry and printing and dyeing discharging, usually contain a large amount of persistent organisms, yet the production technology of existing wastewater treatment sorbing material and drinking water is difficult to effectively remove this pollutant, cause problems such as water environment POPs pollution and drinking water safety, population health and ecological safety are constituted a serious threat.In addition, in China's rapid economic development process, environmental pollution accident enters the high-incidence season now, and the accident of liquid organic pollution is revealed and happened occasionally.As in November, 2005 China's oil Jilin Petrochemical company blast, cause liquid state organics leakages such as nitrobenzene, serious contaminated Song Hua River water body.Therefore, development of new is efficient, cheap, stable, the sorbing material of safety, environmental protection, be used for efficiently removing waste water or drinking water persistence organic pollutant, the liquid organic pollution of big capacity fast Absorption, to guaranteeing drinking water safety and adopting emergence technology control dump all significant.
Since 20 end of the centurys, many countries drop into lot of manpower and material resources in succession, control and the removing method of research and searching POPs.At present, handle organic wastewater usually and mainly contain three class methods, be i.e. bioanalysis, physical-chemical process and chemical method; Wherein using maximum is the physical chemistry treatment technology, the materialization of persistent organic pollutants is handled then mainly adopted absorption method, Coagulation Method and extraction etc., and wherein using maximum is absorption method.The key of absorption method is to search out big capacity, safety, callable efficient sorbing material.Adsorbent commonly used has active carbon, polymeric adsorbent, active carbon fibre peacekeeping organic modified bentonite.At present both at home and abroad mainly adopt charcoal absorption, activated carbon has the good treatment effect to the dissolubility organic pollution, but its adsorption capacity is little, easily saturated, cost is high.Though the organobentonite absorption property is good, adsorption capacity is big, the easy desorption of surfactant often causes that COD is difficult to qualified discharge in the wastewater treatment.
8,666 hundred million tons of plant organic matters of annual approximately formation are renewable resources that distributed in nature is the widest, content is maximum, cheap on the earth.China only agricultural crop straw annual output can reach 600,000,000 tons more than.Discarded living beings are except that being used for industry such as papermaking, building, weaving on a small quantity or with producing fodder, the fuel wood, major part is not used effectively, and rot in vain or burn, and some also causes environmental pollution (for example burning).Recently, along with the proposition of biomass energy, caused very big concern in the application of energy field.Yet the living beings as renewable resource are blank in the application of field of environment protection always.The general environment adsorbent adopts heat treatment or chemical treatment mode to prepare; And that enzymatic isolation method mild condition, efficiency of pcr product height, equipment require is low, energy consumption is low and environmental protection and receiving much concern.Relevant employing enzyme solution prepares natural adsorbent, and it is then considerably less to be used for the emergency processing of environmental protection such as water treatment or environmental pollution accident.
CN1304303C discloses a kind of preparation method who is used for the controlled high molecule carbon source material of bioanalysis water treatment, comprise that solution is miscible, enzymolysis, mechanical blending and freeze forming step repeatedly, be applicable to various water treatment process and the reparation of underground water biology in situ.
CN101003824A discloses the method for using the cellulase adsorbing stalk cellulose of enzymolysisby, step is as follows: will mix with cellulose enzyme liquid through steam blasting and the dry steam puffed stalk of handling, behind absorption-desorption, with the steam puffed stalk that is adsorbed with cellulase 40 ℃～50 ℃ following enzymolysis 48～72 hours; This absorption-desorption-enzymolysis process can shorten enzymolysis time, save power consumption, and cellulase is recyclable.
CN 101037703A discloses a kind of hydrolysis and fermentation method of reinforcing straw cellulose, with the crops steam-exploded straw is raw material, in solid-state fermentation reactor, add cellulase and rust system sphere, in pH=4～6,30～50 ℃, rock under the dynamic condition, make steam exploded wheat straw high speed enzymolysis produce reduced sugar; The cellulase that is added is a commercial Aspergillus niger; This invention is mainly used in the cellulose solid fermentation field, can significantly improve steam puffed stalk saccharification, fermentation reaction speed, and the energy that solves living beings is converted into problem.
Publication number CN 1 806945A discloses stalk preliminary treatment and enzymolysis group technology, with the method for the complete enzymolysis of stalk cellulose.Stalk at first through the quick-fried processing of vapour, is used hot wash then, removes the hemicellulose polysaccharide, mix with ionic liquid dry back, heating using microwave or directly heating, the stalk water after will handling then washes repeatedly, and the solvent in the cleaning solution can reclaim by methods such as distillations.The processing stalk of rinsing well is used cellulase degradation 48～72 hours in the buffer solution of pH4.8 under 50 ℃, cellulosic enzymatic hydrolyzation can reach 100%.
CN 1763208A discloses the separating and extracting process of two kinds of enzymolysis xylogens, and the method separation and Extraction from the residue of microorganism enzymolysis corn stalk that adopts organic solvent extraction and inorganic chemical to handle respectively obtains enzymolysis xylogen.Enzymolysis xylogen has kept the active group of lignin preferably, is suitable for preparing the modified product of lignin, and good economic worth is arranged.
Summary of the invention
The object of the invention provides a kind of method and purposes of preparing natural adsorption agent by zymolysis.
The method of preparing natural adsorption agent by zymolysis: in fermentation reactor, add discarded living beings, digestive enzyme solution, the pH of enzymolysis cushioning liquid is 3～6, hydrolysis temperature is 30～50 ℃, stir enzymolysis after 1-10 days in 20-200r/min, through washing, filtration, oven dry, pulverizing, then make natural adsorbent; Digestive enzyme is 0.5-8mg/L cellulase, 0.5-8mg/L pectase or cellulase and 1: 1 mixed liquor of pectase, and the digestive enzyme that adds in the biomass material that every gram is discarded is 10-100mL, makes to add the 2-20IU organized enzyme in every gram biomass material.
Described discarded living beings are the accessory substance of plant pericarp, straw or cellulose industry.
The plant pericarp is tomato pericarp, apple pericarp or potato pericarp, and straw is maize straw, straw, sorghum straw, reed, rape straw, cotton straw, peanut seedling, peanut shell or bagasse.
Digestive enzyme solution is 1-6mg/L cellulase, 1-6mg/L pectase or cellulase and 1: 1 mixed liquor of pectase.
Cellulase is trichoderma reesei, Trichoderma viride, aspergillus niger or koning trichoderma.
Buffer solution is the citric acid/sodium citrate of acetic acid/sodium acetate or the 0.01～0.5mol/L of 0.01～0.5mol/L.
The digestive enzyme that adds in the biomass material that every gram is discarded is 20-80mL, makes every gram biomass material add the 5-15IU organized enzyme.
Hydrolysis temperature is 40-50 ℃.
The natural adsorbent of enzymolysis preparation is used for adsorbing the micro-persistence organic pollutant of waste water or drinking original water, and micro-persistence organic pollutant comprises organic by-products, aromatic nitro compounds or many chloros dibenzodioxin English/furans of polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, heteroaromatic compound, organic agricultural chemicals, medication chemistry.
The natural adsorbent of enzymolysis preparation is used to adsorb liquid organic pollution, and organic pollution comprises benzene series thing, petroleum-type, nitrobenzene, phenyl amines, aldoketones, alkanes, alcohols or ester class.
The present invention has that the preparation of adsorbent method is simple, raw material sources extensively, low production cost, production process environmental protection, enzyme liquid is reusable; The natural adsorbent that makes is big to high adsorption capacity, the adsorption capacity of persistence organic pollutant, product is nontoxic, is specially adapted to that micro-persistent organic pollutants are removed in drinking water or the waste water in efficient absorption and big capacity absorbs the liquid organic pollution that leaks because of accident; The easy reclaiming of natural adsorbent after the adsorption treatment is used.Prepare environment adsorbing materials with discarded living beings, reach the purpose of " turning waste into wealth ", " treatment of wastes with processes of wastes against one another ", have dual environment protection significance, have remarkable economic efficiency, have environmental benefit especially.
Description of drawings
Accompanying drawing is the flow chart of the method and the purposes of preparing natural adsorption agent by zymolysis.
The specific embodiment
Preparing natural adsorption agent by zymolysis be in fermentation reactor, to add discarded living beings, digestive enzyme solution, the pH of enzymolysis cushioning liquid is 3～6, hydrolysis temperature is 30～50 ℃, stir enzymolysis after 1-10 days in 20-200r/min, through washing, filtration, oven dry, pulverizing, then make natural adsorbent; Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty.Digestive enzyme is 0.5-8mg/L cellulase, 0.5-8mg/L pectase or cellulase and 1: 1 mixed liquor of pectase, and the digestive enzyme that adds in the biomass material that every gram is discarded is 10-100mL, makes to add 2-20 IU organized enzyme in every gram biomass material.The purposes of this natural adsorbent comprises: be used for efficient absorption and remove the micro-persistence organic pollutant of water, big capacity absorbs the liquid organic pollution of accident leakage.Following examples further specify.
Embodiment 1
With plant pericarps such as discarded tomato pericarp, apple pericarp, potato pericarps is raw material, 1: 1 the mixed liquor that in fermentation reactor, adds 0.5mg/L cellulase and 0.5mg/L pectase, under the buffer solution of acetic acid/SAS of 0.01mol/L (pH=5), under 30 ℃ of fermentation temperatures of control and the 20r/min mixing speed, living beings enzymolysis 10 days.The enzyme liquid that adds 100mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-1 after washing, filtration, oven dry, pulverizing.
Embodiment 2
With plant pericarps such as discarded tomato pericarp, apple pericarp, potato pericarps is raw material, 1: 1 the mixed liquor that in fermentation reactor, adds 2mg/L cellulase and 2mg/L pectase, under the buffer solution of the citric acid/sodium citrate of 0.05mol/L (pH=3), under 40 ℃ of fermentation temperatures of control and the 50r/min mixing speed, living beings enzymolysis 5 days.The enzyme liquid that adds 50mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-2 after washing, filtration, oven dry, pulverizing.
Embodiment 3
With plant pericarps such as discarded tomato pericarp, apple pericarp, potato pericarps is raw material, 1: 1 the mixed liquor that in fermentation reactor, adds 8mg/L cellulase and 8mg/L pectase, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.5mol/L or 0.5mol/L (pH=3), under 50 ℃ of fermentation temperatures of control and the 200r/min mixing speed, living beings enzymolysis 1 day.The enzyme liquid that adds 10mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-3 after washing, filtration, oven dry, pulverizing.
Embodiment 4
With discarded straws such as maize straw, straw, sorghum straw, reed, rape straw, cotton straw, peanut seedling, peanut shell or bagasse is raw material, in fermentation reactor, add the 0.5mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.01mol/L or 0.01mol/L (pH=4), under 30 ℃ of fermentation temperatures of control and the 20r/min mixing speed, living beings enzymolysis 10 days.The enzyme liquid that adds 100mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-4 after washing, filtration, oven dry, pulverizing.
Embodiment 5
With discarded straws such as maize straw, straw, sorghum straw, reed, rape straw, cotton straw, peanut seedling, peanut shell or bagasse is raw material, in fermentation reactor, add the 2mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.05mol/L or 0.05mol/L (pH=3), under 40 ℃ of fermentation temperatures of control and the 50r/min mixing speed, living beings enzymolysis 5 days.The enzyme liquid that adds 50mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-5 after washing, filtration, oven dry, pulverizing.
Embodiment 6
With discarded straws such as maize straw, straw, sorghum straw, reed, rape straw, cotton straw, peanut seedling, peanut shell or bagasse is raw material, in fermentation reactor, add the 8mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.5mol/L or 0.5mol/L (pH=3), under 50 ℃ of fermentation temperatures of control and the 200r/min mixing speed, living beings enzymolysis 1 day.The enzyme liquid that adds 10mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-6 after washing, filtration, oven dry, pulverizing.
Embodiment 7
Accessory substance with discarded cellulose industry is a raw material, in fermentation reactor, add the 0.5mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.01mol/L or 0.01mol/L (pH=3), under 30 ℃ of fermentation temperatures of control and the 20r/min mixing speed, living beings enzymolysis 10 days.The enzyme liquid that adds 100mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-7 after washing, filtration, oven dry, pulverizing.
Embodiment 8
Accessory substance with discarded cellulose industry is a raw material, in fermentation reactor, add the 2mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.05mol/L or 0.05mol/L (pH=3), under 40 ℃ of fermentation temperatures of control and the 50r/min mixing speed, living beings enzymolysis 5 days.The enzyme liquid that adds 50mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-8 after washing, filtration, oven dry, pulverizing.
Embodiment 9
Accessory substance with discarded cellulose industry is a raw material, in fermentation reactor, add the 8mg/L cellulase solution, under the citric acid/sodium citrate buffer solution of the acetic acid/SAS of 0.5mol/L or 0.5mol/L (pH=3), under 50 ℃ of fermentation temperatures of control and the 200r/min mixing speed, living beings enzymolysis 1 day.The enzyme liquid that adds 10mL in every gram biomass material.Cellulose and the pectin isopolarity component in the biomass material removed in dissolving; The component of residue is mainly non-polar component, comprises the plant lignin of armaticity and the plant cutin of fatty; The residue that obtains makes natural adsorbent NS-9 after washing, filtration, oven dry, pulverizing.
Embodiment 10
Natural adsorbent NS-1～NS-9 to the present invention's preparation is used for removing the micro-persistence organic pollutant of water, as organic by-products, aromatic nitro compounds, many chloros dibenzodioxin English/furans PCDD of polycyclic aromatic hydrocarbon PAHs, Polychlorinated biphenyls PCBs, heteroaromatic compound, organic agricultural chemicals, medication chemistry; When soil ratio is 1: 1000～1: 10000, natural adsorbent to the clearance of organic pollution in the water greater than 90%; To PAHs, PCBs and PCDD, then greater than 99%.
Embodiment 11
Natural adsorbent NS-1～NS-9 to the present invention's preparation is used to absorb liquid organic pollution, as benzene series thing, petroleum-type, nitrobenzene, phenyl amines, aldoketones, alkanes, alcohols, ester class etc.; Uptake＞the 0.5g/g of natural adsorbent liquid towards organic pollution, wherein maximal absorptive capacity can reach 2.2g/g.
Claims (10)
1. the method for a preparing natural adsorption agent by zymolysis, it is characterized in that, in fermentation reactor, add discarded living beings, digestive enzyme solution, the pH of enzymolysis cushioning liquid is 3～6, hydrolysis temperature is 30～50 ℃, stir enzymolysis after 1-10 days in 20-200r/min, through washing, filtration, oven dry, pulverizing, then make natural adsorbent; Digestive enzyme is 0.5-8mg/L cellulase, 0.5-8mg/L pectase or cellulase and 1: 1 mixed liquor of pectase, and the digestive enzyme that adds in the biomass material that every gram is discarded is 10-100mL, makes to add the 2-20IU organized enzyme in every gram biomass material.
2. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 1 is characterized in that described discarded living beings are the accessory substance of plant pericarp, straw or cellulose industry.
3. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 2, it is characterized in that described plant pericarp is tomato pericarp, apple pericarp or potato pericarp, straw is maize straw, straw, sorghum straw, reed, rape straw, cotton straw, peanut seedling, peanut shell or bagasse.
4. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 1 is characterized in that described digestive enzyme solution is 1-6mg/L cellulase, 1-6mg/L pectase or cellulase and 1: 1 mixed liquor of pectase.
5. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 2 is characterized in that described cellulase is trichoderma reesei, Trichoderma viride, aspergillus niger or koning trichoderma.
6. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 1 is characterized in that described buffer solution is the citric acid/sodium citrate of acetic acid/sodium acetate or the 0.01～0.5mol/L of 0.01～0.5mol/L.
7. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 1 is characterized in that the digestive enzyme that adds in the discarded biomass material of the described every gram of its feature is 20-80mL, makes every gram biomass material add the 5-15IU organized enzyme.
8. the method for a kind of preparing natural adsorption agent by zymolysis according to claim 1 is characterized in that the described hydrolysis temperature of its feature is 40-50 ℃.
9. purposes of the natural adsorbent of method enzymolysis preparation as claimed in claim, it is characterized in that being used for adsorbing the micro-persistence organic pollutant of waste water or drinking original water, micro-persistence organic pollutant comprises organic by-products, aromatic nitro compounds or many chloros dibenzodioxin English/furans of polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, heteroaromatic compound, organic agricultural chemicals, medication chemistry.
10. purposes of the natural adsorbent of method enzymolysis preparation as claimed in claim, it is characterized in that being used to adsorb liquid organic pollution, organic pollution comprises benzene series thing, petroleum-type, nitrobenzene, phenyl amines, aldoketones, alkanes, alcohols or ester class.
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| CN104801285A (en) * | 2015-05-06 | 2015-07-29 | 哈尔滨工业大学 | Preparation method of mycete and agricultural and forestry waste mixed bio-adsorbent |
| CN107698330A (en) * | 2017-11-02 | 2018-02-16 | 中山国晟生物工程有限公司 | A kind of full-service fluid fertilizer of degradable residues of pesticides and preparation method thereof |
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