CN101575135A - Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 - Google Patents
Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 Download PDFInfo
- Publication number
- CN101575135A CN101575135A CNA2009100526001A CN200910052600A CN101575135A CN 101575135 A CN101575135 A CN 101575135A CN A2009100526001 A CNA2009100526001 A CN A2009100526001A CN 200910052600 A CN200910052600 A CN 200910052600A CN 101575135 A CN101575135 A CN 101575135A
- Authority
- CN
- China
- Prior art keywords
- sba
- enzyme
- water
- phenol
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a method for separating out phenols substances in water by catalytic oxidation with an enzyme-carrying silicon-based mesoporous molecular sieve SBA-15, which belongs to the technical field of application of immobilized enzyme biocatalyst. The method comprises the following steps of: using the silicon-based mesoporous molecular sieve SBA-15 as a carrier, fixing horse radish peroxidase (HRP) simultaneously in the mesoporous duct and the external surface of the SBA-15, using H2O2 as an oxidant, and using the mechanism that the HRP performs catalytic oxidation to the phenols compound to generate sedimentary so as to achieve the aim of separating out phenols pollutants in water. The method can achieve the favorable effect of removing phenols in water under the assistance of solid-liquid separation means. The produced enzyme-carrying SBA-15 has favorable reusability, in particular to the enzyme-carrying SBA-15 after twice fossilization, and the phenols pollutant still can achieve a removal rate of above 60 percent after the enzyme-carrying SBA-15 is reused for six times.
Description
Technical field
The present invention relates to a kind of method of using the enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 catalyzed oxidation to separate out aldehydes matter in the water, belong to the immobilized enzyme biocatalyst applied technical field.
Background technology
Phenolic wastewater is mainly from industrial sector and production processes such as petroleum cracking system ethene, synthesizing phenol, tynex, synthetic dyestuff, organic pesticide and resol such as coke-oven plant, producer gas plant, petrochemical plant, insulating material factorys.Phenolic compound is an organic pollutant common in the water surrounding, belongs to polarity, ionizable, slightly acidic organism, is a kind of protoplasma poisonous substance.The water that long-term drinking is polluted by phenol can cause chronic accumulation poisoning, has only 0.002mg/L even contain phenol concentration in the tap water, also can influence HUMAN HEALTH.Phenol all has certain murder by poisoning to hydrobiont, farm crop, and when containing phenol 0.1～0.2mg/L in the water, the flesh of fish is that the frowziness anorexia is used.With containing the direct irrigated farmland of water that phenol concentration is higher than 100mg/L, can cause the underproduction of farm crop even withered.Therefore, the improvement to phenolic wastewater is very necessary.
The enzymatic oxidation facture of phenolic wastewater is promptly separated out phenol with a kind of specific enzymatic oxidation from water, remove phenol through solid-liquid separation from water again, and most widely used enzyme is horseradish peroxidase (HRP).HRP extracts refining forming from the intravital enzyme of biology, under the effect of HRP, and oxygenant (H
2O
2) with the phenol oxidation, having produced active high intermediates such as benzene oxyradical, they are diffused into solution everywhere from the active centre of enzyme, itself react with enzyme molecule or benzene oxyradical, have generated a series of polymkeric substance.These polymkeric substance have the characteristic of high molecular and low water solubility, thereby easily precipitate from solution and separate out.But free HRP is the same with other resolvases, be subject to environmental influence and inactivation, and be difficult to realize recycling, and immobilization HRP improves its reusability and improves its stable effective means, utilize the good enzyme dispersiveness of immobilized enzyme biocatalyst, higher carry the enzyme amount and higher enzyme is lived, thereby phenol in the water is had higher removal efficient.
Traditional immobilization HRP method uses silica gel, Mierocrystalline cellulose and micropore glass etc. as carrier immobilized HRP, but or between enzyme and the carrier a little less than the bonding force, to conditional request harshnesses such as pH, salt concn, temperature; Or the immobilized enzyme preparation process is difficult, and the enzyme reusability is poor; Or the immobilized enzyme that makes easily misses, and exists diffusional limitation, catalyzed reaction is subjected to problems such as resistance to mass transfer influences, unsuitable catalyzing reaction of macromolecule substrate.Therefore, the new enzyme immobilization carrier of employing is meaningful and presses for.Use mesopore molecular sieve as carrier, have the potential advantage.At first, the mesopore molecular sieve surface is rich in hydroxyl, can play shock absorption to the pH value of solution in the duct, make that the pH value of solution variation range is compared with the main body solution of outside in the duct to want narrower, thereby make the stability of immobilization HRP reduced by the influence that pH changes in the solution.Secondly, because mesopore molecular sieve has the aperture of homogeneous and big pore volume, select fixedly HRP of suitable mesopore molecular sieve for use, the HRP molecule that major part is fixed is in the duct of mesopore molecular sieve, according to heat passage theory, temperature in the duct is lower than the body temperature of solution, so the optimum temperuture of the HRP after the immobilization also has corresponding raising.At last, HRP be fixed in the mesopore orbit can with the hydroxyl generation hydrogen bond action on the hole wall, and the influence of the nano effect that produces in mesopore orbit can make the stability of its conformation that to a certain degree enhancing is arranged, thereby make HRP strengthen at the immobilization rear stability.
At present with the report of mesopore molecular sieve immobilization HRP and few, with SBA-15 immobilization HRP and be used for the processing of water phenol and do not appear in the newspapers yet.The present invention uses SBA-15 immobilization HRP to make and carries enzyme SBA-15, and be applied to catalyzed oxidation and separate out phenol in the water, by adopting sodium alginate to carry out the secondary immobilization, reduced enzyme spillage in use in addition, improved the repeated use number of times of enzyme carrying enzyme SBA-15.
Summary of the invention
The purpose of this invention is to provide a kind of use carries enzyme SBA-15 catalyzed oxidation and separates out the method for aldehydes matter in the water.The present invention is carrier with the silicon-based mesoporous molecular sieve SBA-15, at the mesopore orbit of SBA-15 and outside surface fixing horseradish peroxidase (HRP) simultaneously, with H
2O
2Be oxygenant, utilize HRP that the phenolic compound catalyzed oxidation is generated sedimentary mechanism, reach the purpose of from water, separating out phenolic comp ' ds pollution.
The present invention is that a kind of enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 catalyzed oxidation is separated out the method for aldehydes matter in the water, it is characterized in that having following process and step:
A. the preparation of silicon-based mesoporous molecular sieve SBA-15: the poly-oxyethylene ether of 4 weight parts-poly-propylene oxide ether-poly-oxyethylene ether triblock copolymer (P123) is dissolved in the deionized water of the hydrochloric acid soln of 2M of 120 weight parts and 30 weight parts, the tetraethoxy (TEOS) that adds 8.5 weight parts then, and at 35 ℃ of lasting down 20h that stir; Subsequently with reactant transfer in the teflon-lined reactor, leave standstill under the condition at 80 ℃ and to react 24h; At last solid product is collected washing, drying at room temperature; In 8h, temperature is slowly risen to 500 ℃, and calcining at constant temperature 6h, silicon-based mesoporous molecular sieve SBA-15 obtained;
B. carry the preparation of enzyme SBA-15: the SBA-15 of 0.1～0.5g that step a is made joins in Sodium phosphate dibasic-sodium dihydrogen phosphate buffer of 10～50ml, the control pH value in reaction is 4～12, and place and stir 1～2h on the magnetic stirring apparatus, reactant is uniformly dispersed in solution; Stirring finishes, and the horseradish peroxidase (HRP) of 1～15mg is joined solution for continuous stir, and the time is 1～10h; Subsequent filtration, and wash SBA-15 repeatedly in turn with secondary water and phosphate buffer soln, afterwards product is carried out drying at room temperature, obtain carrying an enzyme SBA-15.
C. carry the secondary immobilization of enzyme SBA-15: above-mentioned dried 0.1～0.5g is carried enzyme SBA-15 join in 5ml 3%～10% (w/w) sodium alginate soln, after stirring, with syringe above-mentioned solution is splashed in 2%～5% (w/w) calcium chloride solution, make its reaction 1-4h; Make the gel beads that particle diameter is 2～6mm, be the secondary immobilization and carry enzyme SBA-15.
D. use simple year enzyme SBA-15 or secondary immobilization to carry enzyme SBA-15 catalyzed oxidation and separate out aldehydes matter in the water
(1). use simple year enzyme SBA-15 catalyzed oxidation to separate out phenol in the water: 0.1～0.5g is carried enzyme SBA-15, and to join 15ml phenol concentration be in 1～500mg/L, the phenol-water solution of pH value as 2-10, adds the H of 2～5mmol/L simultaneously
2O
2, continue to stir 0.5～6h, finally separate out aldehydes matter;
(2). use the secondary immobilization to carry enzyme SBA-15 catalyzed oxidation and separate out phenol in the water: enzyme SBA-15 gel beads is carried in above-mentioned secondary immobilization, and to join 15ml phenol concentration be that 1～500mg/L, pH value are in 4～10 the phenol-water solution, adds 2～5mmol/L H simultaneously
2O
2, continue to stir 0.5～6h, finally separate out aldehydes matter.
That phenol concentration is that the catalyzed oxidation of the phenol-water solution of 1～500mg/L is separated out effect is better for the enzyme SBA-15 that carries for preparing among the present invention, through year enzyme SBA-15 gel beads after the secondary immobilization, its repeat performance is better, reuse 6 times after, phenol is removed efficient and still can be reached more than 60%.The present invention can reach the good result of removing aldehydes matter from water down the auxiliary of solid-liquid separation means.
Description of drawings
Fig. 1 carries the process flow sheet that enzyme SBA-15 catalyzed oxidation is separated out phenol for the present invention.
Fig. 2 separates out the effect of phenol for carrying enzyme SBA-15 catalyzed oxidation under the initial phenol concentration of difference.
Fig. 3 separates out the effect of phenol for carrying enzyme SBA-15 under the time at different catalytic oxidation.
Fig. 4 separates out the effect of phenol for carrying enzyme SBA-15 catalyzed oxidation when the initial pH of different phenol-water solutions.
Fig. 5 is for carrying the repeated use effect of enzyme SBA-15.
Fig. 6 carries the repeated use effect of enzyme SBA-15 for the secondary immobilization.
Embodiment
In conjunction with following specific embodiment, the present invention is described in further detail.
Embodiment 1: referring to the process flow sheet of accompanying drawing 1.At first under normal temperature condition, prepare SBA-15.With segmented copolymer P123 is template, is the silicon source with the tetraethoxy.The weighing 2g P123 of elder generation adds the hydrochloric acid soln of 15g water and 60g 2M subsequently in beaker, be stirred to P123 and dissolve fully under 35 ℃, adds 4.25gTEOS then, and continues to stir 20h down at 35 ℃.Subsequently with reactant transfer in the teflon-lined reactor, leave standstill under the condition at 80 ℃ and to react 24h.At last solid product is collected washing, drying at room temperature.In 8h, temperature is slowly risen to 500 ℃, and calcining at constant temperature 6h.Powder after the calcining promptly is the SBA-15 that has the duct.The SBA-15 that 0.4g is made joins in the phosphate buffer soln that the pH value is 8 30ml, places and stirs 1h on the constant temperature blender with magnetic force, and it is uniformly dispersed in solution.Stirring finishes, and in the HRP adding solution with 8mg, and continues to stir 6h.Subsequent filtration, and wash SBA-15 repeatedly in turn with secondary water and phosphate buffer soln, afterwards product is carried out drying at room temperature, obtain carrying an enzyme SBA-15.Dried 0.2g is carried in the sodium alginate soln that enzyme SBA-15 joins 5ml 3% (w/w), after stirring, above-mentioned solution is splashed in the calcium chloride solution of 2% (w/w), make its reaction 1h with syringe.Make the gel beads that particle diameter is about 4mm, be and carry enzyme SBA-15 after the secondary immobilization.
Every test that enzyme SBA-15 catalyzed oxidation is separated out phenol in the water is carried in the present invention:
Carry enzyme SBA-15 catalyzed oxidation under the initial phenol concentration of difference and separate out the effect of phenol: 0.2g being carried enzyme SBA-15, to add phenol concentration be that 5～200mg/L, pH are in 8 the phenol-water solution, H
2O
2Adding concentration is 2mmol/L, continues to stir 3h.By accompanying drawing 2 as can be seen, when phenol concentration was low, the clearance of phenol was higher.When phenol concentration was lower than 10mg/L, the clearance of phenolic comp ' ds pollution can arrive more than 90%, and along with the increase of phenol concentration, the phenol clearance descends gradually.When handling the phenol-water solution of 200mg/L, the phenol clearance still can reach about 60%.
Carry enzyme SBA-15 and separate out the effect of phenol under the time at different catalytic oxidation: 0.2g is carried enzyme SBA-15, and to join phenol concentration be that 50mg/L, pH are in 8 the phenol-water solution, H
2O
2Adding concentration is 2mmol/L, continues to stir 0.5～6h.By accompanying drawing 3 as seen, in initial 2h, the clearance of phenol increases sharply with the reaction times increase, and being linear substantially increases, by 40% clearance of 0.5h, be increased to 75% clearance of 2h, behind the 2h, it is mild that the phenol clearance increases beginning, along with the increase in reaction times, the phenol clearance does not increase substantially, therefore can think that catalytic oxidation reaches balance behind 2h.
Carry enzyme SBA-15 catalyzed oxidation when the initial pH of different phenol-water solutions and separate out the effect of phenol: 0.2g being carried enzyme SBA-15, to join phenol concentration be in the 50mg/L phenol-water solution, H
2O
2Adding concentration is 2mmol/L, continues to stir 3h, and regulating the phenol-water solution initial pH value is 4-10.By accompanying drawing 4 as seen, the phenol-water solution initial pH value is bigger to the influence of phenol clearance.Because enzyme is to the susceptibility of pH, when pH is 4 and 10, the activity of enzyme a little less than, the phenol clearance is very low, the pH value is 4 o'clock, the clearance of phenolic comp ' ds pollution has only about 40%.When pH when neutral, the phenol clearance is higher, pH is increased at 8 o'clock by 6, the phenol clearance increases very fast, is to reach the highest at 8 o'clock at pH, can reach about 75%.
Carry the repeated use effect of enzyme SBA-15: 0.2g is carried enzyme SBA-15, and to join phenol concentration be that 20mg/L, pH are in 8 the phenol-water solution, H
2O
2Adding concentration is 2mmol/L, continues to stir 3h.After reacting completely, phenol-water solution is filtered, and will remove that the enzyme SBA-15 that carries of phenol washes repeatedly through secondary water in the water, be used further to use next time.As seen from Figure 5, along with the increase of carrying enzyme SBA-15 repeated use number of times, the phenol clearance reduces gradually, more than 90%, reduce to about 40% of the 5th by initial, this may be because HRP can produce passivation on the one hand, make its activity reduce, to carry enzyme SBA-15 on the other hand be Powdered and be dispersed in the solution, has partial loss during recovery, and causing in experiment next time effectively, the content of HRP descends.In addition because phenol generates water-fast throw out after treatment, be easier to be deposited in the outside surface that carries enzyme SBA-15, though the enzyme SBA-15 that carries that uses washes repeatedly with secondary water, but still have a spot of throw out and stay its outside surface, make that HRP can not fully contact with reaction substrate when reacting once more, thereby make the clearance of phenol reduce.
The repeated use effect of enzyme SBA-15 is carried in the secondary immobilization: enzyme SBA-15 is carried in the 0.3g secondary immobilization that makes, and to join phenol concentration be that 20mg/L, pH value are in 8 the phenol-water solution, H
2O
2Adding concentration is 2mmol/L, and the reaction times is 3h.After reacting completely, phenol-water solution is filtered, and the secondary immobilization that will remove phenol in the water carries enzyme SBA-15 and wash the back drying at room temperature repeatedly with secondary water, be used further to use next time.By accompanying drawing 6 as seen, the secondary immobilization of preparation is carried enzyme SBA-15 gel beads and is had good repeat performance, reusing after 6 times, still has the phenol clearance more than 60%.Compare with the reusability of immobilized year enzyme SBA-15 of secondary not, after the secondary immobilization, its reusability has had enhancing to a certain degree, this may be because the particulate matter size is bigger after the secondary immobilization, compare with Powdered year enzyme SBA-15 and to be easy to reclaim, and Powdered relatively year enzyme SBA-15 of macrobead gel beads, the sepn process of itself and reaction precipitation thing also is easier to.
Claims (1)
1. an enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 catalyzed oxidation is separated out the method for aldehydes matter in the water, it is characterized in that having following process and step:
The preparation of a.SBA-15: the poly-oxyethylene ether of 4 weight parts-poly-propylene oxide ether-poly-oxyethylene ether triblock copolymer (P123) is dissolved in the deionized water of the hydrochloric acid soln of 2M of 120 weight parts and 30 weight parts, the tetraethoxy (TEOS) that adds 8.5 weight parts then, and at 35 ℃ of lasting down 20h that stir; Subsequently with reactant transfer in the teflon-lined reactor, leave standstill under the condition at 80 ℃ and to react 24h; At last solid product is collected washing, drying at room temperature; In 8h, temperature is slowly risen to 500 ℃, and calcining at constant temperature 6h, silicon-based mesoporous molecular sieve SBA-15 obtained;
B. carry the preparation of enzyme SBA-15: 0.1～0.5g SBA-15 that step a is made joins in Sodium phosphate dibasic-sodium dihydrogen phosphate buffer of 10～50ml, the control pH value in reaction is 4～12, and place and stir 1～2h on the magnetic stirring apparatus, reactant is uniformly dispersed in solution; Stirring finishes, and the horseradish peroxidase (HRP) of 1～15mg is joined solution for continuous stir, and the time is 1～10h; Subsequent filtration, and wash SBA-15 repeatedly in turn with redistilled water and phosphate buffer soln, afterwards product is carried out drying at room temperature, obtain carrying an enzyme SBA-15;
C. carry the secondary immobilization of enzyme SBA-15: above-mentioned dried 0.1～0.5g is carried enzyme SBA-15 join in 5ml 3%～10% (w/w) sodium alginate soln, after stirring, with syringe above-mentioned solution is splashed in 2%～5% (w/w) calcium chloride solution, make its reaction 1-4h; Make the gel beads that particle diameter is 2～6mm, i.e. enzyme SBA-15 is carried in secondary immobilization;
D. use simple year enzyme SBA-15 or secondary immobilization to carry enzyme SBA-15 catalyzed oxidation and separate out aldehydes matter in the water (1). use simple year enzyme SBA-15 catalyzed oxidation to separate out phenol in the water: 0.1～0.5g is carried enzyme SBA-15, and to join 15ml phenol concentration be that 1～500mg/L, pH value are in 2～10 the phenol-water solution, adds the H of 2～5mmol/L simultaneously
2O
2, continue to stir 0.5～6h, finally separate out aldehydes matter.
(2). use the secondary immobilization to carry enzyme SBA-15 catalyzed oxidation and separate out phenol in the water: enzyme SBA-15 gel beads is carried in above-mentioned secondary immobilization, and to join 15ml phenol concentration be that 1～500mg/L, pH value are in 4～10 the phenol-water solution, adds 2～5mmol/L H simultaneously
2O
2, continue to stir 0.5～6h, finally separate out aldehydes matter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100526001A CN101575135B (en) | 2009-06-05 | 2009-06-05 | Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100526001A CN101575135B (en) | 2009-06-05 | 2009-06-05 | Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101575135A true CN101575135A (en) | 2009-11-11 |
| CN101575135B CN101575135B (en) | 2011-12-21 |
Family
ID=41270233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100526001A Expired - Fee Related CN101575135B (en) | 2009-06-05 | 2009-06-05 | Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101575135B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321605A (en) * | 2011-10-21 | 2012-01-18 | 江南大学 | Method for immobilizing fructosyl transferase by taking mesoporous molecular sieve-chitosan as carrier |
| CN101724619B (en) * | 2009-12-24 | 2012-02-01 | 南京工业大学 | Enzyme immobilization application of mesoporous molecular sieve modified by functionalized ion liquid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314800C (en) * | 2005-07-06 | 2007-05-09 | 江南大学 | Fixation method of microbiological lactase and its application |
| CN101235368A (en) * | 2008-02-29 | 2008-08-06 | 上海大学 | Method for preparing immobilized enzyme biological catalyst |
-
2009
- 2009-06-05 CN CN2009100526001A patent/CN101575135B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724619B (en) * | 2009-12-24 | 2012-02-01 | 南京工业大学 | Enzyme immobilization application of mesoporous molecular sieve modified by functionalized ion liquid |
| CN102321605A (en) * | 2011-10-21 | 2012-01-18 | 江南大学 | Method for immobilizing fructosyl transferase by taking mesoporous molecular sieve-chitosan as carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101575135B (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Enhanced anaerobic digestion of cow manure and rice straw by the supplementation of an iron oxide–zeolite system | |
| CN108855083B (en) | Method for removing sulfonamides in water by activating peracetic acid with modified zeolite | |
| CN101759809B (en) | Method for preparing dithiocarbamate-based modified porous starch | |
| Chen et al. | Biodegradability enhancement of coking wastewater by catalytic wet air oxidation using aminated activated carbon as catalyst | |
| CN104415754A (en) | Synthesizing method of immobilized multi-phase Fenton catalyst | |
| JP2006129735A (en) | Method for hydrolyzing cellulose using catalyst and method for producing glucose using the catalyst | |
| CN112047491A (en) | Method for removing phenolic substances in phenol aqueous solution by tyrosinase-metal organic framework compound | |
| CN107927528B (en) | Bionic membrane for removing aflatoxin and preparation method and treatment method thereof | |
| CN108654678A (en) | One type Fenton oxidation catalyst and its application | |
| CN108970608A (en) | Loaded noble metal catalyst with clad structure and preparation method thereof and the application in Cu (II) liquid phase catalytic reduction | |
| CN104096540A (en) | Preparation method of adsorption and catalysis material for removing heavy metals and organic pollutants in municipal sludge | |
| CN110668525A (en) | Method for extracting phenolic wastewater based on hydrophobic eutectic solvent | |
| CN101451133B (en) | Method for preparing silicon base mesoporous molecular sieve SBA-15 immobilized enzyme biocatalyst | |
| CN102382811B (en) | Preparation method of attapulgite immobilized enzyme for ester exchange reaction | |
| CN101575135B (en) | Method for separating out phenols substances in water by catalytic oxidation with enzyme-carrying silicon-based mesoporous molecular sieve SBA-15 | |
| CN113713855A (en) | Ferric alginate-ascorbic acid gel ball and preparation method and application thereof | |
| CN103846099A (en) | Supported polyoxometallate and preparation method thereof | |
| CN104418423A (en) | Method for processing reverse-osmosis concentrated water through catalytic ozone oxidation | |
| CN112110535A (en) | Method for removing phenolic substances in phenol aqueous solution by using tyrosinase nanoflower | |
| CN102773079B (en) | System for coproducing sulfonated coal and humic acid by using sulfuric acid | |
| CN101759278B (en) | Ozonation water treatment method taking nanometer zinc oxide as catalyst | |
| CN108993609B (en) | Preparation method and application of high-dispersion metal catalyst | |
| CN111111617A (en) | Photocatalyst-loaded Co-based MOFs-porous carbon composite adsorption material and preparation method thereof | |
| CN111068739B (en) | Preparation method and application of copper ferrite/zeolite spinel composite material | |
| CN110935129B (en) | Application of syringaldehyde as redox mediator for degrading stilbestrol by laccase and method for improving degradation rate of stilbestrol degraded by laccase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111221 Termination date: 20140605 |