CN105688938B - A kind of preparation method of cheap, efficient degradation of organic dye compound bio material - Google Patents
A kind of preparation method of cheap, efficient degradation of organic dye compound bio material Download PDFInfo
- Publication number
- CN105688938B CN105688938B CN201610111347.2A CN201610111347A CN105688938B CN 105688938 B CN105688938 B CN 105688938B CN 201610111347 A CN201610111347 A CN 201610111347A CN 105688938 B CN105688938 B CN 105688938B
- Authority
- CN
- China
- Prior art keywords
- preparation
- organic dye
- cheap
- compound bio
- dye compound
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A kind of preparation method of cheap, efficient degradation of organic dye compound bio material, the present invention relates to the preparation method of the composite of degradating organic dye, it is higher in order to solve the material cost of existing degradating organic dye, and degradation rate is not high, easily causes the problem of secondary pollution.Preparation method：First, copper chloride and ferric trichloride are added in the mixed solution of oleic acid and n- dodecyl mereaptan, dissolved by heating, then added the n- dodecyl mereaptan solution of sodium diethyldithiocarbamate trihydrate, superfines chalcopyrite is obtained after cleaning；2nd, biological material powder, which is placed in distilled water, heats, the powdered biomass after being cleaned；3rd, superfines chalcopyrite and cleaning after powdered biomass mixing.Superfines chalcopyrite and biological material are mixed with to obtain the compound bio material of low price by the present invention, beneficial to recovery and repeatable utilization, do not cause secondary pollution, reaction condition is gentle, degradation rate efficiency high.
Description
Technical field
The present invention relates to a kind of preparation method of the composite of degradating organic dye.
Background technology
There is substantial amounts of organic pollution in the whole world as industrial wastewater discharge is into environment every year.These organic pollutions
Water source dyeing, On The Deterioration of Visibility Over can not only be made, it is often more important that its toxicity even can bring harmful effect to the whole ecosystem.
Although people are carrying forward vigorously environment-friendly technological means, the water consumption in industry and the wastewater flow rate of discharge are reduced, is given up
The pollution of water is still extremely serious.Due to organic pollution generally under sunlight and high temperature it is very stable, and be not easy by micro- life
Thing is degraded, so most of organic pollution can not be degraded by traditional wastewater processing method.
Chinese patent CN201410418546.9, patent name《Fe3O4-MnO2The preparation of composite catalyst and gone using it
Except the method for organic dyestuff in dyeing waste water》Disclosed in utilize FeSO4·7H2O, polyvinylpyrrolidone, water, deionized water,
NaOH and KMnO4Prepare Fe3O4-MnO2Composite catalyst, the method for removing organic dyestuff in dyeing waste water.Patented method master
To be directed to degradation of dye effluent, restricted application.Degradation reaction is less efficient, and recycling number is less, and recovery process
Complexity, influenceing dye decolored rate with external environment can significantly decline.
Chinese patent CN201210076843.0, patent name are《Can photocatalytically degradating organic dye polyoxometallic acid
Salt/resin hybridized material》, disclose the preparation that polyoxometallate is loaded to degradating organic dye on Merrifield resins
Method.Using the method for polyoxometallate/resin hybridized material degradation organic dyestuff in actual industrial production metal used
Salt consumption is larger, though excessive metal salt can improve degradation of organic dyes efficiency, causes secondary pollution to environment simultaneously,
The colourity increase of processed water is obvious.The addition of a large amount of metal salts produces counter productive, also needs additional process to remove metal salt, drop
Low production efficiency.
The content of the invention
Higher the invention aims to solve the material cost of existing degradating organic dye, degradation rate is not high, Yi Yin
The problem of playing secondary pollution, and a kind of preparation method of cheap, efficient degradation of organic dye compound bio material is provided.
The preparation method of cheap, efficient degradation of organic dye the compound bio material of the present invention follows these steps to realize：
First, copper chloride and ferric trichloride are added in the mixed solution of oleic acid and n- dodecyl mereaptan in a nitrogen environment,
After being heated to 120~150 DEG C uniform stirring until solid particle be completely dissolved, obtain reaction solution, diethyl injected into reaction solution
Base nabam trihydrate ((C2H5)2NCSSNa·3H2O n- dodecyl mereaptan solution), at 180~220 DEG C
At a temperature of be incubated 10~20min, collect solid formation after being cooled to room temperature, clean solid formation using absolute ethyl alcohol and acetone successively,
Obtain superfines chalcopyrite；
2nd, biological material powder is placed in the distilled water that temperature is 75~85 DEG C and heated 5~15 minutes, is then placed in
It is dried in vacuum drying chamber, the powdered biomass after being cleaned；
3rd, the powdered biomass after superfines chalcopyrite and cleaning is mixed, using ball mill grinding until composite wood
The color of material is dispersed, obtains compound bio material.
Superfines chalcopyrite and biological material Poplar Powder are mixed with to obtain low price, efficient degradation organic by the present invention
The compound bio material of dyestuff, beneficial to recovery and repeatable utilization, secondary pollution is not caused, reaction condition is gentle, operative employee
Sequence is easy, and it is higher to overcome the cost of traditional catalyst degraded, the problem of easily causing secondary pollution.Using 1g of the present invention
Composite biomass powder can degrade 339.6mg methylene blues, 282.8mg rhodamine Bs and 235.5mg rhodamine 6Gs respectively, use
The degradation effect for the compound bio material that superfines mixes with Poplar Powder is more organic than single superfines degraded variety classes
Dyestuff is higher by 3.41 times, 3.12 times, 2.62 times successively.Cost savings 85% are prepared, and biological material is given full play to and reached
Purpose is used to low-quality is excellent.
Brief description of the drawings
Fig. 1 is the superfines chalcopyrite (CuFeS that the step 1 of embodiment one obtains2Powder) TEM figures (resolution ratio is
50nm)；
Fig. 2 is the histogram of particle size distribution for the superfines chalcopyrite that the step 1 of embodiment one obtains；
Fig. 3 is the superfines chalcopyrite (CuFeS that the step 1 of embodiment one obtains2Powder) HRTEM figure；
Fig. 4 is that the change of dye strength in application composite biomass material degradation organic dyestuff course of reaction of the invention is bent
Line chart, wherein ■ represent methylene blue, ● rhodamine B is represented, ▲ represent rhodamine 6G；
Fig. 5 is that concentration is at any time in different pH value ranges for the obtained composite biomass material degradation methylene blue of embodiment one
Between change curve, wherein ■ represents pH=1.5, ● represent pH=2.5, ▲ represent pH=3.5, ▼ represents pH=4.5, ◆ generation
Table pH=5.5,Represent pH=6.5；
Fig. 6 is that concentration is at any time in different pH value ranges for the obtained composite biomass material degradation rhodamine B of embodiment one
Between change curve, wherein ■ represents pH=1.5, ● represent pH=2.5, ▲ represent pH=3.5, ▼ represents pH=4.5, ◆ generation
Table pH=5.5,Represent pH=6.5；
Fig. 7 is that concentration is at any time in different pH value ranges for the obtained composite biomass material degradation rhodamine 6G of embodiment one
Between change curve, wherein ■ represents pH=1.5, ● represent pH=2.5, ▲ represent pH=3.5, ▼ represents pH=4.5, ◆ generation
Table pH=5.5,Represent pH=6.5.
Embodiment
Embodiment one：Present embodiment is cheap, the preparation of the compound bio material of efficient degradation of organic dye
Method follows these steps to implement：
First, copper chloride and ferric trichloride are added in the mixed solution of oleic acid and n- dodecyl mereaptan in a nitrogen environment,
After being heated to 120~150 DEG C uniform stirring until solid particle be completely dissolved, obtain reaction solution, diethyl injected into reaction solution
Base nabam trihydrate ((C2H5)2NCSSNa·3H2O n- dodecyl mereaptan solution), at 180~220 DEG C
At a temperature of be incubated 10~20min, collect solid formation after being cooled to room temperature, clean solid formation using absolute ethyl alcohol and acetone successively,
Obtain superfines chalcopyrite；
2nd, biological material powder is placed in the distilled water that temperature is 75~85 DEG C and heated 5~15 minutes, is then placed in
It is dried in vacuum drying chamber, the powdered biomass after being cleaned；
3rd, the powdered biomass after superfines chalcopyrite and cleaning is mixed, using ball mill grinding until composite wood
The color of material is dispersed, obtains compound bio material.
Superfines containing iron sulfide is prepared in present embodiment step 1, then by sulfide superfines with it is porous
Biological material carry out it is compound.Reaction equation is as follows：
Fe3++H2O2→Fe(HO2)2++H+
Fe(HO2)2+→Fe2++HO2
Fe2++H2O2→Fe3++·OH+OH-
·OH+H2O2→HO2+H2O
Superfines chalcopyrite (CuFeS2Powder) with hydrogen peroxide effect generation divalence ferrous ion, ferrous ion again with it is double
Oxygen water reaction generation hydroxyl radical free radical, makes its organic compound of degrading.The present invention can increase specific surface area by superfines,
More ferric ions are made to be exposed under hydrogen peroxide, so as to generate more hydroxyl radical free radicals.
Embodiment two：Present embodiment and copper chloride and trichlorine in step 1 unlike embodiment one
The mol ratio for changing iron is 1：1.5~2.Other steps and parameter are identical with embodiment one.
Embodiment three：In present embodiment step 1 unlike embodiment one or two oleic acid with just
The volume ratio of lauryl mercaptan is 1：1.2~3.6.Other steps and parameter are identical with embodiment one or two.
Embodiment four：N- dodecyl mereaptan unlike one of present embodiment and embodiment one to three is molten
The concentration of sodium diethyldithiocarbamate trihydrate is 8~16mol/L in liquid.Other steps and parameter and specific implementation
One of mode one to three is identical.
Embodiment five：Diethyl in step 1 unlike one of present embodiment and embodiment one to four
Base nabam trihydrate is 1 with the mol ratio of copper chloride or ferric trichloride：1.1~3.9.Other steps and
Parameter is identical with one of embodiment one to four.
Embodiment six：Step 1 unlike one of present embodiment and embodiment one to five is to reaction
The n- dodecyl mereaptan solution of sodium diethyldithiocarbamate trihydrate is injected in liquid, with 5~10 DEG C/min speed liter
Temperature is to 180~220 DEG C.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven：What step 1 unlike one of present embodiment and embodiment one to six obtained
The average grain diameter of superfines chalcopyrite is 3.2~8nm.One of other steps and parameter and embodiment one to six phase
Together.
Embodiment eight：Described in step 2 unlike one of present embodiment and embodiment one to seven
Biological material powder is Poplar Powder, bamboo powder or toothed oak wood powder.One of other steps and parameter and embodiment one to seven
It is identical.
The timber of present embodiment can be wood residues.
Embodiment nine：Step 2 is at 60 DEG C unlike one of present embodiment and embodiment one to eight
Vacuum drying chamber in be dried in vacuo 24 hours.Other steps and parameter are identical with one of embodiment one to eight.
Embodiment ten：Step 3 unlike one of present embodiment and embodiment one to nine presses quality
Than for 1：(1~23) mixes the powdered biomass after superfines chalcopyrite and cleaning.Other steps and parameter and specific reality
It is identical to apply one of mode one to nine.
Embodiment one：The present embodiment is cheap, the preparation method of the compound bio material of efficient degradation of organic dye is pressed
Row step is implemented：
First, 0.085g copper chlorides and 0.081g ferric trichlorides are added to oleic acid and n- dodecyl mereaptan in a nitrogen environment
Mixed solution (volume ratio 1:0.67) in, after being heated to 140 DEG C uniform stirring until solid particle be completely dissolved, reacted
Liquid, sodium diethyldithiocarbamate the trihydrate ((C containing 0.2mol is injected into reaction solution2H5)2NCSSNa·
3H2O n- dodecyl mereaptan solution 15ml), 200 DEG C of temperature is warming up to 15 DEG C/min speed, is incubated 10min, is cooled to room
Solid formation is collected after temperature, 2 solid formations is cleaned using absolute ethyl alcohol and acetone successively, obtains superfines chalcopyrite；
2nd, Poplar Powder is placed in the distilled water that temperature is 80 DEG C and heated 10 minutes, be then placed in 60 DEG C of vacuum drying chambers
In be dried 24 hours, the powdered biomass after being cleaned；
3rd, the powdered biomass after 0.05g superfines chalcopyrite and 0.95g cleanings is mixed, uses ball mill grinding
Until the color of composite is dispersed, compound bio material is obtained.
Superfines chalcopyrite (the CuFeS that the present embodiment step 1 obtains2Powder) histogram of particle size distribution such as Fig. 2 institutes
Show, show CuFeS2The average grain diameter of superfines is 6.4 ± 0.5nm, and HRTEM is schemed as shown in figure 3, being transmitted by high-resolution
Electron microscopic observation superfines crystal morphology.
The test process of degradating organic dye is as follows：
The compound bio material that 1g embodiments one obtain is placed in titration bottom of the tube, outlet at bottom position places 1 millimeter
Thick cotton is to prevent mixture from being flowed out from outlet, successively by 250 μ l H2O2(concentration 30%) drips with 3 kinds of organic dyestuff injections
In fixed tube, respectively containing the organic dyestuff that 50ml concentration is 100mg/L in buret, opening bottom switch valve flows through organic dyestuff
Instilled after the degraded of mixture area in beaker.
Test result show mixture that superfines mixes with biological material Poplar Powder can all efficient degradations it is organic
Dyestuff, 1g compound bios material can degrade 339.6mg methylene blues, 282.8mg rhodamine Bs and 235.5mg rhodamines respectively
6G, degradation effect is higher successively than single superfines degraded variety classes organic dyestuff after being mixed using superfines with Poplar Powder
Go out 3.41 times, 3.12 times, 2.62 times.In addition biological material Poplar Powder is cheap, and it is combined to raising drop with superfines
Efficiency is solved, reaches cheap, efficient degradation of organic dye purpose.
The present embodiment compound bio material is respectively to methylene blue, rhodamine B and rhodamine 6G in different pH value ranges
Interior concentration changes with time curve as shown in Figures 5 to 7, it can be seen that pH value shadow of the compound bio material with reaction system
Sound is smaller, applied widely.
Claims (9)
1. the preparation method of cheap, efficient degradation of organic dye compound bio material, it is characterised in that be by following step
It is rapid to realize：
First, copper chloride and ferric trichloride are added in the mixed solution of oleic acid and n- dodecyl mereaptan in a nitrogen environment, heated
After to 120~150 DEG C uniform stirring until solid particle be completely dissolved, obtain reaction solution, into reaction solution inject diethyl two
The n- dodecyl mereaptan solution of thiocarbamic acid sodium trihydrate, 10~20 min are incubated at a temperature of 180~220 DEG C, it is cold
But to solid formation is collected after room temperature, solid formation is cleaned using absolute ethyl alcohol and acetone successively, obtains superfines chalcopyrite；
2nd, biological material powder is placed in the distilled water that temperature is 75~85 DEG C and heats 5~15 min, be then placed in vacuum
It is dried in drying box, the powdered biomass after being cleaned；
3rd, it is 1 in mass ratio by the powdered biomass after superfines chalcopyrite and cleaning：1~23 mixing, is ground using ball mill
Mill is dispersed up to the color of composite, obtains compound bio material.
2. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is 1 in the mol ratio of the copper chloride in step 1 and ferric trichloride：1.5~2.
3. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is 1 in the volume ratio of the oleic acid in step 1 and n- dodecyl mereaptan：1.2~3.6.
4. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is 8~16mol/L in the concentration of the sodium diethyldithiocarbamate trihydrate in n- dodecyl mereaptan solution.
5. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
It is 1 to levy in the mol ratio of the sodium diethyldithiocarbamate trihydrate in step 1 and copper chloride or ferric trichloride：
1.1~3.9.
6. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is injecting the n- dodecyl mereaptan solution of sodium diethyldithiocarbamate trihydrate in step 1 into reaction solution, with 5
~10 DEG C/min speed is warming up to 180~220 DEG C.
7. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is that the average grain diameter for the superfines chalcopyrite that step 1 obtains is 3.2~8nm.
8. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is that the biological material powder described in step 2 is Poplar Powder, bamboo powder or toothed oak wood powder.
9. the preparation method of cheap, efficient degradation of organic dye compound bio material according to claim 1, it is special
Sign is being dried in vacuo 24 hours in vacuum drying chamber of the step 2 at 60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610111347.2A CN105688938B (en) | 2016-02-29 | 2016-02-29 | A kind of preparation method of cheap, efficient degradation of organic dye compound bio material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610111347.2A CN105688938B (en) | 2016-02-29 | 2016-02-29 | A kind of preparation method of cheap, efficient degradation of organic dye compound bio material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105688938A CN105688938A (en) | 2016-06-22 |
| CN105688938B true CN105688938B (en) | 2018-03-23 |
Family
ID=56223625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610111347.2A Expired - Fee Related CN105688938B (en) | 2016-02-29 | 2016-02-29 | A kind of preparation method of cheap, efficient degradation of organic dye compound bio material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105688938B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267810A (en) * | 2011-08-09 | 2011-12-07 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-density ferrite-carbon nanotube composite block material |
| CN102836745A (en) * | 2012-08-24 | 2012-12-26 | 东北林业大学 | Preparation method for photo-catalysis material with aerogel substrate |
| CN104362343A (en) * | 2014-11-21 | 2015-02-18 | 厦门大学 | Preparation method and application of one-dimensional rod-like CuFeS2 compound |
| CN105154060A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101393120B1 (en) * | 2005-09-08 | 2014-05-08 | 리서치 파운데이션 오브 더 시티 유니버시티 오브 뉴욕 | Catalytic adsorbents obtained from municipal sludges, industrial sludges, compost and tobacco waste and process for their production |
-
2016
- 2016-02-29 CN CN201610111347.2A patent/CN105688938B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267810A (en) * | 2011-08-09 | 2011-12-07 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-density ferrite-carbon nanotube composite block material |
| CN102836745A (en) * | 2012-08-24 | 2012-12-26 | 东北林业大学 | Preparation method for photo-catalysis material with aerogel substrate |
| CN104362343A (en) * | 2014-11-21 | 2015-02-18 | 厦门大学 | Preparation method and application of one-dimensional rod-like CuFeS2 compound |
| CN105154060A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for three-element copper-iron-sulfur (CuFeS2) fluorescent quantum dot with magnetic property by aqueous-phase synthesis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105688938A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Persulfate activation towards organic decomposition and Cr (VI) reduction achieved by a novel CQDs-TiO2− x/rGO nanocomposite | |
| CN106313221B (en) | A kind of preparation method of fluorescent transparent magnetic timber | |
| CN105964256B (en) | A kind of preparation method of hud typed ferroso-ferric oxide/graphene oxide composite nano catalyst | |
| CN106045130B (en) | A method of persulfate degradation of organic waste water is catalyzed using Bayan Obo ore | |
| CN103521229A (en) | Preparing method for iron-cobalt Fenton-like catalyst, products of iron cobalt Fenton-like catalyst and application of iron cobalt Fenton-like catalyst | |
| CN104399742A (en) | Method for repairing organic polluted soil by intensifying Fenton oxidation | |
| CN103170501B (en) | Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material | |
| CN106513017A (en) | Compound photocatalytic material and preparation method and application thereof | |
| CN108212127A (en) | A kind of preparation method and application of function nano composite hydrogel | |
| CN108636370A (en) | A kind of nano-magnetic powder body material preparation method and application based on oyster shell | |
| CN106045152A (en) | Method for degrading rhodamine B through nanometer Fe3O4/Na2S2O8 jointly | |
| CN102745683B (en) | Biological oxidation graphite and preparation method thereof | |
| CN109607704A (en) | Using rare-earth tailing as multiple catalyzing iron carbon microelectrode filler of raw material and the preparation method and application thereof | |
| CN105056926A (en) | Novel TiO2/WO3 coated magnetic nano composite particles and preparation method therefor and use thereof | |
| CN106799208A (en) | A kind of biomass carbon carried magnetic material composite adsorbing material and preparation method thereof, application process | |
| An et al. | Oxygen vacancies enhance Fe-doped BiOCl photocatalysis-Fenton synergy degradation of phenol | |
| Ma et al. | A highly active Z-scheme NiGa2O4/anthraquinone/MoO3 photocatalyst via charge transfer for sunlight photocatalytic simultaneous conversions of nitrite and sulfite | |
| CN105688938B (en) | A kind of preparation method of cheap, efficient degradation of organic dye compound bio material | |
| CN105502564B (en) | Adsorbent for selectively removing dye containing sulfonic acid group in wastewater and method thereof | |
| CN108554458A (en) | Core/membranous type composite bismuth vanadium photocatalyst and preparation method thereof | |
| CN104496109B (en) | The device and method of a kind of electrolysis-perstraction-biological coupling technical finesse height salt organic wastewater with difficult degradation thereby | |
| CN106669740B (en) | A kind of titanium dioxide/Schwertmannite composite catalyst and its preparation method and application | |
| CN106179223A (en) | The method of modifying of a kind of activated carbon and application | |
| CN104927197A (en) | Antibacterial wood plastic composite preparation method through gamma rays | |
| CN103708658B (en) | Iron aluminium Aerated micro-electrolysis sewage treatment process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180323 Termination date: 20200229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |