CN101486769A - Preparation of amidoxime group bacteria cellulose - Google Patents
Preparation of amidoxime group bacteria cellulose Download PDFInfo
- Publication number
- CN101486769A CN101486769A CNA2009100461223A CN200910046122A CN101486769A CN 101486769 A CN101486769 A CN 101486769A CN A2009100461223 A CNA2009100461223 A CN A2009100461223A CN 200910046122 A CN200910046122 A CN 200910046122A CN 101486769 A CN101486769 A CN 101486769A
- Authority
- CN
- China
- Prior art keywords
- bacteria cellulose
- solution
- amidoxime group
- heavy metal
- preparation
- 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.)
- Pending
Links
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for preparing amidoxime base bacterial cellulose, comprising (1) preparation of cyanoethyl bacterial cellulose: a. powder-shaped bacterial cellulose is immersed in four n-chloride-based solution with the concentration of 5%-10% and then stirred; b. acrylonitrile and alkali solution with the concentration of 30%-40% are added into the solution and then reacted at room temperature; c. deionized water is used for washing till neutral, and then dried in vacuum; and (2) preparation of amidoxime bacterial cellulose: d. the cyanoethyl bacterial cellulose is added into hydroxylamine or hydroxylamine hydrochloride solution, and later the pH vale is adjusted to be 9-10, and then the reaction is carried out at 60 DEG C-90 DEG C; and e. the product is washed till neutral, and then dried in vacuum at 60 DEG C-70 DEG C, and finally the amidoxime bacterial cellulose is prepared. The amidoxime base bacterial cellulose prepared by the method has good stability and high processing speed, and fully meets the requirements of heavy metal wastewater processing; and compared with the conventional heavy metal processing, the process has low process cost, and is technically and economically feasible.
Description
Technical field
The invention belongs to the modification preparation field of bacteria cellulose, particularly relate to a kind of preparation method of amidoxime group bacteria cellulose.
Background technology
The standard of living that the economy of China has obtained the very big development people since the reform and opening-up is greatly improved, but because extensive production and operation pattern is not broken away from our industrial and agricultural production as yet, when industrial and agricultural production develops rapidly, discharged waste water is also increasing sharply, wherein the quantity discharged of trade effluent has accounted for very big ratio, as China's wastewater discharge in 1997 is 41,600,000,000 tons, and the quantity discharged of trade effluent is 22,700,000,000 tons, and the trade effluent composition is complicated and contain a large amount of available stocks.If not treated trade effluent directly discharges, it has also caused the loss of ample resources when water body and people's lives are caused direct economic loss and harm.In trade effluent, scientist has detected more than 150 kind of pollution substance, and heavy metal then is to one of the most serious pollutent of environmental influence, be atmosphere, water, the common pollutent of soil, compare with other many pollutents, the pollution threat of heavy metal is that it can not be by microbiological degradation.Heavy metal ion enters after the environment, most of passive plant absorbing and enrichment or be accumulated in the settling of water bottom, animals and plants absorb after the heavy metal, effect by food chain, can make the intravital heavy metal accumulation coefficient of animals and plants reach several thousand even several ten thousand times, and they are converted into the bigger organometallic compound of toxicity.That is to say that the heavy metal that enters in the environment can only be another kind of form from a kind of form transformation, moves to another place from a place, and can't disappear from environment.Like this, even source of pollution are effectively controlled, the environmental hazard that has polluted still can long-term existence.
At present, the method that improvement contains the waste water of heavy metal ion has a lot, wherein most widely used is that chemiadsorption is handled effluent containing heavy metal ions, traditional have a charcoal absorption, ion-exchange absorption etc., however its production cost is higher, reacts slower, the residue instability often also has secondary pollution.Mierocrystalline cellulose is a natural macromolecular material, and wide material sources, nontoxic carry out the amidoxim modification to it and are used to remove heavy metal ion, carried out a large amount of work, but its clearance is undesirable, and removal speed are slower.Bacteria cellulose (BC) is a kind of new bio nano material, compares with the general fibre element, has the purity height, the surface energy height, and the characteristics that surface-area and specific surface area are big are so showing great potential aspect the preparation high-performance adsorbent.
The chelate fibre adsorbing metal ions that contains amidoxime group has selectivity height, easily wash-out, advantage such as regeneration easily, is widely used in reclaiming from the aqueous solution, concentrated, enrichment and separation of heavy metal ions.Study on the modification to bacteria cellulose also is in the starting stage at present, utilizes amidoxime group to come modified bacteria cellulose and use to remove the report that effluent containing heavy metal ions does not also have this respect.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of amidoxime group bacteria cellulose, the prepared amidoxime group bacteria cellulose good stability of this method, processing speed is fast, satisfy the requirement of handling heavy metal wastewater thereby fully, this technology is lower than using conventional heavy metal treatment process cost, is feasible technically, economically.
A kind of amidoxime group bacteria fiber of the present invention::
A, with acetobacter xylinum (bacterium numbering 1.1812, China common micro-organisms culture presevation administrative center) 1-2 weeks of static cultivation in constant incubator, prepare bacteria cellulose, through purifying, grind and obtain below particle diameter to 200 μ Powdered bacteria cellulose, to be immersed in concentration be in 5%～10% the tetraalkyl ammonia chloride solution and stir 15～30min, the quality of bacteria cellulose with it: tetraalkyl ammonia chloride quality is 1:0.2～0.5;
B, to add vinyl cyanide and concentration in above-mentioned solution be 30%～40% alkaline solution, and the vinyl cyanide quality: the quality of bacteria cellulose is 20～30:1; The alkaline solution quality: the bacteria cellulose quality is 1:1～2, reacts 30min～120min under room temperature;
C, reacted the back be washed till neutrality with deionized water, at 25 ℃～40 ℃ following vacuum-drying 5～6h promptly; Its molecular structural formula is:
(2) preparation of amidoxim bacteria cellulose:
D, step (1) cyanoethyl bacteria cellulose joined 5%～15% azanol (NH
2OH) solution or 10%～30% oxammonium hydrochloride (NH
2OHHCl) in the solution, the quality of azanol: the quality of cyanoethyl bacteria cellulose is 5～20:1, regulates pH=9～10 simultaneously, reacts 2～4h down at 60～90 ℃;
E, with deionized water wash above-mentioned reaction product to neutral, get the amidoxime group bacteria cellulose of white powder at 60～70 ℃ of following vacuum-drying 4～5h, its molecular structural formula is:
As optimized technical scheme:
Described step (1) tetraalkyl ammonia chloride solution is that in tetramethyl-ammonia chloride solution, tetraethyl-ammonia chloride solution, the tetrabutylammonium chloride solution one or more must mix.
Described step (1) alkaline solution be NaOH solution, KOH solution in a kind of or its mixing solutions.
Described step (2) is used NaCO
3Or NaOH regulates the pH value.
The present invention also provides a kind of method of using amidoxime group bacteria cellulose to handle effluent containing heavy metal ions, it is characterized in that, concrete treatment process is:
A, get the waste water that contains heavy metal ion;
B, adjusting waste water ph are 4～6;
C, add amidoxime group bacteria cellulose in waste water, dosage is 0.5～1kg/T;
The mixed solution of d, stirring waste water and amidoxime group bacteria cellulose, churning time is 2～4h;
E, filtration, water outlet.
Filtrate can be carried out concentration of heavy metal ion mensuration with Atomic Absorption Spectroscopy AAS, and through test, after effluent containing heavy metal ions was handled through amidoxime group bacteria cellulose, the removal of heavy metal ions rate reached more than 85%.
Described heavy metal ion is Cu
2+, Pb
2+, Cr
6+One or more.
A kind of or its mixing solutions in described adjusting waste water ph NaOH solution, the KOH solution.
Utilize amidoxim to come modified bacteria cellulose, and study its counterweight Adsorption Properties for Metal Ions, the three-dimensional netted microfibrillar structure of bacteria cellulose uniqueness, specific surface area is bigger, utilize these characteristics that it is carried out chemical modification and introduce amidoxime group, can improve its coordination greatly, add original electrostatic adhesion like this, strengthen its adsorptive power greatly heavy metal ion to heavy metal ion.This technology is used for the improvement of heavy metal wastewater thereby, has that operation is simple, and speed is fast, and the clearance of heavy metal ion is reached more than 85%, can effectively remove heavy metal ion, all is the Perfected process of handling heavy metal wastewater thereby technically and economically.
Utilize the coordination and the electrostatic adsorption of amidoxime group bacteria cellulose that the heavy metal ion in the waste water is adsorbed, it is big to the invention solves present heavy metal ions in wastewater recovery difficult, the problem that clearance is not high, it is low to have remedied the prior art clearance, reaction is slow, the deficiency that can not recycle etc.
Beneficial effect
(1) utilizes the unique texture of bacteria cellulose and character to carry out the amidoxime group bacteria cellulose that modification makes high absorption property, reach the purpose of handling heavy metal wastewater thereby;
(2) amidoxime group bacteria cellulose good stability, processing speed is fast, satisfies the requirement of handling heavy metal wastewater thereby fully, and this technology is lower than using conventional heavy metal treatment process cost, is feasible technically, economically;
(3) amidoxime group bacteria cellulose of Adsorption of Heavy Metal Ions only needs simple method just can regenerate, and has avoided secondary pollution;
(4) amidoxime group bacteria cellulose good stability, also available technology realizes the recovery of heavy metal, reaches the purpose of resource rational utilization.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Reaction times is to the influence of amidoxime group bacteria cellulose substitution value
Get the 3g bacteria cellulose, be immersed in the tetramethyl-ammonia chloride solution of 0.6g5% and stir 15min, the NaOH that adds 60g vinyl cyanide and 3g30% then, at room temperature react 30min, 60min, 120min respectively, reacted the back and be washed till neutrality with deionized water, at 25 ℃ of following vacuum-drying 5h, obtain the cyanoethyl bacteria cellulose, the substitution value that records the cyanoethyl bacteria cellulose is respectively 0.48,1.33,0.78.Get the cyanoethyl bacteria cellulose 0.25g for preparing, join the hydroxylamine solution of 25g5%, regulate pH=9 with yellow soda ash, under 60 ℃, react 2h, 3h, 4h respectively, use the above-mentioned reaction product of deionized water wash to neutral then, at 60 ℃ of following vacuum-drying 4h, obtain amidoxime group bacteria cellulose, the substitution value that records amidoxime group bacteria cellulose simultaneously is 0.34,0.86,0.54.
Embodiment 2
Temperature of reaction is to the influence of amidoxime group bacteria cellulose substitution value
Get the 3g bacteria cellulose, be immersed in the tetraethyl-ammonia chloride solution of 1.5g10% and stir 30min, the potassium hydroxide that adds 90g vinyl cyanide and 1.5g40% then, at room temperature react 30min, reacted the back and be washed till neutrality with deionized water, at 27 ℃ of following vacuum-drying 6h, obtain the cyanoethyl bacteria cellulose, the substitution value that records the cyanoethyl bacteria cellulose is 1.12.Get the cyanoethyl bacteria cellulose 0.25g for preparing, the oxammonium hydrochloride solution that adds 33g 15%, regulate pH=10 with NaOH, under 60 ℃, 70 ℃, 80 ℃, 90 ℃, react 4h respectively respectively, use the above-mentioned reaction product of deionized water wash to neutral then, at 70 ℃ of following vacuum-drying 5h, obtain amidoxime group bacteria cellulose, the substitution value that records amidoxime group bacteria cellulose simultaneously is 0.64,0.68,0.87,0.78.
Embodiment 3
The consumption of azanol is to the influence of amidoxime group bacteria cellulose substitution value
Get the 3g bacteria cellulose, be immersed in the tetrabutylammonium chloride solution of 1g8% and stir 25min, the NaOH that adds 70g vinyl cyanide and 2g35% then, at room temperature react 120min, reacted the back and be washed till neutrality with deionized water, at 30 ℃ of following vacuum-drying 5.5h, obtain the cyanoethyl bacteria cellulose, the substitution value that records the cyanoethyl bacteria cellulose is 1.02.Get the cyanoethyl bacteria cellulose 0.25g for preparing, the hydroxylamine solution that adds 12.5g, 30g, 50g10% respectively, regulate pH=9.5 with yellow soda ash, at 90 ℃ of reaction 2h, use the above-mentioned reaction product of deionized water wash to neutral then, at 65 ℃ of following vacuum-drying 4.5h, obtain amidoxime group bacteria cellulose, the substitution value that records amidoxime group bacteria cellulose simultaneously is 0.69,0.90,0.81.
(2) heavy metal ion adsorbed embodiment
Embodiment 4
Amidoxime group bacteria cellulose is to containing Cu
2+The treatment effect of waste water
Get and contain Cu
2+1 ton of waste water solution, with 1% NaOH and 1% salpeter solution regulate pH value be about 4, add amidoxime group bacteria cellulose 0.5kg, stir the mixed solution of waste water and amidoxime group bacteria cellulose, churning time is 2h, filtration, water outlet.Get filtrate detection, record amidoxime group bacteria cellulose Cu
2+Clearance be 91%.
Embodiment 5: amidoxime group bacteria cellulose is to containing Pb
2+The treatment effect of waste water
Get and contain Pb
2+1 ton of waste water solution, regulating pH value with 1% NaOH and 1% salpeter solution is about 6, adds amidoxime group bacteria cellulose 1kg, stirs the mixed solution of waste water and amidoxime group bacteria cellulose, churning time is 4h, filtration, water outlet.Get filtrate detection, record amidoxime group bacteria cellulose Pb
2+Clearance be 87%.
Embodiment 6: amidoxime group bacteria cellulose is to containing Cr
6+The treatment effect of waste water
Get and contain Cr
6+1 ton of waste water solution, regulating pH value with 1%NaOH and 1% salpeter solution is about 5, adds amidoxime group bacteria cellulose 0.8kg, stirs the mixed solution of waste water and amidoxime group bacteria cellulose, churning time is 3h, filtration, water outlet.Get filtrate detection, record amidoxime group bacteria cellulose Cr
6+Clearance be 93%.
Claims (7)
1. the preparation method of an amidoxime group bacteria cellulose comprises:
(1) preparation of cyanoethyl bacteria cellulose:
A, with acetobacter xylinum, 1-2 weeks of static cultivation in constant incubator, prepare bacteria cellulose, through purifying, grind and obtain below particle diameter to 200 μ Powdered bacteria cellulose, to be immersed in concentration be in 5%～10% the tetraalkyl ammonia chloride solution and stir 15min～30min, the quality of bacteria cellulose with it: tetraalkyl ammonia chloride quality is 1:0.2～0.5;
B, to add vinyl cyanide and concentration in above-mentioned solution be 30%～40% alkaline solution, and the vinyl cyanide quality: the quality of bacteria cellulose is 20～30:1; The alkaline solution quality: the bacteria cellulose quality is 1:1～2, reacts 30min～120min under room temperature;
C, reacted the back be washed till neutrality with deionized water, at 25 ℃ of-30 ℃ of following vacuum-drying 5～6h promptly;
(2) preparation of amidoxim bacteria cellulose:
D, step (1) cyanoethyl bacteria cellulose joined 5%～15% azanol NH
2OH solution or 10%～30% oxammonium hydrochloride NH
2In the OHHCl solution, the quality of azanol: the quality of cyanoethyl bacteria cellulose is 5～20:1, regulates pH=9～10 simultaneously, reacts 2～4h down at 60 ℃～90 ℃;
E, the above-mentioned reaction product of usefulness deionized water wash get the amidoxime group bacteria cellulose of white powder to neutral at 60 ℃～70 ℃ following vacuum-drying 4～5h.
2. the preparation method of a kind of amidoxime group bacteria cellulose according to claim 1 is characterized in that: described step (1) tetraalkyl ammonia chloride solution is that in tetramethyl-ammonia chloride solution, tetraethyl-ammonia chloride solution, the tetrabutylammonium chloride solution one or more must mix.
3. the preparation method of a kind of amidoxime group bacteria cellulose according to claim 1 is characterized in that: described step (1) alkaline solution be NaOH solution, KOH solution in a kind of or its mixing solutions.
4. the preparation method of a kind of amidoxime group bacteria cellulose according to claim 1, it is characterized in that: described step (2) is used NaCO
3Or NaOH regulates the pH value.
5. the preparation method of a kind of amidoxime group bacteria cellulose according to claim 1 is characterized in that: described amidoxime group bacteria cellulose is as follows in the application of handling effluent containing heavy metal ions:
(1) gets the waste water that contains heavy metal ion;
(2) regulating waste water ph is 4～6;
(3) add amidoxime group bacteria cellulose in waste water, dosage is 0.5～1kg/T;
(4) mixed solution of stirring waste water and amidoxime group bacteria cellulose, churning time is 2～4h;
(5) filter water outlet.
6. a kind of method that amidoxime group bacteria cellulose is handled effluent containing heavy metal ions of using according to claim 5, it is characterized in that: the heavy metal ion of described step (1) comprises Cu
2+, Pb
2+, Cr
6+One or more.
7. a kind of method that amidoxime group bacteria cellulose is handled effluent containing heavy metal ions of using according to claim 5, it is characterized in that: described step (2) is regulated a kind of or its mixing solutions in waste water ph NaOH solution, the KOH solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100461223A CN101486769A (en) | 2009-02-12 | 2009-02-12 | Preparation of amidoxime group bacteria cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100461223A CN101486769A (en) | 2009-02-12 | 2009-02-12 | Preparation of amidoxime group bacteria cellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101486769A true CN101486769A (en) | 2009-07-22 |
Family
ID=40889841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100461223A Pending CN101486769A (en) | 2009-02-12 | 2009-02-12 | Preparation of amidoxime group bacteria cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101486769A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031391A (en) * | 2010-12-30 | 2011-04-27 | 宾丽萍 | Method for extracting gold from gold mine tailings |
| CN104492486A (en) * | 2014-12-22 | 2015-04-08 | 中国科学院化学研究所 | Biomass load type nano-metal catalyst and preparation method and application thereof |
| CN108395563A (en) * | 2018-05-30 | 2018-08-14 | 陕西科技大学 | A kind of preparation method of bacteria cellulose powder |
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
| CN112808244A (en) * | 2021-01-11 | 2021-05-18 | 浙江理工大学 | Amidoximation adsorbing material and preparation method and application thereof |
| CN113231038A (en) * | 2021-04-09 | 2021-08-10 | 哈尔滨工程大学 | Braided type adsorption material for extracting uranium from seawater and flexible regulation and control preparation method thereof |
| CN114602335A (en) * | 2022-04-19 | 2022-06-10 | 海南大学 | Nanofiber membrane for uranium enrichment and preparation method thereof |
| CN114773490A (en) * | 2022-05-09 | 2022-07-22 | 北控水务(中国)投资有限公司 | Cellulose-based cationic flocculant, preparation method thereof and sludge precipitation method |
-
2009
- 2009-02-12 CN CNA2009100461223A patent/CN101486769A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031391A (en) * | 2010-12-30 | 2011-04-27 | 宾丽萍 | Method for extracting gold from gold mine tailings |
| CN104492486A (en) * | 2014-12-22 | 2015-04-08 | 中国科学院化学研究所 | Biomass load type nano-metal catalyst and preparation method and application thereof |
| CN108395563A (en) * | 2018-05-30 | 2018-08-14 | 陕西科技大学 | A kind of preparation method of bacteria cellulose powder |
| CN108395563B (en) * | 2018-05-30 | 2021-03-09 | 陕西科技大学 | Preparation method of bacterial cellulose powder |
| CN110229384A (en) * | 2019-06-19 | 2019-09-13 | 安徽农业大学 | Silver-colored diamine oxime Cellulose/Chitosan/fibroin composite aerogel of a kind of load and preparation method thereof |
| CN110229384B (en) * | 2019-06-19 | 2021-07-23 | 安徽农业大学 | Silver-loaded diamidoxime cellulose/chitosan/fibroin composite aerogel and preparation method thereof |
| CN112808244A (en) * | 2021-01-11 | 2021-05-18 | 浙江理工大学 | Amidoximation adsorbing material and preparation method and application thereof |
| CN113231038A (en) * | 2021-04-09 | 2021-08-10 | 哈尔滨工程大学 | Braided type adsorption material for extracting uranium from seawater and flexible regulation and control preparation method thereof |
| CN113231038B (en) * | 2021-04-09 | 2022-04-12 | 哈尔滨工程大学 | Braided type adsorption material for extracting uranium from seawater and flexible regulation and control preparation method thereof |
| CN114602335A (en) * | 2022-04-19 | 2022-06-10 | 海南大学 | Nanofiber membrane for uranium enrichment and preparation method thereof |
| CN114773490A (en) * | 2022-05-09 | 2022-07-22 | 北控水务(中国)投资有限公司 | Cellulose-based cationic flocculant, preparation method thereof and sludge precipitation method |
| CN114773490B (en) * | 2022-05-09 | 2023-03-17 | 北控水务(中国)投资有限公司 | Cellulose-based cationic flocculant, preparation method thereof and sludge precipitation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101486769A (en) | Preparation of amidoxime group bacteria cellulose | |
| CN107983300B (en) | The charcoal composite material and preparation method and application of manganese dioxide modification | |
| CN107694510B (en) | Method for removing methylene blue in printing and dyeing wastewater by two-dimensional magnetic MXene | |
| CN103769058B (en) | The preparation method of carbonization chitosan absorbent, product and application process | |
| CN113877521A (en) | Preparation method and application of clay/tannin/metal ion composite material for efficiently adsorbing antibiotics | |
| CN113070036A (en) | Biomass-based functional carbon, preparation method thereof and application of biomass-based functional carbon in removal of micro-plastics in water body | |
| CN106006998A (en) | Attapulgite/denitrifier composite type wastewater treating agent and preparation method thereof | |
| CN103816903B (en) | The synthetic method of iron-base magnetic nanoneedle iron ore | |
| CN104888705A (en) | Preparation method of magnetic ferric oxide/bagasse active carbon | |
| CN110394170A (en) | A kind of preparation method of Ca-Ti ore type zirconic acid calcium catalyst and its application in O3 catalytic oxidation | |
| CN105771912B (en) | A kind of multifunctional bio adsorbent material and preparation method thereof | |
| CN111001374A (en) | Preparation method and application of strontium-doped hydroxyapatite heavy metal adsorption material | |
| CN109133287A (en) | Handle the precipitating reagent and its configuration method of dyeing and printing sewage | |
| CN112675810B (en) | Amorphous high-efficiency phosphorus removal adsorption material, preparation method and water treatment application thereof | |
| CN106732428A (en) | A kind of absorption of drinking water heavy metal depth removal brews agent | |
| CN100400668C (en) | Biosynthesis of obligate adsorbent and its usage in adsorbing to eliminate As and Cr from water | |
| CN106345429A (en) | Bagasse based anion adsorbent and preparation method and application thereof | |
| CN109133290A (en) | The precipitating reagent and preparation method thereof of efficient process chemical engineering sewage | |
| CN105642241A (en) | Biomass-based adsorption material for removing harmful anions in water and preparation method thereof | |
| CN109179615B (en) | Modified cotton fiber adsorbent for removing nitrate nitrogen and preparation method and application thereof | |
| CN113913482A (en) | Plant-based solid-liquid mixed carbon source and preparation method thereof | |
| CN102160988A (en) | Method for preparing dyeing wastewater treatment material | |
| CN105254124A (en) | Steel rolling wastewater treating method | |
| CN106582553A (en) | Preparation method of adsorbent for heavy metal waste liquid treatment | |
| CN109225174A (en) | A kind of modified calcium alginate fibre heavy-metal adsorption material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090722 |