CN108993409A - A kind of preparation method of the sewage treatment porous adsorbing material based on biomass - Google Patents
A kind of preparation method of the sewage treatment porous adsorbing material based on biomass Download PDFInfo
- Publication number
- CN108993409A CN108993409A CN201810768400.5A CN201810768400A CN108993409A CN 108993409 A CN108993409 A CN 108993409A CN 201810768400 A CN201810768400 A CN 201810768400A CN 108993409 A CN108993409 A CN 108993409A
- Authority
- CN
- China
- Prior art keywords
- preparation
- ligand
- biomass
- solution
- prepared
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The preparation method of the invention discloses a kind of sewage treatment porous adsorbing material based on biomass, including following preparation step: the preparation of organic ligand: by agricultural wastes through acid solution or dipping by lye, and then washing and neutralize；Compound cellulose enzyme solutions are added in the biomass material that pretreatment is obtained and carry out biodegrade, obtain the micromolecular polysaccharide ligand prepared for MOFs material；The ligand solution being prepared is mixed with alkali metal salt soln, ligand and metal ion molar ratio are 1~30:1~50, and methanol or alcohol vapour are slowly diffused into solution, after growing crystal, for several times by ethanol washing.The porous adsorbing material with extra specific surface area prepared by the present invention based on biomass material, can consume some of the contaminants, can also achieve the effect that " treatment of wastes with processes of wastes against one another " while reducing environmental pressure；Cheap and easy to get with method raw material provided by the invention, simple process, reaction condition are mild, are suitble to large-scale production.
Description
Technical field
The invention belongs to nanocomposites and field of environment pollution control, and in particular to one kind is for sewage absorption and nothing
The preparation method of the biomass porous adsorbent material of evilization processing.
Background technique
Water is primary condition for the survival of mankind, but in the past few decades, and due to mankind's activity, population increases, city
City, industrialization and cause global water quality heavily contaminated using natural water resources without limitation.The pollution and dirt of water resource
The discharge of water is global environmental issue urgently to be resolved in recent years.The concentration raising of toxic pollutant leads to the mankind's in water body
Health is on the hazard, therefore develops strong, economically feasible, the environmental-friendly wastewater treatment method of one kind and compel in eyebrow
Eyelash.
At present China's year water total amount oneself break through 6000 billion cubic meters, water resource of per capita only has 2100 cubic metres, only
The 28% of world's per capita share.National more than 500 billion cubic meters of annual water deficit, 2/3rds urban water shortage, the north has 9
A provinces and cities account for water per capita and are less than 500 cubic metres, far less than the minimum standard of international regulations (1000 cubic metres), are listed in generation
One of poor-water state of boundary.And with the rapid development of social economy, China's sewage quantity has reached 82,000,000,000 tons at present, and year growth is
2000000000 tons, daily quantity of wastewater effluent reaches 200,000,000 tons.Due to relatively lagging behind for water pollution control, contaminated water body increases year by year,
Exacerbate the shortage of water resource.Water pollution speed is inevitably accelerated in industrialization, the urbanization that beautiful China carries out rapidly.
Wherein most sewage are without being effectively treated beautiful row people's rivers,lakes and seas.The urban waters in 90% or more the whole nation are by different degrees of
Pollution, it is difficult that the concentration drinking water of nearly 50% key cities does not meet water intaking mark.Therefore, field of water pollution control there is an urgent need to
It solves, it will be with important environment protection significance.
Waste water largely containing heavy metal is discharged in the industrial processes such as mine controls, chemical industry, electronics, instrument, machine-building,
Waste water containing heavy metal (such as containing cadmium, nickel, mercury, zinc) is to pollute most serious to natural environment and endanger the mankind maximum
One of industrial wastewater.Heavy metal is generally not easy to disappear in nature, cannot decompose destruction, can only change its Material Form and turn
Moving it, there are positions, they can be enriched with by the way that food chain is beautiful: heavy metal is in addition to directly acting on human body and causing disease, it is also possible to
Promote the development of chronic disease.Therefore very urgent to the processing of heavy metal containing sewage.Sewage containing heavy metal is effectively treated into
To clean sustainable development head technical problems to be solved at this stage.It Cr(VI) is heavy metal common in current polluted-water
One of, it is mainly derived from " three wastes " that the industry such as metallurgy, machinery, plating, process hides, medicine, dyestuff and chemical industry is discharged.Cr(VI)
With carcinogenic and mutagenesis ability, also there is quite high toxicity, and Cr(VI even at a low concentration) it is easy migration, also have
There is very strong oxidability, there is very big harm to environment.
The physico-chemical process of traditional wastewater treatment mainly have ion-exchange, lime softening method, sand filtering, precipitating,
The methods of extraction, ultrafiltration, reverse osmosis, electrodialysis, activated carbon adsorption.These traditional methods have certain application limitation, deposit
Treatment effeciency is low, service condition is stringent, it is at high cost, generate secondary sludge and its high, the difficult regeneration of disposal costs etc. and ask
Topic.In sewage treatment, equipment mainly by waste water by being equipped with adsorbent, some harmful ions and adsorbent in waste water
Other ions or base exchange and stay on the sorbent to being removed, adsorbent then restores exchange capacity by regenerating.
More application at present is inorganic adsorbent.Inorganic adsorbent mainly has zirconium oxide, flyash, aluminium hydroxide, natural
Zeolite, modified molecular screen, activated magnesia, serpentine, activated alumina, hydroxyapatite carry aluminium ion, bauxite, polymerization
Aluminium salt, activation aluminium, titanium dioxide, silica gel load titanium dioxide etc..In general, a kind of good carrier should have the following conditions:
(1) it can provide higher specific surface area；(2) there is preferable suction-operated to the pollutant in sewage；(3) there is fixed physics shape
Shape, convenient for final two-phase laminated flow；(4) stability itself is high, is in chemical inertness, will not be oxidized or restore.
For current widely used active carbon adsorption, since active carbon has the thin of porous hydrophobic and prosperity
Pore structure and huge specific surface area are considered as all-round absorbent, commonly used in the various pollutants gone in water removal, still, by
Difficulty is regenerated in addition in its use cost height limits its being widely used in field of water pollution control.Therefore it is a kind of suitable to find
Adsorbent material, to reach the coordination of economy and efficiency, this also becomes the emphasis studied at present.Due to Cr(VI) discharge standard
Severization, oneself is not able to satisfy emission request to some in these methods, though to carry out cost sufficiently expensive for other methods.
Therefore a kind of sewage that can cope with big flow and less expensive processing method are needed.
Metal-organic framework material (MOFs) is formed by connecting by metal node and organic ligand with infinite network knot
The framework material of structure has the characteristics that bigger serface, high porosity, it is most important that, the aperture of MOFs material and topology knot
Structure has very flexible Modulatory character, can design for the specific adsorption application of dirty water pollutant and prepare its correspondence
Optimal material, therefore MOFs material is considered as the sewage treatment adsorbent for most having promotion prospect and application value.
However, since MOFs material needs the skeleton using the organic ligand constituent material containing groups such as carboxyl, pyridines
Structure causes the cost of MOFs material to increase, is unfavorable for the application of MOFs material to a certain extent.Therefore, with it is low at
This obtains a kind of adsorbent material with extra specific surface area and micro hole construction, then field of water pollution control has very extensively
Wealthy application prospect.
The annual agricultural crop straw yield in China is up to 700,000,000 tons or more, but these resources, except minute quantity is with big in addition to for feed
It is incinerated, this had not only caused the huge waste of resource but also had caused serious environmental pollution more.Rice and kernel straw are rich to be contained largely in
Carbon source, utility value with higher, therefore how to efficiently use rice wheat straw reduces pollution, improves resource utilization one
It is directly that people make every effort to solve the problems, such as.Agricultural wastes agricultural crop straw etc. is rich in the organic matters such as cellulose, lignin, is
By glucose group at macromolecular polysaccharide and there are many alcohol molecular composition complicated phenolic compound, contain large number of energy
The functional group for enough forming MOFs material skeleton structure, can be used as one of the component for preparing MOFs material, such one side energy
The waste utilization for enough realizing the substances such as stalk avoids the pollution on the environments such as conventional incineration processing from the other hand using straw
Stalk substance as a raw material for production, is capable of the production cost of the reduction MOFs product of high degree, is conducive to push away MOFs material
Extensively it is applied to sewage treatment field, realizes the target of " treatment of wastes with processes of wastes against one another ".
If described stalk etc. is carried out recycling treatment, local forestry, animal husbandry, agricultural not only can be solved
With the harm of ecological environment, economic benefit can also be increased to be local, realize the purpose of " useless with evil system, to change harmful to treasure ".However,
Stalk short texture, component is similar to sawdust, and ash content is lower, and content of lignin is higher.Oneself, which has, both at home and abroad is made activity for stalk
The related report of charcoal.It is also as secondary in being be easy to cause using chemical activation method but since stalk produces higher cost needed for active carbon
Pollution and the corrosion of equipment.It is using mesopore molecular sieve as carrier mostly now with the heavy metal in absorption method removal water body
Adsorbent material or biological adsorption agent, but these methods exist it is at high cost, vulnerable to ions other in water body influence etc. lack
Point.
Summary of the invention
It is an object of the invention to: with the work such as agricultural wastes such as crop material and food grade materials cheap and easy to get
A kind of porous adsorbing material with extra specific surface area is obtained by simple preparation method for raw material, and then is applied to dirt
Pollutant in sewage is carried out harmless treatment by absorption and subsequent catalysis burning by water process.It can not only maximum journey
The production cost of the reduction material of degree, simultaneously because can disappear in raw material containing discarded and cheap renewable biomass resources
Different types of pollutant is removed or reduced, can also achieve the effect that " treatment of wastes with processes of wastes against one another " while reducing environmental pressure, is had wide
General applicability.
The technical scheme is that: preparation step are as follows:
(1) preparation of organic ligand:
(1) agricultural wastes pretreatment of raw material,
By agricultural wastes through acid solution or dipping by lye, heating treatment can be carried out when necessary, 20-120 DEG C of temperature range, in turn
Washing neutralizes, to remove the impurity component for being difficult to isolate and purify in waste；
(2) cellulose biodegradation,
To pre-process in obtained biomass material and mass ratio is added is being gathered by endoglucanase, circumscribed Portugal for 0.1%-1.0%
The compound cellulose enzyme solutions of sugared cellobiohydrolase composition carry out biodegrade, obtain small point prepared for MOFs material
Sub- polysaccharide ligand, relative molecular weight 50-500；
(2) preparation of three-dimensional green MOFs material:
The ligand solution being prepared is mixed with alkali metal salt soln, ligand and metal ion molar ratio are 1~30:1
~50, and methanol or alcohol vapour are slowly diffused into solution, after growing crystal, pass through ethanol washing 2 times or more.
Biomass of the present invention is the agricultural wastes based on corn stover.
In step (2) of the present invention alkali metal salt soln include one of potassium chloride, potassium hydroxide, potassium bromide etc. or
It is several.
Contain Cr metal ion in sewage of the present invention.
The method of the present invention, will by pre-processing to macromolecular substances such as cellulose, lignin in agricultural wastes
Two kinds of substances are isolated and purified, as organic ligand.Again by the coordination with alkali metal, synthesis have bio-compatible and
Three-dimensional " green " MOFs material of regenerative nature.This method advantage is: prepared having based on biomass material surpasses
The porous adsorbing material of bigger serface can consume some of the contaminants, can also reach while reducing environmental pressure " with useless
Control useless " effect；Cheap and easy to get with method raw material provided by the invention, simple process, reaction condition are mild, are suitble to scale
Production.
Specific embodiment
Below with reference to specific embodiment, technical scheme is described further.
Case study on implementation 1
(1) by the corn stover that crushed (cross 40 mesh: cross 20 mesh: ratio between 20 mesh and 40 mesh is 21:47:32) in
Equilibrium water conten is stayed overnight at 75 DEG C.The corn stover 100g between 20 mesh and 40 mesh is weighed, is 10% addition by solid content
1.0% dilute sulfuric acid keeps the temperature 2h at 120 DEG C.Filtering to filter liquor is in neutrality after taking-up, by corn stover residue at 75 DEG C
It dries for 24 hours, is made to test agent；
(2) the pretreatment corn stover (2.00g) after weighing equilibrium water conten is added pH4.85's by solid content 10%
The hydrolase of endoglucanase containing 0.2g, circumscribed glucan cellobiose is added in 0.05mol/L Acetic acid-sodium acetate buffer
Solution, temperature are kept for 50 DEG C, hydrolyze 8h.The dialysis membrane for the use of molecular cut off being 1000Da, by cellulase and hydrolysate
(M=485) are separated；
(3) will hydrolysis obtained glucan (58.2mg, 0.12 mmol) 5mL KOH(11.2mg, 0.2mmol) aqueous solution is molten
Solution.Then solution is filtered, filtrate is fitted into medium size glass beaker, then medium size glass beaker is sealed into big equipped with methanol
In flint glass F beaker.One week is stood at room temperature, during which methanol steam slowly diffuses into solution, in middle flint glass F
Colourless cubic block crystal is grown in beaker.These crystal are collected, and with ethanol washing 2-5 times.
Case study on implementation 2
(1) by the corn straw smashing of natural air drying and mistake sieve on the 175th, straw powder 1 is obtained；
(2) it takes the straw powder 1 of step 1 to be placed in reaction kettle, its 16 times of deionized water of quality, the 5.4% of 18 times is added thereto
NaOH solution reacts 26min under conditions of 53 DEG C, and vacuum filtration removes filtrate, obtains straw powder 2；
(3) straw powder 2, water are uniformly mixed according to the ratio of weight ratio 1:15, the inscribe Portugal of its quality 0.15% is added
Dextranase, Cellobiohydrolase, digest 22h in water bath with thermostatic control, obtain hydrolyzation of glucose (M=180)；
(4) glucose (180 g, 1mol) KOH(140g, 2.5 mol for obtaining hydrolysis) aqueous solution 500mL dissolution, then
Solution is filtered, filtrate is fitted into medium size glass beaker, then medium size glass beaker is sealed into the big flint glass F that methanol is housed
In beaker.One week is stood at room temperature, during which methanol steam slowly diffuses into solution, in medium size glass beaker
Colourless cubic block crystal is grown, these crystal are collected, and for several times with ethanol washing.
Case study on implementation 3
(1) corn stover first passes through pulverizer and is crushed, and smashes it through 40 meshes；
(2) smashed corn stover is handled with the NaOH solution of mass concentration 1.0%, solid-to-liquid ratio 1:10,100 DEG C of 1h, mistake
Filter, filter residue are washed to neutrality, and drying to constant weight, as fermentation substrate；
(3) every 10mL is first prepared containing FeSO4•7H2O 0.0005g、MnSO4•7H2O 0.0016g、ZnSO4•7H2O 0.0014g、
CaCl2The micro-mixed liquor of 0.002g；Next prepares nutritive solution, and the mass percent of each component is dense in nutritive solution
Degree is: (NH4) 2SO41%, KH2PO40.3%, MgSO40.05%, CaCl20.05%, remaining is water；Then mixed liquor is prepared,
Mixed liquor is made by adding micro-mixed liquor 1mL in every 100mL nutritive solution；Into the fermentation substrate of step 2 according to feed liquid
Than adding mixed liquor for 1:2.25, pH5.5 is adjusted, sterilize 20min at 121 DEG C, obtains solid-state fermentation culture medium；By the inscribe of preparation
Dextranase, Cellobiohydrolase bacterium solution are fermented by solid-liquid ratio 1:0.5% access solid-state fermentation culture medium
10d obtains hydrolysis mutation saccharic acid (M=82)；
(4) glucose (12.3g, 0.15mol) KCl(15.2g, 0.2mol for obtaining hydrolysis) aqueous dissolution；Then
Solution filtering, filtrate is fitted into medium size glass beaker, then medium size glass beaker is sealed into the big flint glass F equipped with methanol and is burnt
In cup；One week is stood at room temperature, during which methanol steam slowly diffuses into solution, raw in medium size glass beaker
Grow colourless cubic block crystal；These crystal are collected, and with ethanol washing 3-5 times.
The biomass porous adsorbent produced using the method handles I containing Cr(V) test method of sewage, the examination
Proved recipe method includes the following steps, initial pH value first is added in the biomass porous adsorbent of 0.05g~0.5g and is 1~9, contains Cr
(VI) amount is in the 100ml sewage of 50mg/L, and then constant temperature oscillation stirs 1.5h~2.0h, can sewage sample after extraction process
Product examine is surveyed therein containing Cr(VI) amount, wherein when carrying out above-mentioned test, is carried out respectively by two groups, Cr is contained described in one group of holding
The initial pH value of sewage be it is 1 constant, then measure weight be 0.05g, 0.lg, 0.15g, 0.2g, 0.25g, 0.3g, 0.35g,
Each portion of biomass porous adsorbent of 0.4g, 0.45g and 0.5g are separately added into different containing in Cr(VI) sewage, constant temperature oscillation
1.5h~2.0h is stirred, then the sewage sample detection after extraction process is therein contains Cr(VI) amount；Another group then keeps from upper
The usage amount of the best stalk adsorbent obtained in battery of tests is constant, then respectively measure initial pH value be 2,3,4,5,6,7,
8,9 each portion of sewage containing Cr(VI), is separately added into the stalk adsorbent of the dosage, and constant temperature oscillation stirring 1.5h~
2.0h, then the sewage sample detection after extraction process is therein contains Cr(VI) amount.
During cellulose biodegradation of the present invention, the relative molecular weight of prepared micromolecular polysaccharide ligand is 50-
500。
Claims (4)
1. a kind of preparation method of the sewage treatment porous adsorbing material based on biomass, which is characterized in that including preparing as follows
Step:
(1) preparation of organic ligand:
(a) agricultural wastes pretreatment of raw material,
By agricultural wastes through acid solution or dipping by lye, heating treatment can be carried out when necessary, 20-120 DEG C of temperature range, in turn
Washing neutralizes, to remove the impurity component for being difficult to isolate and purify in waste；
(b) cellulose biodegradation,
To pre-process in obtained biomass material and mass ratio is added is being gathered by endoglucanase, circumscribed Portugal for 0.1%-1.0%
The compound cellulose enzyme solutions of sugared cellobiohydrolase composition carry out biodegrade, obtain small point prepared for MOFs material
Sub- polysaccharide ligand, relative molecular weight 50-500；
(2) preparation of three-dimensional green MOFs material:
The ligand solution being prepared is mixed with alkali metal salt soln, ligand and metal ion molar ratio are 1~30:1
~50, and methanol or alcohol vapour are slowly diffused into solution, after growing crystal, pass through ethanol washing 2 times or more.
2. preparation method according to claim 1, it is characterised in that: the biomass is the agricultural based on corn stover
Waste.
3. preparation method according to claim 1, it is characterised in that: alkali metal salt soln includes chlorination in the step (2)
One or more of potassium, potassium hydroxide, potassium bromide etc..
4. preparation method according to claim 1, it is characterised in that: contain Cr metal ion in the sewage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810768400.5A CN108993409B (en) | 2018-07-13 | 2018-07-13 | Preparation method of biomass-based sewage treatment porous adsorption material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810768400.5A CN108993409B (en) | 2018-07-13 | 2018-07-13 | Preparation method of biomass-based sewage treatment porous adsorption material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108993409A true CN108993409A (en) | 2018-12-14 |
| CN108993409B CN108993409B (en) | 2021-04-09 |
Family
ID=64599668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810768400.5A Active CN108993409B (en) | 2018-07-13 | 2018-07-13 | Preparation method of biomass-based sewage treatment porous adsorption material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108993409B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068784A (en) * | 2019-12-20 | 2020-04-28 | 江苏理工学院 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245899A (en) * | 2011-10-05 | 2014-12-24 | Sea6能源有限公司 | Process of production of renewable chemicals and biofuels from seaweeds |
| CN106883420A (en) * | 2017-01-24 | 2017-06-23 | 中国科学院福建物质结构研究所 | A kind of metal organic frame crystalline material, its synthesis and application |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| EP3225590A1 (en) * | 2016-03-31 | 2017-10-04 | Université de Strasbourg | Highly selective artificial neurotransmitter receptors |
| CN107837401A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院上海药物研究所 | Cyclodextrin metal-organic framework materials complex microsphere and preparation method thereof |
-
2018
- 2018-07-13 CN CN201810768400.5A patent/CN108993409B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245899A (en) * | 2011-10-05 | 2014-12-24 | Sea6能源有限公司 | Process of production of renewable chemicals and biofuels from seaweeds |
| CN107151329A (en) * | 2016-03-04 | 2017-09-12 | 中国科学院上海药物研究所 | The fast synthesis method of cyclodextrin-metal-organic framework materials |
| EP3225590A1 (en) * | 2016-03-31 | 2017-10-04 | Université de Strasbourg | Highly selective artificial neurotransmitter receptors |
| CN107837401A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院上海药物研究所 | Cyclodextrin metal-organic framework materials complex microsphere and preparation method thereof |
| CN106883420A (en) * | 2017-01-24 | 2017-06-23 | 中国科学院福建物质结构研究所 | A kind of metal organic frame crystalline material, its synthesis and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068784A (en) * | 2019-12-20 | 2020-04-28 | 江苏理工学院 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
| CN111068784B (en) * | 2019-12-20 | 2021-09-21 | 江苏理工学院 | Preparation method and application of lignin ligand hexahedral iron-based catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108993409B (en) | 2021-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102989427B (en) | Enteromorpha absorbent and preparation technology thereof | |
| CN101829545B (en) | Heavy metal biological adsorbent using eggshell membrane as matrix and preparation method thereof | |
| CN102872811B (en) | Water body oil-spilling adsorbent prepared from modified agricultural straws, and preparation method and application of water body oil-spilling adsorbent | |
| CN106732438A (en) | A kind of natural biomass adsorbent and preparation method and application | |
| CN110694588A (en) | Modified composite biochar and preparation method and application thereof | |
| CN104722267A (en) | Preparation method of absorbing material for heavy metals of polluted water body | |
| CN109046229B (en) | Lanthanum hydroxide modified hydroxyapatite material and preparation method and application thereof | |
| CN109317122A (en) | A kind of modified alkali lignin and preparation method thereof and application as heavy metal ion agent for capturing | |
| CN110523379A (en) | A kind of low cost preparation method of porous charcoal | |
| CN102755878B (en) | Chemical modification method for sawdust material used for purification | |
| CN106180140B (en) | A kind of minimizing technology of Heavy Metal Pollution in Municipal Solid Waste object | |
| CN110078332A (en) | A method of promoting excess sludge anaerobic fermentation and acid production using modified steel scoria | |
| CN109647351A (en) | A kind of bagasse load hydrogen iron oxide adsorbent and its preparation method and application | |
| CN109081339A (en) | A kind of novel nitrogen-dopped activated carbon for greenhouse gases trapping | |
| CN101912767B (en) | Method for preparing modified furfural residue heavy metal adsorbent | |
| CN112957927B (en) | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof | |
| CN108421526B (en) | Method for preparing fly ash defluorinating agent by hydrothermal/acid leaching in two steps and application | |
| CN114082404A (en) | Betel nut waste-based biochar material and preparation method and application thereof | |
| CN108993409A (en) | A kind of preparation method of the sewage treatment porous adsorbing material based on biomass | |
| CN106140095B (en) | The modified preparation and application of the tertiary amine oxide modified attapulgite earth adsorbing of Abietyl-containing ternary phenanthrene ring structure | |
| CN109718726B (en) | Production process of amphiphilic silica-chitosan composite aerogel | |
| CN108671897B (en) | Preparation and application of modified straw fiber adsorbing material | |
| CN108993408A (en) | A kind of preparation method of porous absorption-catalysis material for exhaust-gas treatment based on biomass | |
| CN108636365B (en) | Modified straw fiber adsorption material and use method thereof | |
| CN107262128B (en) | Visible light response type porous boron nitride-based composite photocatalytic material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210311 Address after: Room 1003, block a, 159 Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province, 214400 Applicant after: Jiangyin CHUANGYOU New Material Technology Co.,Ltd. Address before: 330025 9th floor, Qinghu building, 669 Shanghai North Road, Nanchang City, Jiangxi Province Applicant before: JIANGXI KANGQING ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |