CN106268980A - A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve - Google Patents
A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve Download PDFInfo
- Publication number
- CN106268980A CN106268980A CN201610780206.XA CN201610780206A CN106268980A CN 106268980 A CN106268980 A CN 106268980A CN 201610780206 A CN201610780206 A CN 201610780206A CN 106268980 A CN106268980 A CN 106268980A
- Authority
- CN
- China
- Prior art keywords
- ion sieve
- ammonium ion
- doping
- mno
- 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.)
- Pending
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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/10—Oxides or hydroxides
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
A kind of NH in selectivity exchange water body4 +Fe3+The preparation method of doping ammonium ion sieve, belongs to ammonium ion sieve technical field.Based on ammonium ion sieve to NH4 +Distinctive adsorptive selectivity, utilizes Fe3+Doping ammonium ion sieve is to NH4 +Realization is separated and recovered from, it is achieved to NH in water body4 +The high efficiente callback of resource.Advantages of the present invention: Fe3+Doping ammonium ion sieve NH under the solution system that multiple cation coexists, in selective absorption solution4 +, advantages of good adsorption effect, low cost, beneficially industrialization promotion.Ammonium ion sieve passes through Fe3+Doping, strengthen the stability of ammonium ion sieve, reduce the molten loss rate in regenerative process, improve the cyclic utilization rate of ammonium ion sieve.Designability is strong, it is possible to by the ion sieve of proportioning raw materials synthesis different structure.This ion sieve achieves the selective recovery of ammonia nitrogen in water, and the development for the utilization of resources and green economy provides strong support.
Description
Technical field
The present invention relates to a kind of NH in selectivity exchange water body4 +Fe3+The preparation method of doping ammonium ion sieve, belongs to
In ammonium ion sieve technical field.
Background technology
Environmental pollution and resource exhaustion have become the restraining factors of China's sustainable development, at present, and can profit in sewage system
Get more and more people's extensive concerning with the recovery of resource.Sewage typically contains more NH4 +、Na+、Ca2+、Mg2+Etc. different sun
Ion, Na+、Ca2+、Mg2+Coexisting to NH etc. cation4 +Recovery produce and hinder greatly.The most industrial also do not have one
Material can realize NH in the case of other different cationes coexist4 +Selective recovery.The present invention is prepared for a kind of to NH4 +Having the Fe2O3 doping ammonium ion sieve that specific selectivity reclaims, it can be to NH in the water body that multiple cation coexists4 +Selectivity
Absorption and reclaiming, has that adsorbance is big, selectivity is high, Stability Analysis of Structures, molten loss rate is low, regenerability good, be prone to industry simultaneously
The advantages such as change.Solve the technical problem that as follows:
(1) ammonium ion sieve prepared by the present invention is for NH in water body4 +Exchange there is high selectivity, solve tradition absorption
Agent is for NH in water body4 +The technical problem of high selectivity exchange cannot be realized.Concrete principle is: utilize NH4 +With K+Size phase
Nearly principle, utilizes ion blotting method first to prepare presoma α-MnO2-K, after the protonation of concentrated nitric acid, obtains ammonium ion sieve
α-MnO2-H.Utilize ammonium ion sieve α-MnO2-H removes the NH in selective absorption water body4 +, obtain α-MnO2-NH4, recycle acid solution
To α-MnO2-NH4Regenerate, obtain ammonium ion sieve α-MnO2-H.The dense NH contained in regenerated liquid4 +Can use as nitrogenous fertilizer, real
The recycling of existing ammonia nitrogen.
(2) in the preparation of ammonium ion sieve, adulterate Fe3+, utilize Fe3+Replace α-MnO2Mn in crystal3+, ammonium can be improved
The oxidation state of manganese element in ion sieve, to reduce Mn3+Content, thus suppress Jahn-Teller to distort, strengthen ammonium ion
The stability of sieve structure, greatly reduces ammonium ion sieve and in use produces serious molten damage phenomenon.Prepared ammonium from
Sub-sifter device has that adsorbance is big, selectivity is high, Stability Analysis of Structures, molten loss rate is low, regenerability good, be prone to the advantages such as industrialization.
Along with the fast development of industrial and agricultural production, a large amount of sanitary sewages, industrial wastewater and agrochemical enter river, lake
In water body so that the ammonia-nitrogen content of water body increases, excess of ammonia nitrogen can cause body eutrophication, algae reproduction, and water quality is serious
Deteriorating, aquatic animal is by serious threat.For a long time, municipal sewage plant is mainly with removal COD and SS as target, to ammonia
The removal effect of nitrogen is the most notable.Therefore, the concentration effectively reducing ammonia nitrogen in sewage has become the new problem of sewage treatment area.Warp
Ji, the ammonia nitrogen removal technology being suitable for are then one of research emphasis.
Process at present the practical method of ammonia nitrogen waste water and mainly have break point chlorination method, stripping air-extraction, biological nitration-anti-
Nitrification process, electrochemical oxidation process and ion exchange etc..Although break point chlorination method has, response speed is fast, nitric efficiency is high
Advantage, but the most easily form the by-products such as chloramines, cause secondary pollution of water, more cannot be to NH4 +Carry out resource to return
Receive.Stripping air-extraction is technically feasible in the case of higher ph, but ammonia nitrogen mass concentration is less than 100mg/L in waste water
Time be uneconomic, and atmospheric pollution can be produced.Although biological nitration-denitrification method is effective, but the bioconversion to ammonia nitrogen
Act on slower so that technique needs bigger floor space, improves capital construction cost.It is a kind of that electrochemical oxidation process removes ammonia nitrogen
New technique, its feature is that floor space is little, to the removal ratio of ammonia nitrogen more thoroughly, can reach the requirement of advanced treating, but its mesh
Front mainly for the treatment of ammonia nitrogen in city garbage percolate, it is uneconomical in the case of in waste water, ammonia nitrogen mass concentration is relatively low
's.Ion exchange is that zeolite granular etc. is by NH4 +It is adsorbed in surface or duct, utilizes its exchangeable ion carried in solid phase
With there is ion exchange process on the interface of gas phase, thus reach to remove the purpose of ammonia nitrogen in waste water.Water-soluble at only ammonia nitrogen
Liquid, zeolite can adsorb and reclaim ammonia nitrogen efficiently, but zeolite is to Na+、Mg2+、Ca2+Etc. cation, there is the strongest suction equally
Attached effect, causes it cannot be to NH in mixing salt solution system4 +Selective recovery utilize.
Cation in sewage is except NH4 +Outside, there is also substantial amounts of Na+、Mg2+、Ca2+Etc. cation.Currently for
NH4 +Adsorbing material be mainly zeolite molecular sieve, but the adsorbance of zeolite molecular sieve is little, poor selectivity, it is impossible at multiple sun
To NH in the system that ion exists4 +Carry out selective recovery.Found by investigation, the waste water that researcher molecular sieve processes contains
There is K+、Ca2+、Na+、NH4 +Etc. cation, (such as Xiao Tian deposits et al., for removing the NaA-1 type ion-exchanger of ammonia nitrogen in water
Research, " chemical industry environmental protection " 1997,6:327-331), result shows K+、Ca2+Existence be unfavorable for the purification of ammonia nitrogen in water.Produce
The reason of this result is mainly K+Compare NH4 +Radius little, higher with the active force of this exchanger skeleton；Ca2+Carry two positive electricity
Lotus, not only strong with the active force of skeleton, and also in exchanger structure, position from monovalent cation is different.Also researcher is had to visit
Study carefully at K+、Mg2+、Na+Under conditions of plasma coexists, the impact of ammonia nitrogen absorption performance (is such as opened by ZSM-5 type zeolite molecular sieve
Strong, ammonia nitrogen studies in two kinds of ZSM-5 zeolite molecular sieve adsorption water, " Environmental science and technology " 2011,8:104-108).Experiment
Result shows that zeolite molecular sieve is to K+、Mg2+、Na+The adsorptivity of ion is higher, has a strong impact on molecular sieve to NH4 +Clearance, because of
This is in the case of multiple cation coexists, and zeolite molecular sieve is to NH4 +Selective adsorption poor, it is impossible to realize to NH4 +Choosing
Selecting property reclaims.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of NH in selectivity exchange water body4 +Fe3+Mix
The preparation method of miscellaneous ammonium ion sieve.
A kind of NH in selectivity exchange water body4 +Fe3+The preparation method of doping ammonium ion sieve, containing following steps；
Step 1), select synthetic material:
Solvent: concentrated sulphuric acid (H2SO4), concentrated nitric acid, deionized water；Bivalent manganese source: manganese sulfate (MnSO4)；
Septivalency manganese source: potassium permanganate (KMnO4)；Ferric iron source: iron sulfate (Fe2(SO4)3)；Synthesis temperature: water-bath 30 DEG C-
90℃；
Step 2), the preparation of presoma:
Step A), weigh 10mL concentrated sulphuric acid (or concentrated nitric acid) and mix with 0-180mL deionized water, prepare 1mol/L-
The sulphuric acid (or nitric acid) of 14mol/L；
Step B), prepared sulphuric acid or nitric acid are divided into two parts, preparation 0.1mol/L-10mol/L manganese sulfate/sulphuric acid
(or nitric acid) solution, is stirred at room temperature 1h, another potassium permanganate/sulphuric acid (or nitric acid) solution preparing 0.5mol/L-5mol/L, 50 DEG C
Lower stirring is completely dissolved to potassium permanganate；
Step C), according to the amount ratio of ferrum and the material of manganese for 0-0.08, in manganese sulfate solution, add iron sulfate (nitric acid
Ferrum), stir certain time；
Step D), potassium permanganate/dilute sulfuric acid (or dust technology) mixed liquor is added dropwise to manganese sulfate/iron sulfate (chlorination
Ferrum) mixed liquor, at water-bath 30-90 DEG C, stirs 5-8h；
Step E), after reaction terminates, be cooled to room temperature, be centrifuged washing to neutral, dry, prepare Fe3+Doping from
Son sieve presoma α-MnO2-K；
Step 3), the protonation of presoma:
Ion sieve presoma α-MnO by synthesis2-K is soaked in the concentrated nitric acid of 6mol/L with the ratio of mass ratio 1:18
24h, centrifuge washing repeatedly, is placed in 80 DEG C of oven dryings after a while, finally obtains Fe3+Ammonium ion sieve α-the MnO of doping2-H。
By preparing presoma α-MnO2-K, after the protonation process of concentrated nitric acid, obtains ammonium ion sieve α-MnO2-H；
K+With NH4 +Close (the K of ionic radius+Radius isNH4 +Radius is), the presoma α of preparation-
MnO2Pore size ≈ of-KAmmonium ion sieve α-the MnO obtained after presoma is acidified2-H remain presoma α-
MnO2The pore size of-K.
Fe3+Doping substitute α-MnO2Part Mn in structure3+, improve the oxidation state of manganese element in ammonium ion sieve,
To reduce Mn3+Content, suppression Jahn-Teller distortion, enhance the stability of ammonium ion sieve structure, ammonium when reducing regeneration
The molten loss rate of ion sieve, improves the cyclic utilization rate of ammonium ion sieve.
Building-up process is water-bath 30-90 DEG C.
Bivalent manganese source is manganese sulfate, its concentration range 0.1mol/L-10mol/L, and septivalency manganese source is potassium permanganate, its concentration
For 0.5mol/L-5mol/L；Solvent is sulphuric acid (or nitric acid), and its concentration range is 1mol/L-14mol/L；Measure Fe3+Doping ammonium
When ion sieve is to the selectivity of ammonia nitrogen, test fluid intermediate ion includes NH4 +、Na+、Ca2+、Mg2+Ion common in surface water body.
It is an advantage of the invention that the Fe of preparation3+Doping ammonium ion sieve has to the ammonia nitrogen in water body that adsorbance is big, selects to inhale
The advantages such as attached property height, Stability Analysis of Structures, molten loss rate is low, regenerability is good, can realize the high selective recovery of ammonium radical ion, contain
In the aqueous systems of multiple cation, ion sieve to the adsorbance of ammonia nitrogen with clearance almost without the shadow by other cationes
Ring, and ammonia nitrogen removal frank be can reach more than 80%, Fe simultaneously3+The effective stability improving ammonium ion sieve of doping, reduces again
The molten loss rate of ion sieve time raw, it is easy to industrial applications.
At present in terms of adsorbing material, also there is no researcher by Fe3+Doped alpha-MnO2Type ion sieve is used for the removal of ammonia nitrogen,
Find through investigation, compare typically zeolite molecular sieve for removing the adsorbing material of ammonia nitrogen, this is because zeolite molecular sieve
Aperture is homogeneous, duct neat, have good absorption property to cation.But the building-up process of zeolite molecular sieve is complicated,
Productivity is low, adsorbance is little, regeneration rate is low and in the case of multiple cation coexists, to NH4 +Do not possess selectivity, it is impossible to
Reach NH4 +The selective recovery of resource.
The purpose of the application is aiming in the mixed system that multiple cation coexists, based on ammonium ion sieve to NH4 +
Distinctive adsorptive selectivity, utilizes Fe3+Doping ammonium ion sieve is to NH4 +Realization is separated and recovered from, it is achieved to NH in water body4 +Resource
High efficiente callback, wherein Fe3+Doping molten loss rate of ammonium ion sieve when can be effectively reduced regeneration, can be mass should with industry
With, there is economic feasibility.
Advantages of the present invention:
(1)Fe3+Doping ammonium ion sieve NH under the solution system that multiple cation coexists, in selective absorption solution4 +, advantages of good adsorption effect, low cost, beneficially industrialization promotion.
(2) ammonium ion sieve passes through Fe3+Doping, strengthen the stability of ammonium ion sieve, reduce the molten loss rate in regenerative process,
Improve the cyclic utilization rate of ammonium ion sieve.
(3) designability is strong, it is possible to by the ion sieve of proportioning raw materials synthesis different structure.
(4) this ion sieve achieves the selective recovery of ammonia nitrogen in water, and the development for the utilization of resources and green economy provides
Strong support.
Accompanying drawing explanation
When considered in conjunction with the accompanying drawings, by referring to detailed description below, it is possible to be more completely more fully understood that the present invention with
And easily learn the advantage that many of which is adjoint, but accompanying drawing described herein is used for providing a further understanding of the present invention,
Constituting the part of the present invention, the schematic description and description of the present invention is used for explaining the present invention, is not intended that this
Bright improper restriction, such as figure wherein:
Fig. 1 is the ammonium ion sieve Selective Separation schematic diagram to ammonium radical ion and sodium ion of the present invention；
Fig. 2 is that the ferrimanganic dosage of the present invention compares experimental data figure than with actual ferrimanganic；
Fig. 3 is that the different theories ferrimanganic ratio (throwing amount than) of the present invention affects figure to the molten loss rate of ammonium ion sieve；
Fig. 4 be the present invention different theories ferrimanganic ratio (throwing amount than) on the cycle performance of ammonium ion sieve affect figure；
Fig. 5 is the Fe of the present invention3+The XRD diffraction analysis figure of doping ammonium ion sieve；
Fig. 6 is the Fe of the present invention3+The NH of doping ammonium ion sieve variable concentrations ammonia nitrogen solution4 +Clearance figure；
Fig. 7 is the Fe of the present invention3+Doping ammonium ion sieve is to Na in variable concentrations sodium chloride solution+Clearance figure；
Fig. 8 is the Fe of the present invention3+Doping ammonium ion sieve is to NH in mixed solution4 +And Na+Clearance figure；
Fig. 9 is the Fe of the present invention3+The doping ammonium ion sieve clearance figure to ion each in mixed liquor；
Figure 10 is the Fe of the present invention3+The doping ammonium ion sieve clearance figure to ion each in tap water；
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
Detailed description of the invention
Obviously, those skilled in the art belong to the guarantor of the present invention based on the many modifications and variations that spirit of the invention is done
Protect scope.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singulative used herein " ", "
Individual ", " described " and " being somebody's turn to do " may also comprise plural form.It is to be further understood that the wording used in this specification " bag
Include " refer to there is described feature, integer, step, operation, element and/or assembly, but it is not excluded that existence or add one or
Other features multiple, integer, step, operation, element, assembly and/or their group.It should be understood that when claiming element, assembly quilt
When ' attach ' to another element, assembly, it can be directly connected to other elements or assembly, or can also there is cental element
Part or assembly.Wording "and/or" used herein includes that one or more any cell listing item being associated is with complete
Portion combines.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, and all terms used herein (include technology art
Language and scientific terminology) have with the those of ordinary skill in art of the present invention be commonly understood by identical meaning.Also should
Being understood by, those terms defined in such as general dictionary should be understood that the meaning having with the context of prior art
The meaning that justice is consistent, and unless defined as here, will not explain by idealization or the most formal implication.
For ease of the understanding to the embodiment of the present invention, explanation will be further explained below, and each embodiment will be not
Constitute the restriction to the embodiment of the present invention.
Embodiment 1: as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8, Fig. 9, Figure 10, a kind of for selectivity
NH in exchange water body4 +Fe3+The preparation method of doping ammonium ion sieve, containing following steps；
Step 1), synthetic material:
Solvent: concentrated sulphuric acid (H2SO4), concentrated nitric acid, deionized water；Bivalent manganese source: manganese sulfate (MnSO4)；
Septivalency manganese source: potassium permanganate (KMnO4)；Ferric iron source: iron sulfate (Fe2(SO4)3)；Synthesis temperature: water-bath 30 DEG C-
90℃。
Step 2), the preparation of presoma:
Step A), weigh 10mL concentrated sulphuric acid (or concentrated nitric acid) and mix with 180mL deionized water, the sulphuric acid of preparation 1mol/L
(or nitric acid)；
Step B), prepared sulphuric acid or nitric acid are divided into two parts, preparation 2mol/L manganese sulfate/sulphuric acid (or nitric acid) molten
Liquid, is stirred at room temperature 1h, another potassium permanganate/sulphuric acid (or nitric acid) solution preparing 0.5mol/L, stirs to potassium permanganate at 50 DEG C
It is completely dissolved；
Step C), be 0.05 according to the amount ratio of ferrum with the material of manganese, in manganese sulfate solution add iron sulfate (ferric nitrate),
Stirring certain time；
Step D), potassium permanganate/dilute sulfuric acid (or dust technology) mixed liquor is added dropwise to manganese sulfate/iron sulfate (chlorination
Ferrum) mixed liquor, at water-bath 60 DEG C, stirs 5h；
Step E), after reaction terminates, be cooled to room temperature, product is centrifuged washing to neutral, dries, prepare Fe3+Mix
Miscellaneous ion sieve presoma α-MnO2-K。
Step 3), the protonation of presoma:
Ion sieve presoma α-MnO by synthesis2-K is soaked in the concentrated nitric acid of 6mol/L with the ratio of mass ratio 1:18
24h, centrifuge washing repeatedly, is placed in 80 DEG C of oven dryings after a while, finally obtains Fe3+Ammonium ion sieve α-the MnO of doping2-H。
The preparation principle of ammonium ion sieve:
KMnO4With MnSO4At H2SO4Generation α-MnO can be reacted under system2Crystal, α-MnO2Crystal in developmental process, pole
Most manganese element is Mn4+But, also can there is part Mn3+, in reactant liquor, therefore add Fe2(SO4)3, in solution
Fe3+The developmental process of crystal can be participated in, and replace part Mn3+, thus obtain Fe3+α-the MnO of doping2Crystal.
Additionally, due to Mn3+With Fe3+Existence, α-MnO can be caused2Crystalline framework entirety shows elecrtonegativity, therefore can suction phase
Answer the K of the quantity of electric charge+Enter α-MnO2The tunnel of crystal, carries out stable alpha-MnO2The skeleton of crystal.
Form α-MnO2The reaction equation of crystal is:
2KMnO4+3MnSO4+2H2O=5MnO2↓+K2SO4+2H2SO4
Due to NH4 +The most easily by MnO4-Oxidation, therefore cannot directly prepare presoma α-MnO2-NH4.Originally grind
Study carefully by preparing presoma α-MnO2-K, after the protonation process of concentrated nitric acid, obtains ammonium ion sieve α-MnO2-H.Select system
Standby presoma α-MnO2The reason of-K is K+With NH4 +Close (the K of ionic radius+Radius isNH4 +Radius is
), the presoma α-MnO of preparation2The pore size of-KWith NH4 +RadiusClosely, presoma
Ammonium ion sieve α-the MnO obtained after acidified2-H remains presoma α-MnO2The pore size of-K, the ammonium therefore prepared from
Son sieve (α-MnO2-H) to NH4 +There is high exchange selectivity.
Fe3+The principle of doping raising ammonium ion sieve structural stability:
Doping Fe3+Purpose be substitute α-MnO2Part Mn in structure3+, the flat of manganese element in ammonium ion sieve can be improved
All oxidation state, to reduce Mn3+Content, thus suppress Jahn-Teller to distort, strengthen the stability of ammonium ion sieve structure.?
During the absorption regeneration of ammonium ion sieve, need the nitric acid using high concentration to process, Mn can be caused3+There is variation of valence
(Mn3+Mn can be become4+With Mn2+, and Mn2+Can dissolve in the solution) so that ammonium ion sieve produces serious molten damage phenomenon.Fe3+
Doping replace part Mn3+, reduce Mn3+Content, improve the stability of ammonium ion sieve.
Ammonium ion sieve has the mechanism of different choice to ammonium radical ion and other cation:
With ammonium ion NH4 +With Na+As a example by analyze ion sieve to NH4 +Selectivity mechanism with other cation.Its mechanism figure
As follows, the pore passage structure of ammonium ion sieve is 2 × 2 types, and duct radius is aboutThe cation that ionic radius is the least, the most easily
Enter the duct of ammonium ion sieve, the duct of the ammonium ion sieve that the most easily dissociates；Ionic radius exceedesCation, the most not
The duct of ammonium ion sieve can be entered；And NH4 +Ionic radius beWith the duct radius of ammonium ion sieve closely, because of
This is in the principle of size coupling, for NH4 +There is high exchange selectivity.Na+RadiusLess than ammonium ion sieve
Duct radius, therefore Na+The duct of ammonium ion sieve can be entered, but work as Na+After entering the duct of ion sieve, due to Na+Half
Footpath and the difference of ammonium ion sieve duct radius so that Na+Cannot stably be present in the duct of ammonium ion sieve.Comparatively speaking,
NH4 +Radius the most close with the duct radius of ammonium ion sieve, matching degree is higher, NH4 +Can be stable be present in ion sieve
In duct.At NH4 +With Na+System in, the duct of ammonium ion sieve can be preferentially by NH4 +Occupying, therefore ammonium ion sieve is to NH4 +With
Na+System in NH4 +Possesses good preference.
Fe2O3 doping is on the molten loss rate of ammonium ion sieve and circulative impact:
The exploration of Fe2O3 doping ratio:
0.5mol/L potassium permanganate/sulfuric acid solution is added drop-wise in 0.5mol/L manganese sulfate/sulfuric acid solution, in manganese sulfate
Add the ferric iron source of iron sulfate in advance, ferrum addition and manganese element (amount of the manganese participating in reaction according to theory calculates, for
The amount of the material of 2.5 times of potassium permanganate) the ratio of amount of material be respectively 0,0.01,0.02,0.03,0.05,0.08, be designated as reason
Opinion ferrimanganic ratio.5h is reacted at water-bath 60 DEG C, the actual ferrimanganic ratio of the sample that the product obtained measures after dissolving, experimental result such as table
1, shown in Fig. 2.
The theoretical ferrimanganic of table 1. is than the relation with actual ferrimanganic ratio
From experimental data, the doping of ferrum increases not quite in the range of dosage is than for 0.05-0.08, thus may be used
Knowing, along with the increase of iron content, actual ferrimanganic ratio can reach the limit values, and the most no longer changes, i.e. at α-MnO2Crystal shape
Fe during one-tenth3+Substitute Mn3+There is a limit.According to analysis, ferrum dosage ratio is 0.05 most suitable.
The different ferrimanganic ratios (the throwing amount ratio) impact on the molten loss rate of ammonium ion sieve:
Six groups of samples of above-mentioned different ferrimanganic ratios (0,0.01,0.02,0.03,0.05,0.08) are weighed respectively 1g in
The nitric acid of 100mL 6mol/L soaks three days, surveys and produce manganese ion content in water, shown in concrete tables of data 2, Fig. 3.
The theoretical ferrimanganic ratio of table 2. (throwing amount ratio) and the experimental data of the molten loss rate of ammonium ion sieve manganese
From experimental data, along with increasing of ferrum dosage, the molten loss rate of manganese presents downward trend, with actual ferrimanganic ratio
Corresponding, when the dosage ratio of ferrum is 0.05, the molten loss rate of ammonium ion sieve basically reaches minimum, and this is due to Fe3+Interpolation,
Replace part Mn3+And the framing structure of firm ion sieve, improves the lattice energy of ammonium ion sieve thus reduces molten damage.When ferrimanganic is thrown
When dosage ratio is more than 0.05, the molten loss rate of ammonium ion sieve changes hardly.
The different theories ferrimanganic ratio (the throwing amount ratio) impact on the cycle performance of ammonium ion sieve:
Six groups of samples of above-mentioned different theories ferrimanganic ratio (0,0.01,0.02,0.03,0.05,0.08) are weighed 1g respectively
After adsorption experiment, regenerating, regeneration condition is the nitric acid of 2mol/L.The performance ammonium ion of the ammonium ion sieve after regeneration
Adsorption capacity (mg/g) represents.Experimental result is as shown in table 3, Fig. 4.
The theoretical ferrimanganic ratio of table 3. (throwing amount ratio) and the experimental data of ammonium ion sieve cycle performance
From above chart, along with the increase of iron content, the initial adsorption capacity of ammonium ion sieve is gradually lowered, but warp
After crossing six circular regenerations, the attenuation of ammonium ion sieve also presents the trend always reduced, and wherein height is wanted in the change of attenuation
Gap between initial capacity.Therefore Fe can be drawn3+Doping enhance the stability of ammonium ion sieve structure, reduce and follow
Adsorption capacity attenuation during ring use, improves the cyclic utilization rate of ammonium ion sieve.Through analysis of experimental data, ferrimanganic
Than (throwing amount ratio), in the range of 0.05-0.06, the adsorption capacity attenuation of ammonium ion sieve is relatively low, and reusable edible rate is higher.
Fe3+The XRD diffraction analysis of doping ammonium ion sieve is evaluated:
Utilize the X-ray diffraction analysis (XRD) Fe to synthesis3+Doping ammonium ion sieve is analyzed, and result is as shown in Figure 5.
From figure 5 it can be seen that the characteristic peak phase of characteristic peak and standard card (the JCPDS No.:72-1982) of the ammonium ion sieve of synthesis
Meet, it was demonstrated that the Fe of synthesis3+Doping ammonium ion sieve is α-MnO2Type ion sieve.
Fe3+The doping ammonium ion sieve removal effect to different ions:
Weigh a certain amount of Fe3+Doping ammonium ion sieve mixes according to the ratio that mass ratio is 1:1000 with solion, machine
Tool stirring 2h, then by testing former water and producing the concentration of each ion in water, calculates ammonium ion sieve and imitates the removal of different ions
Really.
Fe2O3 doping ammonium ion sieve is to NH4 +Removal effect:
With the ammonium chloride solution of ultra-pure water preparation series concentration, the Fe synthesized by utilization3+Doping ammonium ion sieve is tested.
NH in former water, product water4 +Concentration and clearance are as shown in table 4, Fig. 6, it can be seen that along with NH4 +Concentration increases, ammonium ion sieve pair
NH4 +Clearance gradually lower, and the amplitude reduced is more and more less.This is primarily due to ammonium ion sieve and NH4 +Between exist
Select adsorption, work as NH4 +When concentration is relatively low, the empty adsorption site of ammonium ion sieve is the most, NH4 +Clearance higher, when
NH4 +When concentration is more than 40mg/L, the NH of contact in the unit interval4 +Concentration higher, the empty adsorption site of ammonium ion sieve is limited,
Therefore NH4 +Clearance reaches steady statue.
NH in the former water of table 4. and product water4 +Concentration
Fe2O3 doping ammonium ion sieve is to Na+Removal effect:
With the sodium chloride solution of ultra-pure water preparation series concentration, the Fe synthesized by utilization3+Doping ammonium ion sieve is tested.
NH in former water, product water4 +Concentration and clearance are as shown in table 5, Fig. 7, it can be seen that ammonium ion sieve is to Na+Clearance the lowest, this
It is because ammonium ion sieve to Na+Adsorption the most weak.
Na in the former water of table 5. and product water+Concentration
Fe2O3 doping ammonium ion sieve is to NH4 +/Na+The removal effect of system:
With the ultra-pure water preparation ammonium chloride of series concentration and sodium chloride mixed solution (Na in mixed solution+And NH4 +Quality
Concentration is equal), the Fe synthesized by utilization3+Doping ammonium ion sieve is tested.NH in former water, product water4 +Concentration and clearance such as table
6, shown in Fig. 8, it can be seen that ammonium ion sieve is to NH4 +And Na+There is different selectivitys, under variable concentrations, ammonium ion sieve pair
NH4 +Clearance all more than 85%, but to Na+Clearance be only about 3%, illustrate that ammonium ion sieve is to NH4 +And Na+Tool
Have and significantly select adsorption, Fe3+Doping ammonium ion sieve is to NH4 +/Na+Selective factor B be about 238.7.Therefore this ion sieve
Can be used in NH4 +/Na+NH in system4 +Efficient recovery.
Table 6.Fe3+Doping ammonium ion sieve is to NH in mixed solution4 +And Na+Removal effect
Fe2O3 doping ammonium ion sieve is to the removal effect of different ions in mixed solution:
With the ultra-pure water preparation ammonium chloride of series concentration, sodium chloride, calcium chloride and mixed solution (every kind of mixing of magnesium chloride
Na in solution+、NH4 +、Ca2+、Mg2+Mass concentration equal), the Fe synthesized by utilization3+Doping ammonium ion sieve is tested.Former
NH in water, product water4 +Concentration and clearance are as shown in table 7, Fig. 9, it can be seen that in the water body that multiple cation coexists, ammonium from
Son sieve is to NH4 +Clearance all more than 83%, and to Na+、Ca2+、Mg2+The clearance of three kinds of cationes is low, illustrate other from
Ammonium ion sieve specific selectivity is adsorbed NH by son4 +Have little to no effect.
Table 7.Fe3+The doping ammonium ion sieve removal effect to ion each in mixed solution
Fe2O3 doping ammonium ion sieve is to containing NH4 +The removal effect of each ion in tap water:
NH is prepared with tap water4 +Concentration is the ammonium chloride solution of 40mg/L, the Fe synthesized by utilization3+Doping ammonium ion sieve
Test.NH in former water, product water4 +Concentration and clearance are as shown in table 8, Figure 10.
Table 8.Fe3+The doping ammonium ion sieve removal effect to ion each in tap water
From table 8, Figure 10 it can be seen that Fe3+Doping ammonium ion sieve is to containing NH4 +Tap water in each ion clearance with
In pure water, the clearance of each ion is close, and ammonium ion sieve is to NH4 +There is higher clearance, and to Na+、Ca2+、Mg2+Three kinds from
The clearance of son is the lowest.Illustrate that ion sieve is capable of the selective recovery of ammonia nitrogen in fresh water.
The key point of the application with being intended to protect is a little:
(1) preparation principle of ammonium ion sieve and the principle of selective absorption ammonium ion: due to NH4 +The most easily quilt
MnO4-oxidation, therefore cannot directly prepare presoma α-MnO2-NH4.The application is by preparing presoma α-MnO2-K, through overrich
After the protonation process of nitric acid, obtain ammonium ion sieve α-MnO2-H.Presoma α-MnO is prepared in selection2The reason of-K is K+With NH4 +
Close (the K of ionic radius+Radius isNH4 +Radius is), the presoma α-MnO of preparation2The pore radius of-K
SizeWith NH4 +RadiusClosely, the ammonium ion sieve α-MnO obtained after presoma is acidified2-H
Remain presoma α-MnO2The pore size of-K, the ammonium ion sieve therefore prepared (α-MnO2-H) to NH4 +Have high
Exchange selectivity.
(2)Fe3+Doping substitute α-MnO2Part Mn in structure3+, improve the average oxidation of manganese element in ammonium ion sieve
State, to reduce Mn3+Content, suppression Jahn-Teller distortion, enhance the stability of ammonium ion sieve structure, reduce regeneration
Time ammonium ion sieve molten loss rate, improve the cyclic utilization rate of ammonium ion sieve.
(3) raw material is simple, and mild condition, building-up process is water-bath 30-90 DEG C.
(4)α-MnO2Preparation principle be comproportionation reaction, generate without other by-products.
(5) bivalent manganese source is manganese sulfate, its concentration range 0.1mol/L-10mol/L, and septivalency manganese source is potassium permanganate, its
Concentration is 0.5mol/L-5mol/L.
(6) solvent is sulphuric acid (or nitric acid), and its concentration range is 1mol/L-14mol/L.
(7) under conditions of multiple cation coexists, Fe3+Doping ammonium ion sieve is to NH4 +Possess and significantly select absorption
Property, therefore ammonium ion sieve is capable of NH in cation mixed system4 +High efficiente callback.
(8) Fe is measured3+When doping ammonium ion sieve is to the selectivity of ammonia nitrogen, test fluid intermediate ion includes NH4 +、Na+、Ca2+、
Mg2+In ion common in surface water body.
Utilize the presoma α-MnO that other method synthesizes2-K, after the protonation process of concentrated nitric acid, can obtain ammonium
Ion sieve α-MnO2-H, and the ammonium ion sieve of the type has selective absorption effect for ammonium ion in water body.
As it has been described above, embodiments of the invention are explained, but as long as essentially without departing from this
Bright inventive point and effect can have a lot of deformation, and this will be readily apparent to persons skilled in the art.Therefore, this
Within the variation of sample is also integrally incorporated in protection scope of the present invention.
Claims (6)
1. a NH in selectivity exchange water body4 +Fe3+The preparation method of doping ammonium ion sieve, based on ammonium ion sieve pair
NH4 +Distinctive adsorptive selectivity, utilizes Fe3+Doping ammonium ion sieve is to NH4 +Realization is separated and recovered from, it is achieved to NH in water body4 +Money
The high efficiente callback in source.
One the most according to claim 1 is NH in selectivity exchange water body4 +Fe3+The preparation side of doping ammonium ion sieve
Method, it is characterised in that containing following steps；
Step 1), select synthetic material:
Solvent: concentrated sulphuric acid (H2SO4), concentrated nitric acid, deionized water；Bivalent manganese source: manganese sulfate (MnSO4)；
Septivalency manganese source: potassium permanganate (KMnO4)；Ferric iron source: iron sulfate (Fe2(SO4)3)；Synthesis temperature: water-bath 30 DEG C-90 DEG C；
Step 2), the preparation of presoma:
Step A), weigh 10mL concentrated sulphuric acid (or concentrated nitric acid) and mix with 0-180mL deionized water, preparation 1mol/L-14mol/L's
Sulphuric acid (or nitric acid)；
Step B), prepared sulphuric acid or nitric acid are divided into two parts, manganese sulfate/sulphuric acid (or nitre of preparation 0.1mol/L-10mol/L
Acid) solution, 1h is stirred at room temperature, another potassium permanganate/sulphuric acid (or nitric acid) solution preparing 0.5mol/L-5mol/L, stirs at 50 DEG C
Mix to potassium permanganate and be completely dissolved；
Step C), according to the amount ratio of ferrum and the material of manganese for 0-0.08, in manganese sulfate solution, add iron sulfate (ferric nitrate), stir
Mix certain time；
Step D), potassium permanganate/sulphuric acid (or nitric acid) mixed liquor is added dropwise to manganese sulfate/iron sulfate (iron chloride) mixing
Liquid, at water-bath 30-90 DEG C, stirs 5-8h；
Step E), after reaction terminates, be cooled to room temperature, be centrifuged washing to neutral, dry, prepare Fe3+The ion sieve of doping
Presoma α-MnO2-K；
Step 3), the protonation of presoma:
Ion sieve presoma α-MnO by synthesis2-K is soaked in the concentrated nitric acid 24h of 6mol/L with the ratio of mass ratio 1:18, centrifugal
Washing repeatedly, is placed in 80 DEG C of oven dryings after a while, finally obtains Fe3+Ammonium ion sieve α-the MnO of doping2-H。
One the most according to claim 2 is NH in selectivity exchange water body4 +Fe3+The preparation side of doping ammonium ion sieve
Method, it is characterised in that by preparing presoma α-MnO2-K, after the protonation process of concentrated nitric acid, obtain ammonium ion sieve α-
MnO2-H；
K+With NH4 +Close (the K of ionic radius+Radius isNH4 +Radius is), the presoma α-MnO of preparation2-
The pore radius of K is more than ≈Ammonium ion sieve α-the MnO obtained after presoma is acidified2-H remains presoma α-MnO2-K
Pore size.
One the most according to claim 2 is NH in selectivity exchange water body4 +Fe3+The preparation side of doping ammonium ion sieve
Method, it is characterised in that Fe3+Doping substitute α-MnO2Part Mn in structure3+, improve the averaged oxygen of manganese element in ammonium ion sieve
Change state, to reduce Mn3+Content, suppression Jahn-Teller distortion, enhance the stability of ammonium ion sieve structure, reduce again
Time raw, the molten loss rate of ammonium ion sieve, improves the cyclic utilization rate of ammonium ion sieve.
One the most according to claim 2 is NH in selectivity exchange water body4 +Fe3+The preparation side of doping ammonium ion sieve
Method, it is characterised in that building-up process is water-bath 30-90 DEG C.
One the most according to claim 2 is NH in selectivity exchange water body4 +Fe3+The preparation side of doping ammonium ion sieve
Method, it is characterised in that bivalent manganese source is manganese sulfate, its concentration range 0.1mol/L-10mol/L, septivalency manganese source is potassium permanganate,
Its concentration is 0.5mol/L-5mol/L；Solvent is sulphuric acid (or nitric acid), and its concentration range is 1mol/L-14mol/L；Measure Fe3+
When doping ammonium ion sieve is to the selectivity of ammonia nitrogen, test fluid intermediate ion includes NH4 +、Na+、Ca2+、Mg2+In surface water body common
Ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610780206.XA CN106268980A (en) | 2016-08-30 | 2016-08-30 | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610780206.XA CN106268980A (en) | 2016-08-30 | 2016-08-30 | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106268980A true CN106268980A (en) | 2017-01-04 |
Family
ID=57673687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610780206.XA Pending CN106268980A (en) | 2016-08-30 | 2016-08-30 | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268980A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975438A (en) * | 2017-04-19 | 2017-07-25 | 天津碧水源膜材料有限公司 | A kind of preparation method of titanyl matrix type ammonium ion sieve |
| CN114632801A (en) * | 2022-03-10 | 2022-06-17 | 湖南博一环保科技有限公司 | Method for carrying out deamination and desulfurization on manganese slag by using rotary kiln |
| CN117228750A (en) * | 2023-09-11 | 2023-12-15 | 北京科净源科技股份有限公司 | Composite reagent suitable for spore transfer all-in-one machine and used for strengthening removal of COD (chemical oxygen demand) or ammonia nitrogen |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121724A (en) * | 2012-12-24 | 2013-05-29 | 华东理工大学 | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 |
| CN103991908A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Method for regulating and controlling stability of lithium ion sieve by cation doping |
-
2016
- 2016-08-30 CN CN201610780206.XA patent/CN106268980A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121724A (en) * | 2012-12-24 | 2013-05-29 | 华东理工大学 | Method for preparing lithium ion sieve MnO2.0.5H2O and precursor thereof Li1.6Mn1.6O4 |
| CN103991908A (en) * | 2014-05-08 | 2014-08-20 | 华东理工大学 | Method for regulating and controlling stability of lithium ion sieve by cation doping |
Non-Patent Citations (2)
| Title |
|---|
| A.BILEWICZ, L.FUKS: "New selective adsorbents for ammonium ions regeneration of dialysate in portable artificial kideny", 《CHEM.ANAL.(WARSAW)》 * |
| JINZHU MA ET AL.: "Transition metal doped cryptomelane-type manganese oxide catalysts for ozone decomposition", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106975438A (en) * | 2017-04-19 | 2017-07-25 | 天津碧水源膜材料有限公司 | A kind of preparation method of titanyl matrix type ammonium ion sieve |
| CN114632801A (en) * | 2022-03-10 | 2022-06-17 | 湖南博一环保科技有限公司 | Method for carrying out deamination and desulfurization on manganese slag by using rotary kiln |
| CN117228750A (en) * | 2023-09-11 | 2023-12-15 | 北京科净源科技股份有限公司 | Composite reagent suitable for spore transfer all-in-one machine and used for strengthening removal of COD (chemical oxygen demand) or ammonia nitrogen |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101569852B (en) | Method for modifying natural zeolite powder | |
| CN102151546B (en) | Modified zeolite as well as preparation method and application thereof | |
| CN106512950A (en) | Preparation method of surfactant-modified zeolite adsorbent | |
| CN107486130A (en) | Prussian-blue takes off the application in ammonium material preparation method and the de- ammonium of sewage | |
| CN105541009A (en) | Treatment method for anionic azo dye wastewater | |
| CN102350303B (en) | Zeolite molecular sieve material which has high-efficiency CO2 capturing function and preparation method thereof | |
| CN104437354A (en) | Method for preparing improved coal ash-zeolite composite particles | |
| CN107262071A (en) | A kind of industrial production process of iron oxide resin compounded adsorbent | |
| CN103599745A (en) | Modified calcium silicate and its application in sewage dephosphorization | |
| CN106268980A (en) | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve | |
| CN109012586A (en) | Uranium absorption agent and preparation method thereof | |
| CN108905976A (en) | Manganese ion doping metal-organic framework materials and its preparation method and application | |
| CN104722282A (en) | Synthesizing method of fly ash magnetic bead magnetic adsorbent coated by chitosan | |
| CN108671886A (en) | A kind of magnetic active carbon adsorbent and the preparation method and application thereof based on abandoned biomass | |
| CN112090392A (en) | Recyclable bimetal modified magnetic phosphorus removal adsorbent and preparation method and application thereof | |
| CN112675810B (en) | Amorphous high-efficiency phosphorus removal adsorption material, preparation method and water treatment application thereof | |
| CN107572557B (en) | Salt slag refined highly effective combined depth processing method | |
| CN113578263A (en) | Preparation method of adsorption material and wastewater dephosphorization process | |
| CN108911009A (en) | Utilize the method for antibiotic in nickel doping metals organic framework material removal water body | |
| CN103418333B (en) | A kind of Bi 3.64mo 0.36o 6.55the preparation method of nano particle and Bi thereof 3.64mo 0.36o 6.55nano material | |
| CN106693884A (en) | Heavy metal adsorbent and preparing method and application thereof | |
| CN103272654A (en) | High specific surface area magnetic anion exchange resin, and preparation method and application of resin | |
| CN103755004A (en) | Strong acid resin composite material of load zero-valence composite metal, preparation method and application thereof | |
| CN102925683B (en) | Indium-iron separation method by using persimmontannin | |
| CN106378147B (en) | A kind of magnetism Au/Fe3O4 catalyst and the preparation method and application 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |
|
| RJ01 | Rejection of invention patent application after publication |