CN106975438A - A kind of preparation method of titanyl matrix type ammonium ion sieve - Google Patents
A kind of preparation method of titanyl matrix type ammonium ion sieve Download PDFInfo
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- CN106975438A CN106975438A CN201710255361.4A CN201710255361A CN106975438A CN 106975438 A CN106975438 A CN 106975438A CN 201710255361 A CN201710255361 A CN 201710255361A CN 106975438 A CN106975438 A CN 106975438A
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
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Abstract
The invention provides a kind of preparation method of titanyl matrix type ammonium ion sieve, including raw material be：Nano titanium oxide or metatitanic acid, potassium hydroxide；Wherein preparation method is, the raw material is mixed to form mixed liquor according to setting ratio, mixed liquor control heating sintering is formed into mixture, naturally cooled to after room temperature, the mixture is put into progress acid treatment in the hydrochloric acid solution of setting ratio obtains titanyl matrix type ammonium ion sieve.The technology of the present invention product selectivity is good, there is special selectivity to ammonium ion in surface water containing ammonium ion, adsorbance is big, the adsorbance of this product material is in 101.3mg/g, adsorbance exceedes existing ammonium sorbing material, cyclicity is good, circular regeneration 10 times, and adsorbance does not substantially decay and keeps its selectivity.
Description
Technical field
The present invention relates to chemical materials preparation technology field, more particularly to a kind of preparation side of titanyl matrix type ammonium ion sieve
Method.
Background technology
Mostly using biochemical process such as A in the processing of municipal wastewater2The ammonia nitrogen that O modes are gone in water removal, it is well known that biochemical
The floor space of method is larger, and capital construction cost is higher, and the cultivation cycle of bacterium is longer, and the processing one of Low Concentration Ammonia Containing Wastewater
It is directly the key index of municipal wastewater processing.Ion-exchange processing nitrogen-containing wastewater is not required to add medicament into water and is not required to add
Heat, is a kind of very promising method except ammonia nitrogen process on water quality substantially without influence.But conventional adsorbent has exchange capacity
The shortcomings of low, poor selectivity, reproducibility are poor, causes the method it is difficult to large-scale application.
Because water body ammonia nitrogen is exceeded, cause body eutrophication, algae distorted proliferation takes place frequently, and the nitrogen in water body is to organism
For be most basic nutriment, but excessive nitrogen compound can make algal bloom, and dissolved oxygen falls sharply, and water quality is serious
Degenerate, effective removal of water body ammonia nitrogen is fwaater resources protection and the important step that utilizes.
Traditionally for high concentration ammonium ion sewage processing more than evade using regulation pH value and then with high-temperature steam
Ammonium ion is removed in reinforcing.In advanced treating and reused sewage, bio-contact oxidation or biofilter are used the removal of ammonium ion more
Etc. method.The practical method of processing ammonia nitrogen waste water mainly has stripping air- extraction, break point chlorination method, electrochemical oxidation at present
Method, biological nitration-denitrification method and ion-exchange etc..Stripping air- extraction is technically feasible in the case of higher ph
, but be uneconomic when ammonia nitrogen mass concentration is less than 100mg/L in waste water, and atmosphere pollution can be produced.Break point chlorination
Although method has the advantages that reaction speed is fast, nitric efficiency is high, the accessory substances such as chloramines are easily formed in the process, cause water
Body secondary pollution, more can not be to NH4 +Carry out resource reclaim.It is a kind of new technology, its feature that electrochemical oxidation process, which removes ammonia nitrogen,
It is that floor space is small, the requirement of advanced treating can be reached to the removal ratio of ammonia nitrogen more thoroughly, but it is currently used primarily in processing city
Ammonia nitrogen in city's percolate, when in waste water ammonia nitrogen mass concentration it is relatively low in the case of be uneconomic.Biological nitration-denitrification
It is slower to the biotransformation of ammonia nitrogen although method is effectively so that technique needs larger floor space, improve capital construction into
This.Ion-exchange is zeolite granular etc. by NH4 +It is adsorbed in surface or duct, using the exchangeable ion of its band in solid phase
Occurs ion exchange process with the interface of gas phase, so as to reach the purpose for removing ammonia nitrogen in waste water.In the water-soluble of only ammonia nitrogen
Liquid, zeolite-type molecular sieve can efficiently adsorb and reclaim ammonia nitrogen, but zeolite-type molecular sieve is to Na+、Mg2+、Ca2+Deng cation
It is same that there is very strong suction-operated, cause it can not be in mixing salt solution system to NH4 +Selective recovery utilize.
Cation in sewage is except NH4 +Outside, also there is substantial amounts of Na+、Mg2+、Ca2+Deng cation.At present, for
NH4 +Sorbing material be mainly zeolite molecular sieve, but the adsorbance of zeolite molecular sieve is small, poor selectivity, it is impossible in a variety of sun
To NH in the system that ion is present4 +Carry out selective recovery.Found, contained in the waste water that researcher is handled with molecular sieve by investigating
There is K+、Ca2+、Na+、NH4 +Deng cation, (such as Xiao Tian deposits et al., the NaA-1 type ion-exchangers for removing ammonia nitrogen in water
Research,《Chemical industry environmental protection》1997,6：327-331), K is as a result shown+、Ca2+Presence be unfavorable for the purification of ammonia nitrogen in water.Produce
The reason for this result, is mainly K+Compare NH4 +Radius it is small, the active force with the exchanger skeleton is stronger；Ca2+Two positive electricity of band
Lotus, not only the active force with skeleton is strong and different from the position of monovalent cation in exchanger structure.Also there is researcher's spy
Study carefully in K+、Mg2+、Na+Under conditions of plasma coexists, influence of the ZSM-5 types zeolite molecular sieve to ammonia nitrogen absorption performance (is for example opened
It is strong, ammonia nitrogen studies in two kinds of ZSM-5 zeolite molecular sieve adsorption water,《Environmental science and technology》2011,8：104-108).Experiment
As a result show zeolite molecular sieve to K+、Mg2+、Na+The adsorptivity of ion is higher, has a strong impact on molecular sieve to NH4 +Clearance, because
This is in the case where a variety of cations coexist, and zeolite molecular sieve is to NH4 +Selective adsorption it is poor, it is impossible to realize to NH4 +Choosing
Selecting property is reclaimed.
The content of the invention
The embodiment provides a kind of preparation method of titanyl matrix type ammonium ion sieve, by novel material system
The layer structure ammonium ion sieve that standby synthesis is obtained, reaches the effect of ammonium ion in more effective absorption water.
To achieve these goals, this invention takes following technical scheme：
A kind of preparation method of titanyl matrix type ammonium ion sieve, including raw material be：Nano titanium oxide or metatitanic acid, hydrogen
Potassium oxide；Characterized in that, the raw material is mixed to form mixed liquor according to setting ratio, the mixed liquor is controlled to rise
Temperature sintering forms mixture, naturally cools to after room temperature, and the mixture is put into the hydrochloric acid solution of setting ratio and carries out acid
Processing obtains titanyl matrix type ammonium ion sieve.
The nano titanium oxide or metatitanic acid are 0.5 according to mol ratio with the potassium hydroxide:1~3:1 mixed grinding
0.5h~3h.
Mixed liquor control heating sintering is formed into mixture, described controls heating to be 450 DEG C~1050 DEG C, heating
Speed is 1~10 DEG C/min, fires 3h~24h.
The mixture is put into progress acid treatment in the hydrochloric acid solution of setting ratio and obtains titanyl matrix type ammonium ion sieve,
It by solid-to-liquid ratio is 1 that the setting ratio, which is,:50~1:100 ratio adds the water-bath under the conditions of 70 DEG C of 1mol/L hydrochloric acid solutions
2h, then pours out the hydrochloric acid solution, repeats the acid treatment flow three times.
The mixture is carried out before and after acid treatment step, cleaned the mixture to neutrality with deionized water
Matter.
Described titanyl matrix type ammonium ion sieve belongs to layer structure, and each layer of titanyl skeleton lattice sites can adsorb ammonium
Ion, while the site of interlayer can also adsorb ammonium ion.
Described titanyl matrix type ammonium ion sieve is circular regeneration material, the raw material that the circular regeneration is used for 0.1~
5mol L-1The mixed solution that is made of strong acid solution and water, the titanyl matrix type ammonium ion sieve and the mixed solution according to
10:1 ratio is stirred, and stirring 1h~5h completes the circular regeneration.
The embodiment of the present invention is selectively good it can be seen from the technical scheme that embodiments of the invention described above are provided, containing
There is special selectivity in ammonium ion surface water to ammonium ion, adsorbance is big, the adsorbance of this material is in 101.3mg/g, absorption
Amount exceedes existing ammonium sorbing material, and cyclicity is good, circular regeneration 10 times, and adsorbance does not substantially decay and keeps its selectivity.
The additional aspect of the present invention and advantage will be set forth in part in the description, and these will become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 synthesizes for a kind of ammonium ion sieve of preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention
Process chart；
Fig. 2 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to ammonium
The removal effect schematic diagram of ion and sodium ion two-component system；
Fig. 3 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to certainly
Each cation removal effect schematic diagram in the ammonium chloride solution that water is prepared；
Fig. 4 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to certainly
Each cation effect diagram is removed in each solion that water is prepared；
Fig. 5 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to reality
The removal effect schematic diagram of each ion of border water body.
Embodiment
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element or element with same or like function are represented to same or similar label eventually.Below by ginseng
The embodiment for examining accompanying drawing description is exemplary, is only used for explaining the present invention, and is not construed as limiting the claims.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singulative " one " used herein, " one
It is individual ", " described " and "the" may also comprise plural form.It is to be further understood that what is used in the specification of the present invention arranges
Diction " comprising " refer to there is the feature, integer, step, operation, element and/or component, but it is not excluded that in the presence of or addition
Other one or more features, integer, step, operation, element, component and/or their group.It should be understood that when we claim member
Part is " connected " or during " coupled " to another element, and it can be directly connected or coupled to other elements, or can also exist
Intermediary element.In addition, " connection " used herein or " coupling " can include wireless connection or coupling.Wording used herein
"and/or" includes one or more associated any cells for listing item and all combined.
Those skilled in the art of the present technique are appreciated that unless otherwise defined, all terms used herein (including technology art
Language and scientific terminology) with the general understanding identical meaning with the those of ordinary skill in art of the present invention.Should also
Understand, those terms defined in such as general dictionary, which should be understood that, to be had and the meaning in the context of prior art
The consistent meaning of justice, and unless defined as here, will not be explained with idealization or excessively formal implication.
For ease of the understanding to the embodiment of the present invention, done below in conjunction with accompanying drawing by taking several specific embodiments as an example further
Explanation, and each embodiment does not constitute the restriction to the embodiment of the present invention.
Fig. 1 synthesizes for a kind of ammonium ion sieve of preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention
Process chart；As shown in Figure 1：
A kind of preparation method of titanyl matrix type ammonium ion sieve, including raw material be：Nano titanium oxide or metatitanic acid, hydrogen
Potassium oxide；Characterized in that, the raw material is mixed to form mixed liquor according to setting ratio, the mixed liquor is controlled to rise
Temperature sintering forms mixture, naturally cools to after room temperature, and the mixture is put into the hydrochloric acid solution of setting ratio and carries out acid
Processing obtains titanyl matrix type ammonium ion sieve.
It is comprised the following steps that：
Nano titanium oxide or metatitanic acid are 0.5 according to mol ratio with potassium hydroxide:1~3:1 0.5~3h of mixed grinding
After (a little alcohol assisted milling is added in process of lapping), product is moved into corundum crucible, is placed in high temperature box furnace and controls
450 DEG C~1050 DEG C are warming up to, heating rate is 1~10 DEG C/min, fires 3h~24h, naturally cools to and production is taken out after room temperature
Product.
The said goods are cleaned with deionized water to neutrality, are then 1 by solid-to-liquid ratio:50~1:100 ratio is added
1mol/L hydrochloric acid solutions water-bath 2h under the conditions of 70 DEG C, then pours out liquid, repeats clear with deionized water after acid treatment three times
It is washed till neutral standby.
Take the material 0.1g after processing to be added in 100ml solution, investigate its selectivity to ammonium ion and its originally
Absorption property under water, actual water quality.
Fig. 2 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to ammonium
The removal effect schematic diagram of ion and sodium ion two-component system；As shown in Figure 2：
Above-mentioned titanyl matrix type ammonium ion sieve material clean is taken to neutrality, dry for standby.
Ammonium chloride, the sodium chloride mixed solution of equal substance withdrawl syndrome are prepared with ultra-pure water.
Take the titanyl matrix type ammonium ion sieve 0.1g after processing to be added in the above-mentioned mixed solutions of 100ml, stir at room temperature
2h, takes production water gaging ammonium ion and Na ion concentration.Three groups of parallel laboratory tests, Experiment Data Records are shown in Table 1.
It is apparent from by table 1 and Fig. 2, absorption of the titanyl matrix type ammonium ion sieve described in patent to ammonium ion and sodium ion has choosing
Selecting property is distinguished, and titanyl matrix type ammonium ion sieve is significantly larger than sodium ion to the adsorption capacity of ammonium ion, sodium ion is hardly inhaled
It is attached.
The ammonium ion of the titanyl matrix type ammonium ion sieve of table 1. and the selective experimental result of sodium ion
Fig. 3 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to certainly
Each cation removal effect schematic diagram in the ammonium chloride solution that water is prepared；As shown in Figure 3：
Above-mentioned titanyl matrix type ammonium ion sieve is taken to be washed with deionized water to neutrality, dry for standby.
The ammonium chloride solution prepared with running water, wherein ammonium concentration are 54ppm or so, take the titanyl skeleton after processing
Type ammonium ion sieve 0.1g is added in the above-mentioned mixed solutions of 100ml, and 2h is stirred at room temperature, takes production each ion concentration of water gaging.Two
Group parallel laboratory test, Experiment Data Records are shown in Table 2.
It is apparent from by table 2 and Fig. 3, the ammonium chloride solution system that synthesized titanyl matrix type ammonium ion sieve is prepared in running water
In sodium ion, calcium ion and magnesium ion are far longer than to the absorption of ammonium ion, have to metal cation well selectivity distinguish,
I.e. the titanyl matrix type ammonium ion sieve is hardly adsorbed for sodium ion, calcium ion and magnesium ion.
Each cation removal effect in the ammonium chloride solution that the titanyl matrix type ammonium ion sieve of table 2. is prepared to running water
Fig. 4 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to certainly
Each cation effect diagram is removed in each solion that water is prepared；As shown in Figure 4：
Above-mentioned titanyl matrix type ammonium ion sieve is taken to be washed to neutrality, dry for standby.The amount of equal material is prepared with ultra-pure water
Ammonium chloride, sodium chloride, potassium chloride, calcium chloride, the mixed solution of magnesium chloride of concentration.
Take the titanyl matrix type ammonium ion sieve 0.1g after processing to be added in the above-mentioned mixed solutions of 500ml, stir at room temperature
2h, takes the concentration of the production wherein various metal cations of water gaging.Experiment Data Records are shown in Table 3.
It is apparent from by table 3 and Fig. 4, synthesized titanyl matrix type ammonium ion sieve is in Na+、K+、Ca2+、Mg2+、NH4 +Exist simultaneously
Water body in, be Preferential adsorption to ammonium ion, its selectivity order is：NH4 +＞ K+＞ Ca2+＞ Na+＞ Mg2+。
Removal situation of the titanyl matrix type ammonium ion sieve of table 3. to several cation
Fig. 5 is a kind of ammonium ion sieve of the preparation method of titanyl matrix type ammonium ion sieve provided in an embodiment of the present invention to reality
The removal effect schematic diagram of each ion of border water body；As shown in Figure 5:
In order to investigate synthesized material to the removal effect of ammonium ion in actual water body, we take sanitary sewage to pass through ultrafiltration
Water is produced as the raw water of our titanyl matrix type ammonium ion sieves after film Ghana membrane filtration；Take above-mentioned titanyl matrix type ammonium ion
Sieve is washed to neutrality, dry for standby.
The titanyl matrix type ammonium ion sieve 0.1g after processing is taken to be added in the above-mentioned treated actual sewages of 500ml, room
The lower stirring 2h of temperature, takes the concentration of the production various cations of water gaging.Experiment Data Records are shown in Table 4.
Be apparent from by table 4 and Fig. 5, synthesized titanyl matrix type ammonium ion sieve when handling actual sewage to ammonium ion still
It is Preferential adsorption, the removal ability to ammonium ion is best, and its selectivity order is：NH4 +＞ K+＞ Mg2+＞ Ca2+＞ Na+.As can be seen here, under the actual water plastidome of complicated component, the suction of synthesized titanyl matrix type ammonium ion sieve to ammonium ion
Attached performance does not substantially decay compared with the water quality that pure water or running water are prepared.
Disposition of the titanyl matrix type ammonium ion sieve of table 4. to actual sewage
In order to investigate the cyclicity of synthesized titanyl matrix type ammonium ion sieve, we are repeatedly adsorbed and again to it
It is raw, the effect of ammonium ion is adsorbed after record regenerating to characterize the stability of material.Renovation process is 1molL-1Hydrochloric acid solution.
Experimental method is as follows：
(A) above-mentioned ammonium ion selective material is taken to be washed to neutrality, dry for standby.
(B) 0.1mol L are prepared with running water-1Ammonium chloride solution.
(C) take the titanyl matrix type ammonium ion sieve 0.1g after processing to be added in the above-mentioned mixed solutions of 100ml, stir at room temperature
2h is mixed, production water gaging ammonium concentration is taken.Use 1mol L every time-1The ratio of regeneration of hydrochloric acid, regenerated liquid and material is 10:1, regeneration
Time is 1h~5h.
(D) every time after regeneration according to the Mass Calculation liquid dosage of product, it is ensured that each rate of charge is 0.1%.Absorption
Time is constant, it is ensured that each adsorption time is 1h, and ammonia nitrogen concentration is 1000ppm.
Be apparent from by table 5, synthesized titanyl matrix type ammonium ion sieve regenerate 6 times after to the adsorption capacity decay of ammonium ion compared with
Small, only 0.1% or so, cycle performance is good, it is possible to achieve recycle.
The circularity test result of table 5.
The working mechanism of titanyl matrix type ammonium ion sieve is as follows：
Nano titanium oxide includes rutile-type, Detitanium-ore-type as a kind of regulatable material of polymorphic, common crystal formation
With three kinds of brookite type, wherein rutile titanium dioxide is most stable of crystal formation., can be by introducing by certain condition
Trace ion, heating etc. regulation and control titanium dioxide obtain different crystal formations, the material of different crystalline lattice structure.This patent mainly passes through hydrogen
After potassium oxide is mixed according to a certain percentage with sodium rice titanium dioxide, control Elevated Temperature Conditions are fired into one kind and possess nanometer laminated structure
New titanyl matrix type ammonium ion sieve, due to potassium ion radiusAmmonium ion radiusSize closely, and
The ionic radius of sodium ion isDo not met with the site cavity radius of titanyl matrix type ammonium ion sieve, on site cavity
It can not stablize and adsorb, be easily separated from site, therefore the titanyl matrix type ammonium ion sieve is very poor for the adsorption capacity of sodium ion；It is right
Calcium ion and magnesium ion in water body, due to calcium ion, magnesium ion hydration radius is very big, and hydration free energy is minimum, and normal
In the case of temperature, calcium ion and magnesium ion is more difficult loses with reference to water among entry site hole, even if in addition, calcium ion and magnesium from
Son can remove bound water molecule and entry site hole, but be due to calcium ion and magnesium ion ionic radius it is too small, in place
It is unstable on point hole, site is easily separated from, so, the titanyl matrix type ammonium ion sieve is to calcium ion and the energy of adsorption of magnesium ion
Power is very poor, and the adsorption capacity for ammonium ion and selectivity are very well.
In summary, beneficial effects of the present invention are as follows：
(1) selectivity is good, there is special selectivity to ammonium ion in surface water containing ammonium ion；
(2) adsorbance is big, and the adsorbance of this material is in 101.3mg/g, and adsorbance exceedes the ammonium sorbing material reported；
(3) cyclicity is good, and the material circulation in the present invention regenerates 10 times, and adsorbance does not substantially decay and keeps it to select
Property.
One of ordinary skill in the art will appreciate that：Accompanying drawing be module in the schematic diagram of one embodiment, accompanying drawing or
Flow is not necessarily implemented necessary to the present invention.
Each embodiment in this specification is described by the way of progressive, identical similar portion between each embodiment
Divide mutually referring to what each embodiment was stressed is the difference with other embodiment.Especially for device or
For system embodiment, because it is substantially similar to embodiment of the method, so describing fairly simple, related part is referring to method
The part explanation of embodiment.Apparatus and system embodiment described above is only schematical, wherein the conduct
The unit that separating component illustrates can be or may not be it is physically separate, the part shown as unit can be or
Person may not be physical location, you can with positioned at a place, or can also be distributed on multiple NEs.Can root
Some or all of module therein is factually selected to realize the purpose of this embodiment scheme the need for border.Ordinary skill
Personnel are without creative efforts, you can to understand and implement.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
It is defined.
Claims (7)
1. a kind of preparation method of titanyl matrix type ammonium ion sieve, including raw material be：Nano titanium oxide or metatitanic acid, hydrogen-oxygen
Change potassium；Characterized in that, the raw material is mixed to form mixed liquor according to setting ratio, the mixed liquor is controlled to heat up
Sintering forms mixture, naturally cools to after room temperature, and the mixture is put into the hydrochloric acid solution of setting ratio and carried out at acid
Reason obtains titanyl matrix type ammonium ion sieve.
2. according to the method described in claim 1, it is characterised in that the nano titanium oxide or metatitanic acid and the hydroxide
Potassium is 0.5 according to mol ratio:1~3:1 mixed grinding 0.5h~3h.
3. according to the method described in claim 1, it is characterised in that mixed liquor control heating sintering is formed into mixture,
Described controls heating to be 450 DEG C~1050 DEG C, and heating rate is 1~10 DEG C/min, fires 3h~24h.
4. according to the method described in claim 1, it is characterised in that the mixture is put into the hydrochloric acid solution of setting ratio
Carry out acid treatment and obtain titanyl matrix type ammonium ion sieve, it by solid-to-liquid ratio is 1 that the setting ratio, which is,:50~1:100 ratio adds
Enter 1mol/L hydrochloric acid solutions water-bath 2h under the conditions of 70 DEG C, then pour out the hydrochloric acid solution, repeat the acid treatment flow three
It is secondary.
5. according to the method described in claim 1, it is characterised in that the mixture is carried out before and after acid treatment step, used
Deionized water cleans the mixture to neutral property.
6. according to the method described in claim 1, it is characterised in that described titanyl matrix type ammonium ion sieve belongs to stratiform knot
Structure, each layer of titanyl skeleton lattice sites can adsorb ammonium ion, while the site of interlayer can also adsorb ammonium ion.
7. according to the method described in claim 1, it is characterised in that described titanyl matrix type ammonium ion sieve is circular regeneration thing
Matter, the raw material that the circular regeneration is used is 0.1~5mol L-1The mixed solution that is made of strong acid solution and water, the titanyl
Matrix type ammonium ion sieve is with the mixed solution according to 10:1 ratio is stirred, and stirring 1h~5h completes the circulation again
It is raw.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479686A (en) * | 2018-03-29 | 2018-09-04 | 北京碧水源膜科技有限公司 | Na4Ti5O12Preparation method and its application process in sewage takes off ammonium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824386A (en) * | 2006-01-27 | 2006-08-30 | 天津大学 | Ammonium ion sieve, its preparation method and application |
| CN101157480A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Manganese bioxide ionic sieve |
| CN101157476A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Titania ionic sieve |
| CN101829608A (en) * | 2010-06-11 | 2010-09-15 | 天津大学 | Preparation method and application of ammonium ion exchange material |
| CN106220285A (en) * | 2016-08-10 | 2016-12-14 | 云南省轻工业科学研究院 | The method producing Liquid Fertilizer from alcohol waste mash |
| CN106268980A (en) * | 2016-08-30 | 2017-01-04 | 北京碧水源膜科技有限公司 | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve |
-
2017
- 2017-04-19 CN CN201710255361.4A patent/CN106975438A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1824386A (en) * | 2006-01-27 | 2006-08-30 | 天津大学 | Ammonium ion sieve, its preparation method and application |
| CN101157480A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Manganese bioxide ionic sieve |
| CN101157476A (en) * | 2007-09-18 | 2008-04-09 | 华东理工大学 | Titania ionic sieve |
| CN101829608A (en) * | 2010-06-11 | 2010-09-15 | 天津大学 | Preparation method and application of ammonium ion exchange material |
| CN106220285A (en) * | 2016-08-10 | 2016-12-14 | 云南省轻工业科学研究院 | The method producing Liquid Fertilizer from alcohol waste mash |
| CN106268980A (en) * | 2016-08-30 | 2017-01-04 | 北京碧水源膜科技有限公司 | A kind of NH in selectivity exchange water body4+fe3+the preparation method of doping ammonium ion sieve |
Non-Patent Citations (1)
| Title |
|---|
| 闫会征等: "新型钾离子筛K+-NH4+离子交换平衡研究", 《盐业与化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479686A (en) * | 2018-03-29 | 2018-09-04 | 北京碧水源膜科技有限公司 | Na4Ti5O12Preparation method and its application process in sewage takes off ammonium |
| CN108479686B (en) * | 2018-03-29 | 2021-02-19 | 北京碧水源膜科技有限公司 | Na4Ti5O12Preparation method and application method thereof in sewage deammoniation |
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