CN110465277A - A kind of ammonia molecular imprinting adsorbing agent and its preparation for the separation of sludge aerobic compost mixed gas and Ammonia recovery - Google Patents
A kind of ammonia molecular imprinting adsorbing agent and its preparation for the separation of sludge aerobic compost mixed gas and Ammonia recovery Download PDFInfo
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- CN110465277A CN110465277A CN201910840573.8A CN201910840573A CN110465277A CN 110465277 A CN110465277 A CN 110465277A CN 201910840573 A CN201910840573 A CN 201910840573A CN 110465277 A CN110465277 A CN 110465277A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present invention provides a kind of ammonia molecular imprinting adsorbing agent and its preparation for the separation of sludge aerobic compost mixed gas and Ammonia recovery.The preparation includes: that ammonium hydroxide and acrylic compounds function monomer are added in solvent, is mixed；Azodiisobutyronitrile initiator and ethylene glycol dimethacrylate crosslinking agent are added into system, mixes；Raolical polymerizable collects deposit；It is cleaned by ultrasonic deposit, to remove removing template and reaction dissolvent；Deposit after elution is transferred in the sulfuric acid solution that pH is 0.5, sealing, lower reaction is stirred, so that the ester functional groups in partial cross-linked dose hydrolyze to form carboxyl functional group；Deionized water rinse, vacuum drying to get.The ammonia in mixed gas that the adsorbent that the present invention obtains is generated for sludge composting has a good adsorptive selectivity, and the adsorption capacity of methyl sulfide and methyl disulfide is low, it can be achieved that ammonia and methyl sulfide, methyl disulfide efficiently separate.
Description
Technical field
The invention belongs to gas separations, and in particular to one kind is for the separation of sludge aerobic compost mixed gas and ammonia
The ammonia molecular imprinting adsorbing agent of recycling and its preparation.
Background technique
Aerobic compost is a kind of to realize sludge reduction, innoxious and recycling important process mode.However, in sludge
A large amount of foul gas is generated in aerobic composting process, main component includes ammonia, methyl sulfide and methyl disulfide.It is supervised through scene
Discovery is surveyed, sludge discharge amount of ammonia in aerobic composting process is up to the dry mud of 4.35~10.95g/kg, methyl sulfide and diformazan two
The discharge amount of sulphur is respectively the dry mud of 0.071~0.22 and 0.11~0.25g/kg.If not taking effective treatment measures, directly arrange
It puts pollution surrounding air, be detrimental to health, the serious development for restricting aerobic compost industry.
The main method of foul gas processing has bioanalysis, absorption process, absorption method.The advantages of bioanalysis be it is low in cost,
The disadvantage is that target substance can not be separated and recovered.There are many patent in relation to Biochemical method foul gas, such as patent
201410460781.2 the apparatus and method for of a kind of synchronous removal foul gas and microbial aerosol is reported, good water solubility
Foul gas is removed in wet scrubbing area, and remaining gas is broken down into innocuous substance in biofiltration area.Patent
201310177593.4 a kind of apparatus and method of activated carbon combined method processing foul gas of biofiltration-are reported, it is most of
By the microbial degradation of biofiltration unit, the part not being degraded is adsorbed foul gas (including ammonia) in activated charcoal unit
Removal.The advantages of absorption process is that have high removal rate to the foul gas of good water solubility, the disadvantage is that non-aqueous in foul gas
The component assimilation effect of property is very poor.There are many patent of related absorption process processing foul gas, as patent 201110105217.5 is reported
A kind of ammonia absorption device in road, the device include gas-liquid separation buffer, the cooling absorption tower of the first combined type etc., and ammonia passing through
It is removed after crossing multistage absorption processing.
Absorption method recycles after can realizing adsorbing separation to the substance for having recovery value.Ammonia can -33 DEG C or 700~
800kpa is easily converted to liquefied ammonia, and liquefied ammonia can be used for industrial chemicals and refrigerant or good hydrogen storage fuel.Therefore, sludge is good
The ammonia of maximum discharge amount has very high recovery value in oxygen composting process.It can be closed by the mixed gas during sludge composting
It collects, then after through the adsorbent highly selective to ammonia and methyl sulfide, methyl disulfide, ammonia returns after being adsorbed separation
It receives.
Patent 201610277915.6 reports a kind of application of microballoon graft starch in ammonia gas absorption, anti-by polymerizeing
Carboxylic acid quasi polymer should be grafted on starch, the ammonia generated when for absorbing cigarette burning.But the patent only tests
Pure gas ammonia gas absorption does not study the separation of ammonia in mixed component, such as methyl sulfide and methyl disulfide, and separating effect is not
Know；And tested in the Dynamic Adsorption of ammonia, whether test experiments group extends compared to the time of break-through of blank group, the number provided
According to the adsorbance that can not calculate ammonia；Simulation absorption ammonia research is not carried out for the condition during sludge aerobic compost,
Absorption stability is unknown.
Patent 201410422466.0 reports a kind of active carbon that effectively improves to the modification side of micro-ammonia absorption property
Method can be used for removing the ammonia in room air by the way that active carbon to be successively modified through pernitric acid, citric acid and butane tetracarboxylic acid
Gas, the ammonia given out such as indoor hardware fitting.Patent 200810016263.6 report a kind of purificant for adsorbing ammonia gas and its
Preparation method is modified, the removal of ammonia suitable for room air by the way that the carriers such as active carbon or aluminium oxide are carried out acid.But
The above patent only tests the variation of pure gas ammonia concentration before and after by adsorbent, and the data provided can not calculate ammonia
Adsorbance；The separation of ammonia in mixed component is not studied, separating effect is unknown；Not for during sludge aerobic compost
Condition carry out simulation absorption ammonia research, absorption stability is unknown.
Patent 201810339275.6 reports a kind of preparation of foam metal/metal organic framework composite material, passes through
Benzenetricarboxylic acid is loaded into formation MOF composite material on foam copper skeleton, can be used for adsorbing the ammonia in surrounding air.But it should
Patent only has studied single ammonia Dynamic Adsorption, does not study the separation of ammonia in mixed component, and separating effect is unknown；And in ammonia
The quality that adsorbent is not provided in the Dynamic Adsorption experiment of gas, can not calculate the dynamic adsorbance of ammonia；Not for dirt
Condition in mud aerobic composting process carries out simulation absorption ammonia research, and absorption stability is unknown.
Patent 201210238838.5 reports a kind of mixture solid sample block and its system containing ceramic fibre and silica solution
Preparation Method fills it into closed appearance by the way that anhydrous magnesium chloride, ceramic fibre and industrial silicon etc. to be stirred by a certain percentage
Porosu solid sample block is made after stirring drying in device.Patent 201210238802.7 report a kind of magnesium salts storage ammonia mixture and
Preparation, by the way that the materials such as the powder, molecular sieve, clay of chlorination magnesium salts are filled into tank body, is made porosu solid block.It is above special
Benefit can be applied to the SCR aftertreatment system and fuel cell system of vehicle exhaust.But the above patent only has studied single ammonia
The Static Adsorption of gas under high pressure, can not obtain the dynamic adsorbance under normal pressure；The separation of ammonia in mixed component is not studied,
Separating effect is unknown；Simulation absorption ammonia research, absorption stability are not carried out for the condition during sludge aerobic compost
It is unknown.
Patent 201310013470.7 reports a kind of ammonia removal material preparation method, should be except ammonia agent is by NaY molecular sieve, five water
The composition such as copper sulphate, winestone acid binder, is suitble to the removal of the ammonias such as industrial tail gas, sewage treatment plant.But should except ammonia agent only into
Pure gas ammonia gas absorption is gone, and dynamic adsorbance is lower (1.0~2.35mmol/cc)；Ammonia in mixed component is not studied
The separation of gas, separating effect are unknown；Simulation absorption ammonia research is not carried out for the condition during sludge aerobic compost, is inhaled
Attached stability is unknown, is not suitable for applying to the separation and recovery of sludge aerobic compost ammonia.
Patent 201680071061.4 reports a kind of preparation method except ammonia agent, and the material is by silicon phosphate, sesbania powder, two
The composition such as silica, to different temperature, flow and multiple gases component (SO2、N2O、NH3, humidity) to carry out ammonia gas absorption real
It tests, ammonia dynamic adsorbance is 0.99~1.64mmol/g, is suitable for that flue gas desulphurization is out of stock and continuous flue gas monitoring system
Ammonia processing before system.But it should be lower except the dynamic adsorbance of ammonia agent；The separation of ammonia in mixed component, separation effect are not studied
Fruit is unknown；Simulation absorption ammonia research is not carried out for the condition during sludge aerobic compost, absorption stability is unknown, no
It is suitable for the separation and recovery for applying to sludge aerobic compost ammonia.
Patent 201680071061.4 reports a kind of preparation method of ammonia removal material, and the material is by a variety of different crystal knots
The zeolite of structure forms, and suitable for remove remaining ammonia after the hydrogen energy source by liquefied ammonia conversion that fuel cell uses, ammonia is dynamically
Adsorbance is 2.24~3.76mmol/g.But it should be lower except the dynamic adsorbance of ammonia agent；Ammonia in mixed component is not studied
Separation, separating effect are unknown；Simulation absorption ammonia research is not carried out for the condition during sludge aerobic compost, absorption is steady
It is qualitative unknown, it is not suitable for applying to the separation and recovery of sludge aerobic compost ammonia.
A kind of method of the absorption and separation ammonia from ammonia-contaminated gas of patent 201611031050.1, with hydridization eutectic solvent
(Acidic Compounds, salt compounds and additive) is used as absorbent, and absorption is contacted with ammonia-contaminated gas and is obtained containing ammonia exhaust gas
Absorbing liquid, absorbing liquid parses isolated ammonia again, is suitable for the high concentrations ammonia-contaminated gas such as synthetic ammonia installation, ammonia refrigerating installation
Recycling.Test adsorbed gas component is hydrogen, nitrogen, ammonia, argon gas, methane, and ammonia concentration is 2.5%~72.3%.But
It is patent Static Adsorption under high pressure, the dynamic adsorbance of ammonia can not be obtained；Not for during sludge aerobic compost
Condition carry out simulation absorption ammonia research, absorption stability is unknown.
Patent 201510158450.8 reports a kind of new and effective reversible ionic type ammonia absorbent, is by pyridine or miaow
The Lewis acidic ionic liquid of the anion composition of azoles and its derivative cation and the cobalt ions containing divalent metal, is suitable for urea
Ammonia in the tail gas such as emission, the coke-stove gas of granulation tower absorbs.It is that gas flow is that the patent, which adsorbs test condition,
140ml/min adsorbs pure gas ammonia at multiple temperature and multiple pressure, ammonia gas absorption amount be 0.88~
11.64mmol/g.But the patent does not study the separation of ammonia in mixed component, separating effect is unknown；It is not directed to sludge
Condition in aerobic composting process carries out simulation absorption ammonia research, and absorption stability is unknown.
All in all, according to it has been reported that ammonia gas absorption agent, for mixed gas point during sludge aerobic compost
Be designed, have the following problems from Ammonia recovery purpose: the dynamic adsorbance of ammonia is unknown or lower, ammonia in mixed component
The adsorbing separation effect of gas is unknown, and the absorption stability of different condition is unknown during sludge aerobic compost.Therefore, it needs to send out
A kind of bright material suitable for mixed gas separation and Ammonia recovery during sludge aerobic compost.
Summary of the invention
The purpose of the present invention is to solve defect of the existing technology, provide a kind of ammonia molecular imprinting adsorbing agent and
It is prepared, and ammonia gas absorption separates during being applied to sludge aerobic compost, which is not only able to achieve ammonia in mixed gas
In efficiently separate, and have higher adsorbance to ammonia Dynamic Adsorption, also there is good stabilization in simulated composting environment
Property.
Ammonia molecular imprinting adsorbing agent provided by the present invention is prepared by a method comprising the following steps to obtain:
1) ammonium hydroxide (template) and acrylic compounds function monomer are added in solvent, are mixed；
2) azodiisobutyronitrile initiator and ethylene glycol dimethacrylate crosslinking are added into system obtained by step 1)
Agent (EGDMA) mixes；
3) make system obtained by step 2) carry out Raolical polymerizable, collect deposit；
4) it is cleaned by ultrasonic step 3) gained sediment matter, the sediment to remove removing template and reaction dissolvent, after being eluted
Matter；
5) deposit after elution is transferred in the sulfuric acid solution that pH is 0.5, sealing, lower reaction is stirred, so that portion
The ester functional groups in crosslinking agent are divided to hydrolyze to form carboxyl functional group；
6) by step 5) products therefrom be dried in vacuo to get.
In above method step 1), the acrylic compounds function monomer concretely methacrylic acid；
The solvent concretely toluene.
The molar ratio of ammonia and acrylic compounds function monomer in the ammonium hydroxide can be 1:2~1:4；
The molar ratio of the function monomer and ethylene glycol dimethacrylate crosslinking agent (EGDMA) can be 1:2~1:5；
The quality of polymerized monomer and the volume ratio of solvent can are as follows: 2.5~10mg:100ml, it is single that the quality of initiator accounts for polymerization
The 1%~9% of weight；
Wherein, the quality of the polymerized monomer is the gross mass of function monomer and crosslinking agent；
In above method step 3), the Raolical polymerizable carries out under inert gas protection, the inert gas
Concretely nitrogen；
The Raolical polymerizable carries out in 50~70 DEG C of water-bath, and the time of the Raolical polymerizable can
It is 10-18 hours, concretely 12 hours；
In above method step 4), deposit is repeatedly rinsed using deionized water first, then ultrasound is clear in water again
0.25-1 hours are washed, concretely half an hour, until there is no ammonium ion detections in filtrate.
In above method step 5), the time of the reaction can be 10-14 hours, concretely 12 hours.
In above method step 6), before being dried in vacuo to product, it may also include with deionized water rinsing step
5) operation of products therefrom filters until eluent pH to 5~7 or so, obtained solid is put into vacuum oven, at 80 DEG C
Lower vacuum drying 12 hours, i.e. acquisition ammonia molecular imprinting adsorbing agent, are placed in drier stand-by.
Ammonia molecular imprinting adsorbing agent prepared by the above method also belongs to protection scope of the present invention.
Above-mentioned ammonia molecular imprinting adsorbing agent answering in the separation and recycling of ammonia in sludge aerobic compost mixed gas
With also belonging to protection scope of the present invention.
The present invention has the following beneficial effects: compared with prior art
(1) ammonia in the mixed gas that the adsorbent that the present invention obtains is generated for sludge composting has good absorption to select
The adsorption capacity of selecting property, methyl sulfide and methyl disulfide is low, it can be achieved that ammonia and methyl sulfide, methyl disulfide efficiently separate；
(2) the obtained adsorbent of the present invention is adsorbed in normal temperature and pressure, and adsorption conditions are mild, different flow, concentration,
Temperature and humidity condition, still keeps higher adsorbance to ammonia, and absorption property is stablized；
(3) raw material needed for prepared by this method is easy to get, and preparation condition is simple, is not necessarily to high temperature and pressure, industry easy to accomplish
Change.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the ammonia molecular imprinting adsorbing agent that the embodiment of the present invention 1 is prepared.Wherein, left figure
2000 times of amplification, right figure amplify 8000 times.
Fig. 2 is the schematic diagram of the Dynamic gas-mixing and adsorption devices used in the embodiment of the present invention 2.
Specific embodiment
The present invention will be described below by way of specific embodiments, but the present invention is not limited thereto.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
The preparation of embodiment 1, ammonia molecular imprinting adsorbing agent
48.66 μ l ammonium hydroxide and 219.84 μ l methacrylic acid function monomers are added to three mouthfuls of burnings equipped with 60ml toluene
Bottle, 10min is pre-mixed under the auxiliary of magnetic stirring apparatus, then be added 1.22ml ethylene glycol dimethacrylate crosslinking agent and
10mg azodiisobutyronitrile initiator, stirs and evenly mixs.After candidate agent mixes, nitrogen cylinder is opened, nitrogen is passed through three-necked flask, arranged
Gas 10min.By continuous heating progress free radical polymerization in 12 hours is anti-under 60 DEG C of water-baths after the three-necked flask sealing for draining air
It answers.To after the reaction was completed, remove suspension, deposit, ultrasonic half an hour, until in filtrate not are repeatedly rinsed using deionized water
There is ammonium ion detection (using the absorption property test method in embodiment 2, to measure the ammonia gas absorption of gained sediment matter again
Amount is that (gas flow 200ml/min, temperature are 20 DEG C, ammonia concentration 100ppm to 0.42mmol/g, and relative humidity is
0%).Deposit is added to the sulfuric acid solution (200ml) that pH is 0.5 to stir and evenly mix 12 hours.Then it is rushed with deionized water
Being washed till filtrate is to be filtered after pH is 5~7.It is finally that deposit is 12 hours dry in 80 DEG C of vacuum oven, it obtains
Ammonia molecular imprinting adsorbing agent, it is stand-by to be placed in drier.
Fig. 1 is the scanning electron microscope (SEM) photograph for the ammonia molecular imprinting adsorbing agent being prepared.
Embodiment 2, the test of ammonia molecular imprinting adsorbing agent absorption property
(1) the ammonia molecular imprinting adsorbing agent 0.2g that Example 1 prepares is placed on the absorption of Dynamic gas-mixing and adsorption devices
Column carries out the experiment of ammonia Dynamic Adsorption (Dynamic gas-mixing and adsorption devices schematic diagram is as shown in Figure 2), and adsorption conditions and ammonia gas absorption amount are shown in Table
1。
(2) maximum emission of the ammonia and methyl sulfide, methyl disulfide that are arrived using sludge aerobic compost field monitoring is than equal
About 10:1:1 is the ratio of mixed gas inlet gas concentration, carries out the selective absorption test of ammonia, ammonia is to methyl sulfide and two
The selective factor B (ammonia gas absorption amount/methyl sulfide or methyl disulfide adsorbance) of two sulphur of first is shown in Table 1.
Ammonia molecularly imprinted polymer, which passes through ammonia/methyl sulfide/methyl disulfide adsorbance, draws breakthrough curve, by counting
The mode of calculation obtains.By taking ammonia as an example, fixed bed goes out under the different time points measured in an experiment according to ammonia concentration analyzer
Mouthful ammonia concentration, accumulated with Origin85 Software on Drawing adsorption curve figure corresponding with polymer material, and to adsorption curve
Point, which is the amount of the ammonia overflowed from fixed bed exit.In experiment, ammonia molecularly imprinted polymer is to ammonia
Adsorbance m (mmol) can be calculated by formula (1):
In formula, t (min) --- adsorption time；
C0(mg/m3) --- the inlet gas concentration of gas；
vOutlet(mg/m3) --- the amount for the ammonia that fixed bed exit is overflowed, the i.e. integrated value of adsorption curve；
ν (ml/min) --- charge flow rate.
Ammonia molecularly imprinted polymer is to ammonia/methyl sulfide/methyl disulfide mAdsorbance(mmol/g material) can be by formula (2)
It is calculated:
In formula, m (mmol) --- adsorbance of the polymer to gas in experiment；
mMaterial(g) --- the quality for the ammonia molecularly imprinted polymer being added in adsorption column.
(3) simulate sludge aerobic compost field condition, that is, simulate the different ammonia concentration in compost scene, temperature, humidity,
The dynamic adsorbance that ammonia is determined under flow, the results are shown in Table 2.
The ammonia gas absorption amount of 1 ammonia molecular imprinting adsorbing agent of table and selectivity to methyl sulfide and methyl disulfide
| Flow (ml/min) | 200 |
| Ammonia concentration (ppm) | 100 |
| Temperature (DEG C) | 20 |
| Relative humidity (%) | 0 |
| Ammonia gas absorption amount (mmol/g) | 7.54 |
| Ammonia selectivity factor (methyl sulfide) | 256 |
| Ammonia selectivity factor (methyl disulfide) | 352 |
The ammonia dynamic adsorbance of molecular imprinting adsorbing agent under 2 different condition of table
Comparative example,
Absorption is prepared using acrylamide function monomer as polymerized monomer (other conditions are constant) referring to the method for embodiment 1
The ammonia gas absorption amount of agent, gained sorbent material (before unused acid solution impregnates) is 0.28mmol/g；Wherein, condition are as follows: gas
Flow is 200ml/min, and temperature is 20 DEG C, and ammonia inlet gas concentration is 100ppm, relative humidity 0%.
Embodiment 3
The ammonia gas absorption amount that the product that (step 5) obtains is hydrolyzed in different acid-base property conditions is investigated, as shown in table 3:
Table 3
| The adsorbent prepared under different pH solution | Adsorbance (mmol/g) |
| PH=13.5 aqueous slkali | 0.03 |
| PH=12 aqueous slkali | 0.29 |
| PH=2 acid solution | 0.71 |
| PH=0.5 acid solution | 7.54 |
| It does not hydrolyze | 0.42 |
Wherein, the testing conditions of adsorbance are as follows: gas flow 200ml/min, temperature are 20 DEG C, and ammonia inlet gas concentration is
100ppm, relative humidity 0%.
As shown in Table 3: being hydrolyzed under condition of different pH, the ammonia gas absorption amount for the adsorbent being prepared differs greatly, in pH
It therefore, is selected for the ammonia gas absorption amount highest for hydrolyzing the adsorbent being prepared in 0.5 acid solution up to 7.54mmol/g
Hydrolysis prepares ammonia molecular imprinting adsorbing agent under this pH value condition.
Embodiment 4
Influence of the solvent of Raolical polymerizable to adsorbent absorption property is investigated, when use ethyl alcohol is carried out instead of toluene
The ammonia gas absorption amount for the product (before unused acid solution impregnates) being prepared after Raolical polymerizable is 0.088mmol/g；And
The ammonia for the product (before unused acid solution impregnates) being prepared after replacing toluene progress Raolical polymerizable with chloroform
Adsorbance is 0.082mmol/g；Therefore select toluene for the solvent of Raolical polymerizable.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features,
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. a kind of method for preparing ammonia molecular imprinting adsorbing agent, includes the following steps:
1) ammonium hydroxide and acrylic compounds function monomer are added in solvent, are mixed；
2) azodiisobutyronitrile initiator and ethylene glycol dimethacrylate crosslinking agent are added into system obtained by step 1), mixes
It is even；
3) make system obtained by step 2) carry out Raolical polymerizable, collect deposit；
4) it is cleaned by ultrasonic step 3) gained sediment matter, the deposit to remove removing template and reaction dissolvent, after being eluted；
5) deposit after elution is transferred in the sulfuric acid solution that pH is 0.5, sealing, lower reaction is stirred, so that part is handed over
Ester functional groups in connection agent hydrolyze to form carboxyl functional group；
6) by step 5) products therefrom be dried in vacuo to get.
2. according to the method described in claim 1, it is characterized by: the acrylic compounds function monomer is methyl in step 1)
Acrylic acid；
The solvent is toluene；
The molar ratio of ammonia and acrylic compounds function monomer in the ammonium hydroxide is 1:2~1:4.
3. method according to claim 1 or 2, it is characterised in that: the function monomer and ethyleneglycol dimethacrylate
The molar ratio of ester crosslinking agent is 1:2~1:5；
The quality of polymerized monomer and the volume ratio of solvent are as follows: 2.5~10mg:100ml, the quality of initiator account for polymerized monomer quality
1%~9%；
Wherein, the quality of the polymerized monomer is the gross mass of function monomer and crosslinking agent.
4. method according to any one of claim 1-3, it is characterised in that: in institute's step 3), the free radical polymerization
Reaction carries out under inert gas protection, the inert gas concretely nitrogen；
The Raolical polymerizable carries out in 50~70 DEG C of water-bath, and the time of the Raolical polymerizable is 10-
18 hours.
5. method according to any of claims 1-4, it is characterised in that: in step 5), the time of the reaction is
10-14 hours.
6. method according to any one of claims 1-5, it is characterised in that: in step 6), carrying out vacuum to product
Further including with deionized water rinsing step 5 before drying) operation of products therefrom takes out until eluent pH to 5~7 or so
Filter, is put into vacuum oven for obtained solid, and 12 hours, i.e. acquisition ammonia molecular imprinting adsorbing agent are dried in vacuo at 80 DEG C,
It is placed in drier stand-by.
7. the ammonia molecular imprinting adsorbing agent that method of any of claims 1-6 is prepared.
8. ammonia molecular imprinting adsorbing agent as claimed in claim 7 in sludge aerobic compost mixed gas the separation of ammonia and return
Application in receipts.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083255A (en) * | 2021-04-12 | 2021-07-09 | 浙江工业大学 | High-efficiency ammonia gas adsorption separating agent suitable for sludge anaerobic digestion of biogas |
| CN114471074A (en) * | 2022-02-22 | 2022-05-13 | 华侨大学 | Application of macromolecule-metal complex in reversible ammonia gas trapping |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050189291A1 (en) * | 1999-11-02 | 2005-09-01 | Mip Technologies Ab | Porous, molecularly imprinted polymer and a process for the preparation thereof |
| CN102698721A (en) * | 2012-06-04 | 2012-10-03 | 江苏大学 | Preparation method for adsorbent for separating salicylic acid surface imprint from waste water |
| CN104072692A (en) * | 2014-07-03 | 2014-10-01 | 江苏大学 | Method for preparing magnetic/core-shell molecularly imprinted adsorbent employing miniemulsion polymerization |
| CN104725556A (en) * | 2015-04-08 | 2015-06-24 | 福州大学 | PH-sensitive glucose selective adsorbent and preparation method thereof |
| CN105944704A (en) * | 2016-07-15 | 2016-09-21 | 华北电力大学（保定） | Adsorbent for separating NO in smoke and application thereof |
-
2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050189291A1 (en) * | 1999-11-02 | 2005-09-01 | Mip Technologies Ab | Porous, molecularly imprinted polymer and a process for the preparation thereof |
| CN102698721A (en) * | 2012-06-04 | 2012-10-03 | 江苏大学 | Preparation method for adsorbent for separating salicylic acid surface imprint from waste water |
| CN104072692A (en) * | 2014-07-03 | 2014-10-01 | 江苏大学 | Method for preparing magnetic/core-shell molecularly imprinted adsorbent employing miniemulsion polymerization |
| CN104725556A (en) * | 2015-04-08 | 2015-06-24 | 福州大学 | PH-sensitive glucose selective adsorbent and preparation method thereof |
| CN105944704A (en) * | 2016-07-15 | 2016-09-21 | 华北电力大学（保定） | Adsorbent for separating NO in smoke and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIU FENGLEI ET AL: "Preparation and characterization of molecularly imprinted solid amine adsorbent for CO2 adsorption", 《NEW JOURNAL OF CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083255A (en) * | 2021-04-12 | 2021-07-09 | 浙江工业大学 | High-efficiency ammonia gas adsorption separating agent suitable for sludge anaerobic digestion of biogas |
| CN113083255B (en) * | 2021-04-12 | 2022-08-23 | 浙江工业大学 | High-efficiency ammonia gas adsorption separating agent suitable for sludge anaerobic digestion of biogas |
| CN114471074A (en) * | 2022-02-22 | 2022-05-13 | 华侨大学 | Application of macromolecule-metal complex in reversible ammonia gas trapping |
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| CN110465277B (en) | 2022-06-21 |
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