CN103877938A - Preparation method of modified biogas residue ammonium-nitrogen adsorption agent - Google Patents
Preparation method of modified biogas residue ammonium-nitrogen adsorption agent Download PDFInfo
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- CN103877938A CN103877938A CN201410153239.2A CN201410153239A CN103877938A CN 103877938 A CN103877938 A CN 103877938A CN 201410153239 A CN201410153239 A CN 201410153239A CN 103877938 A CN103877938 A CN 103877938A
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Abstract
The invention provides a preparation method of a modified biogas residue ammonium-nitrogen adsorption agent, and relates to the ammonium-nitrogen adsorption agent. The preparation method comprises the following steps of (1) crushing the dehydrated and dry biogas residue, and screening the crushed biogas residue by a sieve to obtain the biogas residue particles; (2) mixing the biogas residue particles with potassium hydroxide solution, standing the mixed solution, and removing and drying a reaction product of a supernatant; and (3) heating and pyrolyzing the dried product in a nitrogen atmosphere, cooling the product, washing the product by utilizing hydrochloric acid, washing the product by utilizing hot deionized water to be neutral, drying the product, and crushing, grinding and filtering the dried product to obtain the modified biogas residue ammonium-nitrogen adsorption agent. The biogas residue is modified to be made into the adsorption agent with a coarse surface and a mesoporous structure, and the prepared adsorption agent is used for adsorbing ammonium and nitrogen in biogas slurry. The prepared modified biogas residue ammonium-nitrogen adsorption agent has the advantages of low cost, excellent adsorption performance and the like.
Description
Technical field
The present invention relates to ammonia nitrogen adsorbent, especially relate to the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent.
Background technology
Ammonia nitrogen is one of important polluter of body eutrophication and environmental pollution, and the product nitrate and the nitrite that enter nitrification in water body have very large harm to drinking water.Fish are more responsive to ammonia nitrogen in water, and ammonia nitrogen is too high makes aquatile for a long time in stress situation, and in water, balance severe patient is even dead.At present, the method for ammonia nitrogen waste water processing has blow-off method, chemical precipitation method, membrane absorption method, advanced oxidation processes, ion-exchange, biological denitrificaion method and absorption method.Wherein absorption method is owing to having the advantages such as the secondary pollution of not producing, recyclable, low energy consumption, and enjoys attention.In recent years, China's biogas engineering is fast-developing on a large scale, and disposing residue biogas residue and biogas liquid becomes thorny problem.Every year have a large amount of natural pond slags to be landfilled or burning disposal, not only influence ecological environment, and waste resource, turn waste into wealth it if these discarded objects are carried out to recycling, will be significant to human health and ecological environment.As far back as the nineties in 20th century, Namasivayam and Yamuna(Am DyestuffRep, 1994,8,22-28; Dyes and pigments, 2002, Isosorbide-5-Nitrae 7-58; Chemosphere, 1995,3,561-578; Bioresour.Technol; 1998; 1; 77-79) attempt utilizing natural pond slag to be prepared into adsorbent, effectively adsorbed the heavy metals such as Congo red, acid gorgeous indigo plant and chromium, lead, because slag source in natural pond was limited at that time; researchers prepare the research (Bioresour.Technol of adsorbent taking solid waste, plant shell and mud as raw material with rear steering; 2013,140,406-413; J.Hazard Mater, 2005, (1-3), 181-191).Utilize natural pond slag modification to become still rare report of adsorbent adsorb ammonia nitrogen studies, more deficient to the absorption research of ammonia nitrogen in the liquid of natural pond.Adopt chemical activation method to prepare the adsorbent of high absorption property, be applied to the processing of natural pond liquid, after the liquid pollution-free of natural pond, can be reused for biomethanation.Can realize biogas engineering accessory substance integrated treatment, make whole biomethanation system integrated efficient more, financial cost and environmental benefit reach optimum level.
Summary of the invention
Object of the present invention aims to provide the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent.
The present invention includes following steps:
1) by broken the natural pond ground-slag after dehydrating, be screened into natural pond solid impurity particle;
2) natural pond solid impurity particle is added in potassium hydroxide solution and mixed, after leaving standstill, again the product of removing supernatant is dried;
3) product after drying is heated to pyrolysis under nitrogen atmosphere, wait the cooling rear salt acid elution of first using of product, the washing of reusable heat deionized water, to neutral, is pulverized after drying, and grinds, and screening, obtains modification natural pond slag ammonia nitrogen adsorbent.
In step 1), described in sieve and can cross 60～100 mesh sieves.
In step 2) in, the solid-to-liquid ratio of described natural pond solid impurity particle and potassium hydroxide solution can be 1g: 2.5mL, and it is the potassium hydroxide solution of 4～6mol/L that described potassium hydroxide solution can adopt concentration; The described standing time can be 12～24h; The temperature of described oven dry can be 80～105 DEG C.
In step 3), describedly under nitrogen atmosphere, heat pyrolysis and the product after drying can be placed in high temperature process furnances heat pyrolysis under nitrogen atmosphere, firing rate is 5 DEG C/min, and pyrolysis temperature is 500～600 DEG C, and the heat time is 0.5～1h; The concentration of described hydrochloric acid can be 0.5～1mol/L; 80 DEG C of the temperature ﹥ of described hot deionized water; The temperature of described oven dry can be 80～100 DEG C; Described screening can adopt 60 order mesh screen screenings.
Owing to containing some fibre element, hemicellulose and lignin in the slag of natural pond, having abundant carbon source is to prepare the ideal material of adsorbent.It is high that these three kinds of materials form mechanical strength after high temperature pyrolysis, and the charcoal of pore structure prosperity can be used as adsorbent.Particularly cellulose, hemicellulose and lignin contain more hydroxyl and have strengthened adsorption function.Utilize natural pond slag to prepare adsorbent, meet recycling economy scientific principle and read, make discarded object natural pond slag resource, solve again problem of environmental pollution, can also adsorb ammonia nitrogen in the liquid of natural pond and realize natural pond liquid and be recycled and reused for biomethanation process.Natural pond slag modification is prepared into the adsorbent of rough surface, meso-hole structure the absorption for natural pond liquid ammonia nitrogen by the present invention.The advantages such as that modification natural pond slag ammonia nitrogen adsorbent prepared by the present invention has is with low cost, good adsorption performance.
Brief description of the drawings
Fig. 1 is the Pyrolysis Experiment device schematic diagram that embodiment 1 prepares adsorbent.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 1 natural pond slag and KOH-CC.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1:
Fig. 1 provides the Pyrolysis Experiment device schematic diagram that embodiment 1 prepares adsorbent, the outlet of nitrogen cylinder 1 connects the import of spinner flowmeter 2, the discharge connection formula stove 3 of spinner flowmeter 2, adjustable transformer 4 is connected with tube furnace 3 and temperature controller 5 respectively, and the outlet of tube furnace 3 connects the import of device for recovering tail gas 6.
Natural pond slag was pulverized 60 objects and was sieved to obtain ground-slag end, natural pond after dehydrating, and this natural pond solid impurity particle is added to 5M potassium hydroxide solution according to solid-to-liquid ratio 1g: 2.5mL, after standing 24h, supernatant was removed.Product after drying is placed in high temperature process furnances and is heated under nitrogen atmosphere.Taking firing rate as 5 DEG C of min
-1, pyrolysis temperature is to heat 1h under 550 DEG C of states.Cooling rear first with watery hydrochloric acid washing Deng product, then with deionized water washing to neutral, finally transfer to after pulverizing, grind after drying in 60 DEG C of baking ovens and sieve and obtain this ammonia nitrogen adsorbent in 60 order mesh screens, be numbered KOH-CC.The scanning electron microscope (SEM) photograph of natural pond slag and KOH-CC is referring to Fig. 2.
Test example 1
Compound concentration is 100mgL
-1ammonia nitrogen simulation natural pond liquid, get the simulation natural pond liquid of 50mL in 100mL conical flask, the ammonia nitrogen adsorbent that adds 50mg to prepare according to the method for embodiment 1.At 25 DEG C of room temperatures, on magnetic stirring apparatus, after rapid stirring 12h, after vacuumizing filtration, measure the concentration of the ammonia nitrogen of this sewage after absorption.Calculate adsorbance according to following formula:
In formula, q is adsorbance, C
0(mg/L) and Ce(mg/L) be respectively the concentration of solution after initial concentration and adsorption equilibrium, V(L) be the volume of solution, the quality that m (g) is adsorbent.Result: adsorption rate reaches more than 80%, and adsorption rate is more than 80mg/g.
Getting 50ml concentration is 100mgL
-1ammonia nitrogen solution in 100mL conical flask, add 50mg KOH-CC adsorbent at 25 DEG C, rotating speed is 200rmin
-1lower vibration, in the content of 30min, 60min, 90min, 120min, 150min, 180min, 240min, 270min and its ammonia nitrogen of 300min sampling and measuring.Carry out matching to determine best kinetic model by pseudo-first-order, accurate second-order kinetics model and to experiment the data obtained
Test example 2
Can further study the mechanism of action of its absorption ammonia nitrogen by the adsorption dynamics adsorption kinetics of KOH-CC.At 25 DEG C, use pseudo-first-order kinetics equation
accurate second-order kinetic equation
adsorption dynamics adsorption kinetics data are carried out to matching, in formula, q
e(mgg
-1) and q
t(mgg
-1) be respectively equilibrium adsorption capacity and t moment adsorbance; T(min) be the reaction time; k
1(min
-1) and k
2(gmg
-1min
-1) be respectively pseudo-first-order and accurate secondary rate constant.Different dynamic model is as shown in table 1 to the fitting result of ammonia nitrogen in the liquid of KOH-CC absorption natural pond, and result shows, the fitting effect of accurate second-order kinetic equation is best, R
2reach more than 0.99, and calculate the equilibrium adsorption capacity of gained and test institute's measured value and coincide.
Table 1
The concentration of preparing a series of ammonia nitrogens is respectively 100mgL
-1, 200mgL
-1, 400mgL
-1, 600mgL
-1, 800mgL
-1, 1000mgL
-1simulation natural pond liquid, measure 50mL ammonia nitrogen solution and add respectively 50mg KOH-CC adsorbent, rapid stirring reaction on magnetic stirring apparatus at 25 DEG C of room temperatures, detects the concentration of ammonia nitrogen after vacuumizing filtration.
Test example 3
At 25 DEG C, the adsorption isotherm experiment of KOH-CC to ammonia nitrogen in the liquid of natural pond, adopts Langmuir isotherm adsorption model
with Freundlich isotherm adsorption model
to adsorption isotherm data fitting, in formula, C
e(mgL
-1) for remaining the concentration of adsorbate in solution after balance; q
e(mgg
-1) and q
max(mgg
-1) be respectively equilibrium adsorption capacity and maximal absorptive capacity; B is relevant with adsorption strength; N and K are Freundlich isotherm adsorption model equation parameters, relevant with adsorption strength and adsorbance respectively.KOH-CC is as shown in table 2 to the isothermal fitting result of ammonia nitrogen absorption.
Table 2
Result shows, at 25 DEG C, KOH-CC more meets Langmuir model to the adsorption isotherm of ammonia nitrogen, and it is 120mgg to the maximum adsorption capacity of ammonia nitrogen
-1, it is obviously superior that other adsorbents (J.CIESC2013) such as KOH-CC and natural zeolite compare the adsorption effect of ammonia nitrogen.
Claims (10)
1. a preparation method for modification natural pond slag ammonia nitrogen adsorbent, is characterized in that comprising the following steps:
1) by broken the natural pond ground-slag after dehydrating, be screened into natural pond solid impurity particle;
2) natural pond solid impurity particle is added in potassium hydroxide solution and mixed, after leaving standstill, again the product of removing supernatant is dried;
3) product after drying is heated to pyrolysis under nitrogen atmosphere, wait the cooling rear salt acid elution of first using of product, the washing of reusable heat deionized water, to neutral, is pulverized after drying, and grinds, and screening, obtains modification natural pond slag ammonia nitrogen adsorbent.
2. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 1), described in to sieve be 60～100 mesh sieves.
3. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 2) in, the solid-to-liquid ratio of described natural pond solid impurity particle and potassium hydroxide solution is 1g: 2.5mL.
4. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 2) in, described potassium hydroxide solution adopts the potassium hydroxide solution that concentration is 4～6mol/L.
5. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 2) in, the described standing time is 12～24h.
6. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 2) in, the temperature of described oven dry is 80～105 DEG C.
7. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, it is characterized in that in step 3), it is described that under nitrogen atmosphere, to heat pyrolysis be that the product after drying is placed in high temperature process furnances heats pyrolysis under nitrogen atmosphere, firing rate is 5 DEG C/min, pyrolysis temperature is 500～600 DEG C, and the heat time is 0.5～1h.
8. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 3), the concentration of described hydrochloric acid is 0.5～1mol/L; 80 DEG C of the temperature ﹥ of described hot deionized water.
9. the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent as claimed in claim 1, is characterized in that in step 3), the temperature of described oven dry is 80～100 DEG C; Described screening can adopt 60 order mesh screen screenings.
10. the modification natural pond slag ammonia nitrogen adsorbent that as described in as arbitrary in claim 1～9 prepared by the preparation method of a kind of modification natural pond slag ammonia nitrogen adsorbent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108160044A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | A kind of preparation method of the polynary functional group's antibiotic property biogas residue adsorbent of tool for adsorbing heavy metal and anion |
| CN115155547A (en) * | 2022-07-08 | 2022-10-11 | 清华大学 | Method for in-situ utilization of biogas residues as biogas desulfurizer |
| CN115636620A (en) * | 2021-07-19 | 2023-01-24 | 上海市机电设计研究院有限公司 | Preparation method of water treatment filler based on biomass ash and biogas residues |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134070A (en) * | 2010-01-25 | 2011-07-27 | 中国科学院青岛生物能源与过程研究所 | Method for preparing activated carbon by utilizing biogas residues |
-
2014
- 2014-04-16 CN CN201410153239.2A patent/CN103877938A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134070A (en) * | 2010-01-25 | 2011-07-27 | 中国科学院青岛生物能源与过程研究所 | Method for preparing activated carbon by utilizing biogas residues |
Non-Patent Citations (1)
| Title |
|---|
| 郑杨清等: "沼渣制备生物炭吸附沼液中氨氮的研究", 《化工学报》, 26 February 2014 (2014-02-26), pages 1 - 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108160044A (en) * | 2017-12-29 | 2018-06-15 | 山东大学 | A kind of preparation method of the polynary functional group's antibiotic property biogas residue adsorbent of tool for adsorbing heavy metal and anion |
| CN115636620A (en) * | 2021-07-19 | 2023-01-24 | 上海市机电设计研究院有限公司 | Preparation method of water treatment filler based on biomass ash and biogas residues |
| CN115636620B (en) * | 2021-07-19 | 2024-03-15 | 上海市机电设计研究院有限公司 | Preparation method of water treatment filler based on biomass ash residues and biogas residues |
| CN115155547A (en) * | 2022-07-08 | 2022-10-11 | 清华大学 | Method for in-situ utilization of biogas residues as biogas desulfurizer |
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Application publication date: 20140625 |