CN105268399B - Room temperature ammonia efficient process material - Google Patents

Room temperature ammonia efficient process material Download PDF

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Publication number
CN105268399B
CN105268399B CN201410324618.3A CN201410324618A CN105268399B CN 105268399 B CN105268399 B CN 105268399B CN 201410324618 A CN201410324618 A CN 201410324618A CN 105268399 B CN105268399 B CN 105268399B
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ammonia
room temperature
efficient process
air
acid
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CN105268399A (en
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杜峰
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JIANGSU REFONTECH INDUSTRIAL Co Ltd
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JIANGSU REFONTECH INDUSTRIAL Co Ltd
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Abstract

Preparation and its application method the invention discloses a kind of room temperature ammonia efficient process material, belong to indoor air purification Treatment process field.The scavenging material is characterized in that using high specific surface area porous sorbing material as carrier, using aluminium chloride, Aluminum sol or meta-aluminate, zirconium chloride or zirconium oxychloride as mixed modifier, with one kind in sulfuric acid, hydrochloric acid, nitric acid, boric acid or phosphoric acid for surface conditioning agent, using mixed modifier pass sequentially through dipping, aging, separation of solid and liquid, drying, calcining it is modified, then using surface conditioning agent by impregnating, air-dry form.The room temperature ammonia efficient process material anti humility performance of the present invention is good, has multi-cellular structure, specific surface area is big, a large amount of acidic-groups are contained on surface, and adsorption capacity is big, and adsorption rate is fast, anti humility performance is good, and the ammonia in the fast long-acting adsorption cleaning air of energy, can meet under indoor true environment for a long time(>3000 h)The requirement of adsorption cleaning ammonia, suitable for refrigerating plant room and the air purification with ammonia polluted place is handled.

Description

Room temperature ammonia efficient process material
Technical field
Preparation and its application method the present invention relates to a kind of room temperature ammonia efficient process material, especially with compound gold The ammonia decontamination material with high anti humility performance is made in the method for belonging to salt and acid solution step-by-step processing, belongs to indoor air purification Treatment process field.
Background technology
Ammonia relative molecular mass is 17.03, and fusing point is -77.74 DEG C, and boiling point is -33.43 at normal atmospheric pressure DEG C, be under room temperature colourless irritant stench smell, it is soluble easily in water.Promulgated in country in 2002《Indoor air quality Standard》Strict regulations, wherein air have been done to PM10, bacteria containing amount, ammonia amount etc. in room air in (GB/T 1883-2002) Middle ammonia sanitary standard (maximum permissible concentration) is 0.20 mg/m3.The influence of ammonia is mostly derived from its high alkalinity and height is water-soluble Property, the respiratory system and skin of human body can mainly be damaged.
In general, when ammonia concentration reaches 5 ppm, will be arrived by human body sensory;When ammonia concentration reaches 20 ppm During the above, it will cause serious injury to multiple systems such as the respiratory tract of human body, alimentary canals.Sucking in a short time after a large amount of ammonias can Appearance is shed tears, pharyngalgia, hoarseness, cough, phlegm can with the trace of blood, uncomfortable in chest, expiratory dyspnea, can with headache, dizzy, nausea, vomit Tuhe is weak to wait ill symptoms, and severe patient can occur pulmonary edema, adult respiratory distress syndrome, edema of the larynx spasm or bronchus and glue Film necrosis comes off lethal.
At present, indoor air purifying process mainly have photochemical catalytic oxidation, activated carbon adsorption, biocatalyst, ozone oxidation, The multiple technologies means such as precious metal catalyst oxidation, high efficiency particulate air and negative oxygen ion.Wherein, photocatalysis needs substantial amounts of ultraviolet Light, and it is very small to the effect of ammonia;Simple activated carbon adsorption anti humility performance is poor, and easily saturation causes secondary pollution;It is raw The thing catalyst reaction time is longer, and pollutant fast and effectively can not be removed;Ozone oxidation is primarily directed to some and waves Hair property organic gas, it is impossible to effectively handle ammonia;Precious metal catalyst oxidation industrialization causes industrial prospect because its cost is excessive It is uncertain;High efficiency particulate air and negative oxygen ion are more directed to some solid contaminants.Therefore, research and develop one kind can have compared with Big adsorption capacity, the novel strong ammonia gas absorption material of humidity-proof ability at the same time of absorption mode is also the numerous researchers of air purification field Goal in research.
Based on above target, the researcher of various countries has also done substantial amounts of research work, passes through one to occurring in field A little new materials carry out acidifications or are formed organic framework structured to achieve certain effect(1、 Doonan, C. J.; Tranchemontagne, D. J.; Glover, T. G.; Hunt, J.R.; Yaghi, O. M. Exceptional Ammonia Uptake by a Covalent OrganicFramework. Nat. Chem. 2010, 2, 235−238;2、 Furtado, A. M. B.; Wang, Y.; Glover, T. G. MCM-41Impregnated with Active Metal Sites: Synthesis, Characterization,and Ammonia Adsorption. Microporous Mesoporous Mater. 2011, 142,730−739;3、Seredych, M.; Bandosz, T. J. Manganese Oxide and Graphite Oxide/MnO2 Composites as Reactive Adsorbents of Ammonia atAmbient Conditions. Micro. Meso. Mater. 2012, 150, 55−63.).But in the studies above, Used method is all more complicated, and raw material also costly, are unfavorable for industrialized production, and is to be directed to single performance mostly Studied, do not take into account many factors such as adsorption capacity, absorption property and use environment at the same time.Meanwhile for current The increasing market demand, the country also have many researchers to research and develop ammonia gas absorption material, such as CN 101279236A reports a kind of purificant for adsorbing ammonia gas and preparation method thereof, handles to have obtained phase by simple acid solution The material answered, but temperature is relatively low in its preparation process, and ageing time is shorter, effectively can not form acidity in porous material surface Group, and anti humility performance, easy saturation are not considered.And CN 101264434A and CN 103111255A etc. is then reported using boiling Mountain flour, kaolin, Blumea oil etc. are a kind of ammonia gas absorption agent preparation method of raw material, and absorption ammonia is efficient, but can equally deposit Adsorption capacity is too small, anti humility performance is poor the shortcomings of.
Therefore, prepare a kind of can have high anti humility performance and the ammonia gas absorption of adsorption capacity at the same time in efficient absorption ammonia Agent tool is of great significance.
The content of the invention
Preparation and its application method the invention discloses a kind of room temperature ammonia efficient process material, belong to indoor air purification Treatment process field.It is an object of the invention to provide a kind of ammonia gas absorption material, and the material anti humility performance is good, has more micropores Structure, specific surface area is big, and a large amount of acidic-groups are contained on surface, and adsorption capacity is big, and adsorption rate is fast, and anti humility performance is good, can be quick Ammonia in long-acting adsorption cleaning air, can meet under indoor true environment for a long time(>3000 h)Adsorption cleaning ammonia is wanted Ask.
To achieve the above object, the technical solution that the present invention takes is as follows:
A kind of room temperature ammonia efficient process material, comprises the following steps:
(1)It is by high specific surface area porous sorbing material addition mass fraction(5~15)Aluminium salt and the zirconates mixing of wt% is molten Liquid, when dipping aging 8 ~ 16 is small, subsequent separation of solid and liquid, when 80 ~ 100 DEG C of forced air dryings 12 are small;
(2)The material that step 1 obtains is controlled into temperature when 250 ~ 350 DEG C of calcinings 2 ~ 4 are small under protective atmosphere;
(3)Material after step 2 is calcined adds after grinding(1~5)When dipping 12 ~ 16 is small in the acid solution of mol/L, Take out and both obtained room temperature ammonia efficient process material after air-drying;
(4)In use, it is 300 m to take 500 ~ 1000 g of material that step 3 obtains to be encapsulated in air quantity3The m of/h~6003/ h's In air purifier, 30 m in 1h can be made31.6 mg/m under environment3~2.4 mg/m3Ammonia removal rate up to 90 more than %, surely Determine the h of run time >=3000.
High specific surface area porous sorbing material in raw material is activated carbon, one kind in zeolite molecular sieve, activated alumina It is or a variety of.
Aluminium salt in raw material is aluminium chloride, the one or more in Aluminum sol, meta-aluminate.
Zirconates in raw material is one or both of zirconium chloride, zirconium oxychloride.
Acid solution in raw material is sulfuric acid, the one or more in hydrochloric acid, nitric acid, boric acid, phosphoric acid.
The protective atmosphere is one kind in air, nitrogen.
The technique effect and advantage of the present invention is as follows:
1st, the ammonia that room temperature ammonia efficient process material of the invention can rapidly and efficiently in adsorption cleaning air, effectively prevents The injury that ammonia in air is brought to human body;
2nd, room temperature ammonia efficient process material of the invention mixes polycation by forming aluminium pick in carrier surface, to sky Hydrone in gas forms repulsive interaction, can efficiently resist the too early saturation caused by material of the moisture in air;
3rd, room temperature ammonia efficient process material anti humility performance of the invention is good, has multi-cellular structure, specific surface area is big, table A large amount of acidic-groups are contained in face, and adsorption capacity is big, can meet under indoor true environment for a long time(>3000 h)Adsorption cleaning ammonia Requirement, suitable for refrigerating plant room and with ammonia polluted place air purification handle.
Embodiment
The present invention is further illustrated below by way of example:
Embodiment 1
Take 1000 g activated carbons to add in the aluminium chloride and zirconium chloride mixed solution that mass fraction is 10 wt%, impregnate aging 12 it is small when, subsequent separation of solid and liquid, when 90 DEG C of forced air dryings 12 are small, obtained material controls temperature to exist in a nitrogen atmosphere When 300 DEG C of calcinings 3 are small, material after calcining adds that dipping 12 is small in the sulfuric acid solution of 3 mol/L after grinding when, take out and air-dry Room temperature ammonia efficient process material had both been obtained afterwards;
In use, it is 400 m to take 600 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, 30 m in 1h are tested3 2.01 mg/m under environment3Ammonia removal rate be 92 %.
Embodiment 2
1000 g zeolite molecular sieves are taken to add in the meta-aluminate and zirconium chloride mixed solution that mass fraction is 15 wt%, leaching When stain aging 16 is small, subsequent separation of solid and liquid, when 100 DEG C of forced air dryings 12 are small, obtained material controls in air atmosphere Temperature material after calcining adds that dipping 16 is small in the sulfuric acid solution of 5 mol/L after grinding when, takes when 350 DEG C of calcinings 4 are small Go out after air-drying both to have obtained room temperature ammonia efficient process material;
In use, it is 500 m to take 800 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, 30 m in 1h are tested3 2.12 mg/m under environment3Ammonia removal rate be 95 %.
Embodiment 3
1000 g activated aluminas are taken to add in the Aluminum sol and zirconium oxychloride mixed solution that mass fraction is 10 wt%, leaching When stain aging 12 is small, subsequent separation of solid and liquid, when 80 DEG C of forced air dryings 12 are small, obtained material controls temperature in air atmosphere Degree material after calcining adds that dipping 15 is small in the phosphoric acid solution of 2 mol/L after grinding when, takes out when 300 DEG C of calcinings 2 are small Room temperature ammonia efficient process material had both been obtained after air-drying;
In use, it is 600 m to take 600 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, 30 m in 1h are tested3 2.38 mg/m under environment3Ammonia removal rate be 91 %.
Embodiment 4
1000 g activated carbons are taken to add in the aluminium chloride and zirconium oxychloride mixed solution that mass fraction is 15 wt%, dipping is old Change 8 it is small when, subsequent separation of solid and liquid, when 80 DEG C of forced air dryings 12 are small, obtained material controls temperature to exist in a nitrogen atmosphere When 350 DEG C of calcinings 4 are small, material after calcining adds that dipping 12 is small in the salpeter solution of 3 mol/L after grinding when, take out and air-dry Room temperature ammonia efficient process material had both been obtained afterwards;
In use, it is 600 m to take 1000 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, test 30 in 1h m31.98 mg/m under environment3Ammonia removal rate be 98 %.
Embodiment 5
1000 g zeolite molecular sieves are taken to add in the meta-aluminate and zirconium oxychloride mixed solution that mass fraction is 5 wt%, When dipping aging 12 is small, subsequent separation of solid and liquid, when 100 DEG C of forced air dryings 12 are small, obtained material is controlled in air atmosphere Temperature processed is when 250 DEG C of calcinings 2 are small, material after calcining adds that dipping 14 is small in the hydrochloric acid solution of 5 mol/L after grinding when, Take out and both obtained room temperature ammonia efficient process material after air-drying;
In use, it is 500 m to take 800 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, 30 m in 1h are tested3 2.12 mg/m under environment3Ammonia removal rate be 91 %.
Embodiment 6
1000 g activated aluminas are taken to add in the Aluminum sol and zirconium oxychloride mixed solution that mass fraction is 10 wt%, leaching When stain aging 16 is small, subsequent separation of solid and liquid, when 80 DEG C of forced air dryings 12 are small, obtained material controls temperature in air atmosphere Degree material after calcining adds that dipping 15 is small in the boric acid solution of 4 mol/L after grinding when, takes out when 350 DEG C of calcinings 2 are small Room temperature ammonia efficient process material had both been obtained after air-drying;
In use, it is 600 m to take 900 g of above-mentioned material to be encapsulated in air quantity3In the air purifier of/h, 30 m in 1h are tested3 1.68 mg/m under environment3Ammonia removal rate be 92%.

Claims (5)

1. a kind of preparation method of room temperature ammonia efficient process material, it is characterised in that comprise the following steps:
(1)It is by high specific surface area porous sorbing material addition mass fraction(5~15)The aluminium salt and zirconates mixed solution of wt%, leaching When stain aging 8 ~ 16 is small, subsequent separation of solid and liquid, when 80 ~ 100 DEG C of forced air dryings 12 are small;
(2)By step(1)Obtained material controls temperature when 250 ~ 350 DEG C of calcinings 2 ~ 4 are small under air or nitrogen atmosphere;
(3)By step(2)Material after calcining adds after grinding(1~5)When dipping 12 ~ 16 is small in the acid solution of mol/L, take The high specific surface area porous material for being loaded with acidic-group, the efficient process available for ammonia room temperature can both be obtained by going out after air-drying;
(4)In use, take step(3)It is 300 m that obtained 500 ~ 1000 g of material, which is encapsulated in air quantity,3The m of/h~6003The sky of/h In gas purifier, 30 m in 1h can be made31.6 mg/m under environment3~2.4 mg/m3Ammonia removal rate up to 90 more than %, stablize The h of run time >=3000.
2. the preparation method of room temperature ammonia efficient process material according to claim 1, it is characterised in that the height in raw material Specific surface area porous adsorbing material is activated carbon, the one or more in zeolite molecular sieve, activated alumina.
3. the preparation method of room temperature ammonia efficient process material according to claim 1, it is characterised in that the aluminium in raw material Salt is aluminium chloride, the one or more in Aluminum sol, meta-aluminate.
4. the preparation method of room temperature ammonia efficient process material according to claim 1, it is characterised in that the zirconium in raw material Salt is one or both of zirconium chloride, zirconium oxychloride.
5. the preparation method of room temperature ammonia efficient process material according to claim 1, it is characterised in that the acid in raw material Property solution be sulfuric acid, hydrochloric acid, nitric acid, boric acid, the one or more in phosphoric acid.
CN201410324618.3A 2014-07-09 2014-07-09 Room temperature ammonia efficient process material Expired - Fee Related CN105268399B (en)

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CN109550373A (en) * 2019-01-29 2019-04-02 艾易西(中国)环保科技有限公司 One kind is except base material and preparation method thereof
CN111617735B (en) * 2020-05-27 2022-07-05 青岛华世洁环保科技有限公司 Amine odor removal material
CN113600136A (en) * 2021-08-04 2021-11-05 北京市劳动保护科学研究所 Preparation method of solid adsorbent for collecting ammonia in air and sampling pipe

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264434A (en) * 2008-05-05 2008-09-17 中国农业大学 Drying agent for absorbing ammonia
CN101279236A (en) * 2008-05-23 2008-10-08 张宏 Purificant for adsorbing ammonia gas and method of preparing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264434A (en) * 2008-05-05 2008-09-17 中国农业大学 Drying agent for absorbing ammonia
CN101279236A (en) * 2008-05-23 2008-10-08 张宏 Purificant for adsorbing ammonia gas and method of preparing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Activated carbons modified with aluminium–zirconium polycations as adsorbents for ammonia";Camille Petit,et al;《Microporous and Mesoporous Materials》;20080102;第114卷;摘要、第2.1节 *

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