CN104383877A - Rare-earth metal modified integral activated carbon absorbent as well as preparation method and application thereof - Google Patents

Rare-earth metal modified integral activated carbon absorbent as well as preparation method and application thereof Download PDF

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Publication number
CN104383877A
CN104383877A CN201410614878.4A CN201410614878A CN104383877A CN 104383877 A CN104383877 A CN 104383877A CN 201410614878 A CN201410614878 A CN 201410614878A CN 104383877 A CN104383877 A CN 104383877A
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earth metal
rare
monoblock type
acticarbon
preparation
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CN201410614878.4A
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CN104383877B (en
Inventor
何丹农
杨玲
赵昆峰
高振源
蔡婷
袁静
爨谦
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a rare-earth metal modified integral activated carbon absorbent as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing 2ml of a rare-earth metal water solution at room temperature; dropwise adding ammonia water while stirring until the pH value is 8-10; further stirring the mixed solution for 10-30 minutes, and dropwise adding the mixed solution to a dried integral activated carbon carrier which is 2g in weight; and putting the carrier in an oven, and preserving for 1-5 hours at the temperature of 200-250 DEG C, thus obtaining the modified integral activated carbon absorbent. The scavenging material obtained according to the invention has the characteristics of high low-concentration hydrocarbon purifying efficiency, low cost, simple preparing process and the like; the purifying efficiency of the material on hydrocarbons reaches up to 90% above when the concentration of hydrocarbons is smaller than or equal to 10ppm.

Description

A kind of rare-earth metal modified monoblock type acticarbon and preparation method and application
Technical field
The present invention relates to a kind of preparation method and application of rare-earth metal modified monoblock type acticarbon, the purification being applicable to hydrocarbon in environmental contaminants is eliminated.
Background technology
Hydrocarbon is one of main matter of atmosphere pollution, along with increasing considerably of automobile consumption, and the exhaust emissions of the equipment such as boiler, the pollution of hydrocarbon has become an important topic of environmental improvement.Because the Nature comparison of hydrocarbon is stablized, the main method of current process hydrocarbon is catalytic combustion and absorption method, wherein Production by Catalytic Combustion Process be not suitable for the purification of air pollutants, and absorption method technique is relatively simple, can harmful substance that effectively supplementary set concentration is very low can changing waste into resources be realized, be therefore widely used.
Chinese patent CN102000548A discloses " a kind of preparation method of modified activated carbon absorbent of low-concentration organic exhaust gas ", take Alveolate activated carbon capable as carrier, through oxidation modification back loading metal oxide, for the purification of toluene and butylene gaseous mixture, evolution rate is more considerable, but preparation process is comparatively loaded down with trivial details.
Chinese patent CN102451665A discloses " low-concentration hydrocarbon gas adsorbent and preparation method thereof ", its preparation method take bamboo charcoal as carrier, the Multimetal oxide of load simultaneously after Surface Oxidation Modification, for the adsorption cleaning of propane and propylene gaseous mixture, but the adsorbent purification efficiency obtained is lower, all at 90 below %.
Summary of the invention
In order to overcome the defect that above-mentioned existing low concentration hydrocarbon Treatment process exists, the invention provides a kind of cost low, preparation technology is simple, rare-earth metal modified monoblock type acticarbon that can improve low concentration hydrocarbon purification efficiency and its preparation method and application.
A kind of preparation method of rare-earth metal modified monoblock type acticarbon, it is characterized in that, the rare earth metal aqueous solution ammonia spirit configured is precipitated, is then added dropwise to monoblock type activated carbon surface, prepare rare-earth metal modified monoblock type acticarbon, concrete steps are as follows:
At ambient temperature, configure 2 milliliters of rare earth metal aqueous solution, dripping ammonia spirit to pH value is while stirring 8 ~ 10, continue stirring 10 ~ 30 minutes, be added dropwise on dried monoblock type absorbent charcoal carrier, the quality of carrier is 2 grams and then puts into 200 ~ 250 DEG C, baking oven maintenance 1 ~ 5 hour, makes modification monoblock type acticarbon.
The described rare earth metal aqueous solution is lanthanum nitrate, lanthanum chloride, cerous nitrate, ammonium ceric nitrate, neodymium nitrate, the one in the neodymium chloride aqueous solution or its combination.
The concentration of the described rare earth metal aqueous solution is 0.0160 ~ 0.160 mol/L.
The concentration of described ammonia spirit is 1.0 ~ 3.0 mol/L.
A kind of rare-earth metal modified monoblock type acticarbon, prepares according to above-mentioned arbitrary described method.
The application that a kind of rare-earth metal modified monoblock type acticarbon is eliminated at hydrocarbon purification.
With rare-earth metal modified monoblock type acticarbon prepared by said method, the mass percent of its rare-earth oxide is 0.20 % ~ 2.5 %, can be used for the adsorption cleaning of low concentration hydrocarbon.
Compared with prior art, the remarkable advantage of rare-earth metal modified monoblock type acticarbon of the present invention is, high to the purification efficiency of low concentration hydrocarbon, cost is low, and preparation technology is simple.When hydrocarbon concentration≤10 ppm, this material can reach 90 more than % to the purification efficiency of hydrocarbon.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail: the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
100 order active carbons (are made 10*10*48mm with the monoblock type active carbon of non-modified, being weighed 2.10 g) for contrasting adsorbent, being placed on reaction tube (Φ 17 mm by the present invention, long 300 mm) in, pass into unstripped gas propylene, concentration is 10 ppm, all the other are air, volume space velocity 9000 h -1, under normal temperature and pressure conditions, the highest purification efficiency is 54.5 %.
embodiment 1:
Take 0.0124g lanthanum nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.07g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component lanthana is 0.30 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 91.3 %.
embodiment 2:
Take 0.0370g lanthanum nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.14g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component lanthana is 0.86 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 95.7 %.
embodiment 3:
Take 0.0975g lanthanum nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.21g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component lanthana is 2.2 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 96.9 %.
embodiment 4:
Take 0.0176g cerous nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.08g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component ceria is 0.33 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 92.8 %.
embodiment 5:
Take 0.0525g cerous nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.13g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component ceria is 0.97 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 97.5%.
embodiment 6:
Take 0.126g cerous nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.09g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component ceria is 2.4 %.
The modified activated carbon absorbent of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 97.9 %.
embodiment 7:
Take 0.0150g neodymium nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.16g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component neodymia is 0.26 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 90.3 %.
embodiment 8:
Take 0.0452g neodymium nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.11g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component neodymia is 0.82 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 94.7%.
embodiment 9:
Take 0.134g neodymium nitrate and be dissolved in 2.0 ml deionized waters, then dripping 2.0 mol/L ammoniacal liquor to pH value is while stirring 9, continue stirring 20 minutes, obtained uniform suspension is added drop-wise to dried absorbent charcoal carrier and (100 order active carbons is made 10*10*48mm, heavy 2.25g) on, then put into 230 DEG C, baking oven to keep 3 hours, make modification monoblock type acticarbon, the mass percent of its active component neodymia is 2.3 %.
The modification monoblock type acticarbon of the low concentration hydrocarbon purification that the present embodiment obtains, under normal temperature and pressure conditions, unstripped gas is the propylene of 10 ppm, and all the other are air, and volume space velocity is 9000 h -1, the highest purification efficiency is 95.8 %.

Claims (6)

1. the preparation method of a rare-earth metal modified monoblock type acticarbon, it is characterized in that, the rare earth metal aqueous solution ammonia spirit configured is precipitated, is then added dropwise to monoblock type activated carbon surface, prepare rare-earth metal modified monoblock type acticarbon, concrete steps are as follows:
At ambient temperature, configure 2 milliliters of rare earth metal aqueous solution, dripping ammonia spirit to pH value is while stirring 8 ~ 10, continue stirring 10 ~ 30 minutes, be added dropwise on dried monoblock type absorbent charcoal carrier, the quality of carrier is 2 grams and then puts into 200 ~ 250 DEG C, baking oven maintenance 1 ~ 5 hour, makes modification monoblock type acticarbon.
2. the preparation method of a kind of rare-earth metal modified monoblock type acticarbon according to claim 1, it is characterized in that, the described rare earth metal aqueous solution is lanthanum nitrate, lanthanum chloride, cerous nitrate, ammonium ceric nitrate, neodymium nitrate, the one in the neodymium chloride aqueous solution or its combination.
3. the preparation method of a kind of rare-earth metal modified monoblock type acticarbon according to claim 1 and 2, is characterized in that, the concentration of the described rare earth metal aqueous solution is 0.0160 ~ 0.160 mol/L.
4. the preparation method of a kind of rare-earth metal modified monoblock type acticarbon according to claim 1, is characterized in that, the concentration of described ammonia spirit is 1.0 ~ 3.0 mol/L.
5. a rare-earth metal modified monoblock type acticarbon, is characterized in that, according to above-mentioned arbitrary claim, method prepares.
6. the application eliminated at hydrocarbon purification of a kind of rare-earth metal modified monoblock type acticarbon according to claim 5.
CN201410614878.4A 2014-11-05 2014-11-05 A kind of rare-earth metal modified monoblock type acticarbon and preparation method and application Expired - Fee Related CN104383877B (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN105964103A (en) * 2016-07-13 2016-09-28 方龙旺 Formula of air purification and bacterium adsorption material
CN105983389A (en) * 2016-07-15 2016-10-05 宋玉琴 Preparation method of lanthanum-containing activated carbon
CN106040197A (en) * 2016-07-13 2016-10-26 方龙旺 Floating dust and exhaust gas filtering and adsorbing material
CN106064083A (en) * 2016-07-13 2016-11-02 方龙旺 A kind of material for plant gas purification filtering
CN106178688A (en) * 2016-07-13 2016-12-07 方龙旺 A kind of filtering material of indoor air cleaner
CN106268168A (en) * 2016-08-30 2017-01-04 武汉威富永磁科技有限公司 A kind of cleaning equipment for waste organic gas and purification method thereof
CN107537459A (en) * 2017-08-01 2018-01-05 云南省贵金属新材料控股集团有限公司 A kind of preparation method for handling bio-refractory industrial organic waste water catalyst
CN112371084A (en) * 2020-10-20 2021-02-19 广西南宁都宁通风防护设备有限公司 Preparation method and application of sterilized activated carbon

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105964103A (en) * 2016-07-13 2016-09-28 方龙旺 Formula of air purification and bacterium adsorption material
CN106040197A (en) * 2016-07-13 2016-10-26 方龙旺 Floating dust and exhaust gas filtering and adsorbing material
CN106064083A (en) * 2016-07-13 2016-11-02 方龙旺 A kind of material for plant gas purification filtering
CN106178688A (en) * 2016-07-13 2016-12-07 方龙旺 A kind of filtering material of indoor air cleaner
CN105983389A (en) * 2016-07-15 2016-10-05 宋玉琴 Preparation method of lanthanum-containing activated carbon
CN106268168A (en) * 2016-08-30 2017-01-04 武汉威富永磁科技有限公司 A kind of cleaning equipment for waste organic gas and purification method thereof
CN107537459A (en) * 2017-08-01 2018-01-05 云南省贵金属新材料控股集团有限公司 A kind of preparation method for handling bio-refractory industrial organic waste water catalyst
CN112371084A (en) * 2020-10-20 2021-02-19 广西南宁都宁通风防护设备有限公司 Preparation method and application of sterilized activated carbon

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