CN101298037A - Adsorbing agent for removing trace amount of nitric oxide in carbon dioxide and preparation - Google Patents

Adsorbing agent for removing trace amount of nitric oxide in carbon dioxide and preparation Download PDF

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Publication number
CN101298037A
CN101298037A CNA2008100119551A CN200810011955A CN101298037A CN 101298037 A CN101298037 A CN 101298037A CN A2008100119551 A CNA2008100119551 A CN A2008100119551A CN 200810011955 A CN200810011955 A CN 200810011955A CN 101298037 A CN101298037 A CN 101298037A
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China
Prior art keywords
adsorbent
preparation
carbon dioxide
nitric oxide
trace amount
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CNA2008100119551A
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Chinese (zh)
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陈绍云
张永春
郭新闻
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Dalian University of Technology
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Dalian University of Technology
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Priority to CNA2008100119551A priority Critical patent/CN101298037A/en
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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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to an adsorbent for removing trace amount of nitric oxide in carbon dioxide and a preparation method thereof, and pertains to the technical field of environment resources and is characterized by providing the adsorbent prepared by taking alumina-HZSM-5 as a carrier and the preparation method, which is used for removing the trace amount of nitric oxide in carbon dioxide; the carrier of the adsorbent loads an activation auxiliary agent Ce salt and one of active components of Co, Ni and Mn, or two metal salts of Mn and Ni or Mn and Co by an equal volume impregnation-high temperature roasting method. The invention have the effects and benefits that the adsorbent has high purification degree and good thermal stability, can be able to remove the nitric oxide in the carbon dioxide to lower than 0.1ppmv under an oxygen free condition and an aerobic condition, and can be reproduced by being heated and scavenged with dry air, nitrogen and carbon dioxide after adsorption saturation; the invention provides a key technology for the preparation of food-grade carbon dioxide and has wide application prospect.

Description

Remove the adsorbent and the preparation method of trace amount of nitric oxide in the carbon dioxide
Technical field
The invention belongs to the environmental resource technical field, relate to adsorbent that removes trace amount of nitric oxide in the carbon dioxide and preparation method thereof.
Background technology
Food-class CO 2Be not only important additive in the food service industry, and at CO 2The application of polyester industrial and medical field also more and more widely.Reclaim CO in the flue gas 2Often with trace nitrogen oxide (NO and NO 2), wherein NO content accounts for NO xIn more than 90%, and be difficult to remove.CO 2In other light component impurity can it be separated by the method for cryogenic rectification, but since NO concentration very low (＜200ppmv), and be oxidized to NO easily through after a while 2, can't utilize rectification method to remove, make CO 2Reach the food-grade requirement.The main application process that present NO removes is exactly catalytic reduction method (SCR) and absorption method, applies to CO 2In NO xAdsorbent or catalyst yet there are no report both at home and abroad.
Selective catalytic reduction is primarily aimed at NO xThe source of the gas that concentration of emission is higher is for example made nitric acid tail gas, and coal power generation station etc. utilize ammonia, and low-carbon alkanes or alkene are to NO xSelective reduction becomes N 2, H 2O and CO 2But during the selective catalytic reduction reductive NO, degree of purification is not high, reaction temperature height (＞100 ℃), and need to add reducibility gas, cause secondary pollution easily, so be not suitable for CO 2Middle NO xThe application that purifies.
Adsorption method of separation is owing to its operating condition gentleness, and degree of purification height, equipment simply are easy to operate in extensive application in the gas purification field.For CO 2In the trace NO that contains can utilize absorption method with its deep removal, reach food-grade (＜2.5ppmv).In the relevant document (Langmuir9 (1993) 2337-2343), Wenxiang Zhang etc. has reported the reversible and Irreversible Adsorption situation of NO (1910ppmv) on the ZSM-5 of ion-exchange under the oxygen free condition, is mainly used in the PSA technology.But the adsorbance of NO under oxygen free condition is very limited, only is translated into NO 2, just can better adsorb and store.
In the document (Langmuir 17 (2001) 4997-5003), Helen Y.Huang etc. has prepared the Fe-Mn-Ti mixed-metal oxides and has been used under the aerobic conditions absorption to NO, CO 2Adsorbance is had bigger influence, and using rate of metal is lower.
U.S. Pat 005158582A discloses and has utilized zeolite molecular sieve (A, X, Y type) load mantoquita, is used for adsorption of Low Concentration NO (5ppmv).
Patent CN1145272A discloses with titanium dioxide as adsorbing agent carrier, and load manganese isoreactivity component is used for absorbing the low concentration of NO in tunnel x
Summary of the invention
The objective of the invention is to preparation and be used to remove CO efficiently 2The adsorbent of middle trace NO.High silica alumina ratio HZSM-5 (25,38 and 50) is that with the characteristics that boehmite is mixed with the aluminium oxide-molecular sieve complex carrier that obtains specific area is big, the heat endurance height, and resistance to acids and bases is strong, helps the high degree of dispersion of components such as metal ion or oxide.By incipient impregnation-high-temperature roasting method, flood a small amount of transition metal ions and oxide on aluminium oxide-HZSM-5 complex carrier, the adsorbent that obtains applies to absorption-rectifying and prepares high-purity CO 2In the time of in the technology, under oxygen free condition and under the aerobic conditions, trace NO removed have the degree of purification height, oxidation rate is fast, and the rate of adsorption is fast, the big and high characteristics of heat endurance of adsorbance.
Technical scheme of the present invention is: remove CO 2In the trace amount of nitric oxide adsorbent mainly be to be that carrier and active component are formed with aluminium oxide-HZSM-5, wherein:
(1) carrier is formed and content
HZSM-5 (SiO 2/ Al 2O 3=25,38 and 50) zeolite molecular sieve content accounts for the 20-90% of adsorbent total amount
Boehmite content accounts for the 10-80% of adsorbent total amount
(2) active component kind and content
Co salt, content account for the 1-10% of adsorbent gross weight
Ni salt, content account for the 1-10% of adsorbent gross weight
Mn salt, content account for the 1-10% of adsorbent gross weight
Ce salt, content account for the 0.1-2% of adsorbent gross weight
According to claim 1, remove CO under the preparation oxygen free condition 2The method of the adsorbent of middle carbon monoxide.It is characterized in that preparation of adsorbent was divided into for two steps:
The first step, the preparation of carrier
Take by weighing certain amount of H ZSM-5 and a certain amount of boehmite, zeolite molecular sieve: boehmite=20-90: 10-80, after both are fully mixed, rare nitric acid of adding 5% mixes into grains of sand shape, then at once it is extruded into diameter and is the bar about 2.5mm, after drying, room temperature puts into baking oven, 90-120 ℃ of drying 12 hours, place Muffle furnace then, at room temperature, speed with 10 ℃/min is warming up to 550 ℃, and constant temperature calcining 5 hours is made zeolite molecular sieve-alumina composite carrier.
Second step, the load of active component and activation
Adopt the method for incipient impregnation, accurately weighing accounts for the Ce salt of weight 0.1-2% in the adsorbent, add deionized water and dissolve, add the drying and moulding carrier HZSM-5 for preparing, at room temperature placed 4-5 hour, it is following dry 12 hours to put into 105 ℃ in baking oven subsequently, be transferred to then in the Muffle furnace, at room temperature, with 10 ℃/min temperature programming to 400-500 ℃, and constant temperature 3 hours, make the adsorbent precursor; And then accurately weighing accounts for Co, the Ni of the 1-10% of adsorbent weight or a kind of or two kinds (mol ratio of metal is 1: 1 when using bimetallic) in the Mn salt, use deionized water dissolving, add the adsorbent precursor again and carry out double-steeping, then the double-steeping thing is implemented and preparation adsorbent precursor identical operations, obtained adsorbent.
Adsorbent is at CO 2In remove nitric oxide, employing be alternating temperature absorption (TSA) technology, adsorbent carries out Dynamic Selection absorption to NO at normal temperatures and pressures, after the adsorption penetration, with the regeneration of dry gas heating and blowing, regeneration temperature is 350-450 ℃, the enrichment of N O that purges out xCan be by catalytic reduction method reduction or preparation nitric acid.Heating means can be electrical heating or warm air blowoff.
Effect of the present invention and benefit are: adsorbing agent carrier of the present invention is made up of high silicon micro-pore zeolite molecular sieve and amorphous alumina, has good permeability, wearability and heat endurance.Adopt the method carried metal active component and the active component auxiliary agent of incipient impregnation, utilize the even dispersed activity component of method of high-temperature roasting, make active component and auxiliary agent well collaborative simultaneously, can greatly improve it at CO 2In to adsorptive selectivity and the oxidability of NO, not only utilized the high-specific surface area of molecular sieve but also efficiently utilized the metallic atom utilization rate, obtained very high detergent power and adsorbance preferably simultaneously.Adsorbent can be used with under anaerobic and aerobic (concentration＜10%) condition mutually, utilizes advantage separately to replenish mutually; At CO 2In NO can be removed to below the 0.1ppmv, adsorbent can purge regeneration by dry gas.Adsorbent heat stability and hot reproducibility are very high, are that deep removal trace NO prepares food-class CO in the TSA technology 2Desirable adsorbent, this adsorbent also can be used for purifying the trace NO in other high-purity gas, as high-purity N 2And H 2, have broad application prospects.
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1
The accurate former powder 80g of weighing HZSM-5 (25), boehmite 20g (all in butt); With 100-200 mesh sieve both are fully mixed, add 5% nitric acid, stir into grains of sand shape after, gather around the bar that banded extruder is extruded into the 2.5mm diameter; Change in the baking oven after drying under the room temperature, 120 ℃ of dryings 12 hours are put into Muffle furnace, and at room temperature the speed with 10 ℃/min was warming up to 550 ℃ of constant temperature calcinings 5 hours, was prepared into hard white alumina-HZSM-5 complex carrier.
Accurate weighing 309mg Ce (NO 3) 46H 2O adds the 95ml deionized water dissolving, with the above-mentioned complex carrier of this solution impregnation 99.7g.Placed 4 hours under the room temperature of dipping back, change in the baking oven, 105 ℃ dry 12 hours down, put into Muffle furnace then, at room temperature with 10 ℃/min temperature programming to 500 ℃, constant temperature calcining 3 hours prepares adsorbent precursor (P).
Embodiment 2
Accurate weighing 7.902g Co (NO 3) 26H 2O, add the 36ml deionized water dissolving, with this solution impregnation 40g adsorbent precursor P, placed 4 hours under the room temperature of dipping back, change in the baking oven, 105 ℃ dry 12 hours down, put into Muffle furnace then, at room temperature with 10 ℃/min temperature programming to 500 ℃, constant temperature calcining 5 hours prepares NO adsorbent (YC-1).
Embodiment 3
Accurate weighing 7.925g Ni (NO 3) 26H 2O adds the 36ml deionized water dissolving, with this solution impregnation 40g adsorbent precursor P, prepares NO adsorbent (YC-2) according to the method for operating of embodiment 2.
Embodiment 4
Accurate weighing 7.138g Mn (CH 3COO) 24H 2O adds the 37ml deionized water dissolving, with this solution impregnation 40g adsorbent precursor P, prepares NO adsorbent (YC-3) according to the operation of embodiment 2.
Embodiment 5
Accurate weighing 2.941g Mn (CH 3COO) 24H 2O and 3.492g Co (NO 3) 26H 2O adds the 38ml deionized water dissolving, with this solution impregnation 40g adsorbent precursor P, makes adsorbent (YC-4) according to the method for operating of embodiment 2.
Embodiment 6
Accurate weighing 2.941g Mn (CH 3COO) 24H 2O and 3.490g Ni (NO 3) 26H 2O adds the 37ml deionized water dissolving, with this solution impregnation 40g adsorbent precursor P, makes adsorbent (YC-5) according to the method for operating of embodiment 4.
With the above-mentioned adsorbent for preparing, under the normal temperature and pressure in fixed bed isolation of purified CO 2-NO can be removed to 150-200ppmv NO below the 0.1ppmv; Under the oxygen free condition, in the time of 20 ℃, YC-1 and YC-2 to penetrate (the dynamics breakthrough point is set at 1ppmv) adsorbance be 3.7mg/g and 3.5mg/g; (7%O under the aerobic conditions 2), room temperature, YC-1, YC-2, YC-3, YC-4 and YC-5 are to NO xAdsorbance be respectively 6.1mg/g, 3.4mg/g, 4.7mg/g, 7.4mg/g and 5.2mg/g (in NO).

Claims (7)

1. an adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide, it is characterized in that sneaking into aluminium oxide with the molecular sieve of the same race of Different Silicon aluminum ratio is active component as carrier, transition metal ions and oxide thereof, under anaerobic and aerobic conditions, remove trace amount of nitric oxide in the carbon dioxide respectively, this adsorbent is made up of moulded zeolite molecular sieve and active component, and it is specifically composed as follows:
(1) carrier is formed and content
HZSM-5 zeolite molecular sieve content accounts for the 20-90% of adsorbent total amount
Boehmite content accounts for the 10-80% of adsorbent total amount
(2) active component kind and content
Co salt, content account for the 1-10% of adsorbent gross weight
Ni salt, content account for the 1-10% of adsorbent gross weight
Mn salt, content account for the 1-10% of adsorbent gross weight
Ce salt, content account for the 0.1-2% of adsorbent gross weight.
2. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 1; It is characterized in that preparation of adsorbent was divided into for two steps:
The first step, the preparation of carrier
Take by weighing certain amount of H ZSM-5 and a certain amount of boehmite, zeolite molecular sieve: boehmite=20-90: 10-50, after both are fully mixed, add rare nitric acid of 5% and mix into grains of sand shape, it is extruded into diameter is bar about 2.5mm, after drying, room temperature puts into baking oven, 90-120 ℃ of drying 12 hours places Muffle furnace then, and at room temperature the speed with 10 ℃/min is warming up to 550 ℃, constant temperature calcining 5 hours is made zeolite molecular sieve-alumina composite carrier;
Second step, the load of active component and activation
Adopt the method for incipient impregnation, accurately weighing accounts for the Ce salt of weight 0.1-2% in the adsorbent, adding deionized water dissolves, add the drying and moulding carrier HZSM-5 for preparing, at room temperature placed 4-5 hour, it is following dry 12 hours to put into 105 ℃ in baking oven subsequently, be transferred in the Muffle furnace then, under the room temperature with 10 ℃/min temperature programming to 400-500 ℃, and constant temperature 3 hours makes the adsorbent precursor; And then accurately weighing accounts for a kind of in Co, the Ni of the 1-10% of adsorbent weight or the Mn salt or two kinds, use deionized water dissolving, add the adsorbent precursor and carry out double-steeping, then the double-steeping thing is implemented and preparation adsorbent precursor identical operations, make adsorbent.
3. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 2; It is characterized in that the adsorbent for preparing applies to oxygen free condition following time, on the adsorbent precursor for preparing, flood a kind of in Co, Ni or the Mn salt.
4. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 2; It is characterized in that the adsorbent for preparing applies to contain oxygen condition following time, floods a kind of or Co and Mn or Ni and two kinds of slaines of Mn in Co, Ni and the Mn salt on the adsorbent precursor for preparing.
5. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 4, it is characterized in that flooding two kinds of slaine mol ratios is 1: 1.
6. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 4 is characterized in that containing oxygen condition oxygen concentration≤7%.
7. a kind of adsorbent and preparation method who removes trace amount of nitric oxide in the carbon dioxide according to claim 1 is characterized in that the SiO of HZSM-5 molecular sieve 2/ Al 2O 3Be 25,38,50.
CNA2008100119551A 2008-06-19 2008-06-19 Adsorbing agent for removing trace amount of nitric oxide in carbon dioxide and preparation Pending CN101298037A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736458A (en) * 2014-01-08 2014-04-23 中国科学院过程工程研究所 Preparation method of NOx adsorbent operated at room temperature
CN105833867A (en) * 2016-04-22 2016-08-10 大连理工大学 Preparation method for Au-Ce/AlTiOx applied to NO+CO reaction and application thereof
CN112808230A (en) * 2020-12-24 2021-05-18 大连理工大学 Preparation method of Cu (I)/Y adsorbent and application thereof in dynamic removal of low-concentration CO
CN114433011A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 Adsorbent for removing nitride in aromatic hydrocarbon and preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103736458A (en) * 2014-01-08 2014-04-23 中国科学院过程工程研究所 Preparation method of NOx adsorbent operated at room temperature
CN103736458B (en) * 2014-01-08 2016-07-06 中国科学院过程工程研究所 A kind of preparation method of the NOx adsorbent of ambient operation
CN105833867A (en) * 2016-04-22 2016-08-10 大连理工大学 Preparation method for Au-Ce/AlTiOx applied to NO+CO reaction and application thereof
CN105833867B (en) * 2016-04-22 2018-07-13 大连理工大学 A kind of Au-Ce/AlTiO applied to NO+CO reactionsxPreparation method and applications
CN114433011A (en) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 Adsorbent for removing nitride in aromatic hydrocarbon and preparation method and application thereof
CN114433011B (en) * 2020-10-20 2023-07-04 中国石油化工股份有限公司 Adsorbent for removing nitride in aromatic hydrocarbon and preparation method and application thereof
CN112808230A (en) * 2020-12-24 2021-05-18 大连理工大学 Preparation method of Cu (I)/Y adsorbent and application thereof in dynamic removal of low-concentration CO

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Application publication date: 20081105