CN101543761A - Method for improving adsorption quantity of high zeolite carbon dioxide - Google Patents

Method for improving adsorption quantity of high zeolite carbon dioxide Download PDF

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Publication number
CN101543761A
CN101543761A CN200910074031A CN200910074031A CN101543761A CN 101543761 A CN101543761 A CN 101543761A CN 200910074031 A CN200910074031 A CN 200910074031A CN 200910074031 A CN200910074031 A CN 200910074031A CN 101543761 A CN101543761 A CN 101543761A
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zeolite
solution
naoh
value
type body
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CN200910074031A
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CN101543761B (en
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马静红
王云飞
崔杏雨
李瑞丰
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Taiyuan University of Technology
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Taiyuan University of Technology
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention relates to a method for improving adsorption quantity of high zeolite carbon dioxide, and belongs to the field of preparation of inorganic materials and sorbents. The method is characterized in that the method uses mixed dilute alkali solution of sodium carbonate and sodium hydroxide to treat 13X zeolite to improve the CO2 adsorption capacity of the zeolite. The method comprises the following steps: firstly, preparing the mixed solution of the sodium carbonate and the sodium hydroxide, adjusting the pH value of the solution by the concentration and adding amount of the sodium hydroxide, and then putting the powder or bond-containing model 13X zeolite into the mixed solution to carry out thermal treatment. Compared with the untreated zeolite, the relative crystallinity and specific surface area of the treated 13X zeolite are increased so as to improve the CO2 adsorption quantity of the 13X zeolite. The method is simple and practical, has low consumption, and is suitable for separation, reclamation and purification of CO2.

Description

A kind of method that improves adsorption quantity of high zeolite carbon dioxide
Technical field
A kind of method that improves adsorption quantity of high zeolite carbon dioxide of the present invention belongs to inorganic material and adsorbent preparation field.In particular to a kind of method that improves the 13X adsorption quantity of high zeolite carbon dioxide.
Background technology
At fossil fuel, particularly all contain a large amount of CO in the gas that industrial process such as burning of coal gas and steel-making blast furnace gas, lime-kiln gas, synthetic-ammonia transformation gas produce 2, its direct discharging not only causes serious greenhouse effects, but also causes the great wasting of resources, therefore, and research and development CO 2Separation and recovery technology, it is significant to reduce CO2 emission.In addition, in many commercial gas are used, need amounts of carbon dioxide wherein be removed with purified gases, for example use Deep Cooling Method and produce before nitrogen and the oxygen, need airborne CO 2Thereby remove fully with water and to prevent that its freezing at low temperatures from causing that equipment stops up.Transformation (alternating temperature) absorption is a kind of CO with extensive use 2Absorption is reclaimed and purification technique, and it is to utilize the solid porous adsorbent to the CO in the material mixed gas 2Carry out selectable reversible adsorption and realize CO 2Adsorbing separation.Therefore, no matter be from being rich in CO 2Industrial tail gas in reclaim the angle of carbon dioxide, still to containing trace amounts of CO 2Gas carry out the angle of purifying, research and development has high CO 2The sorbing material of absorption property all is crucial.
With respect to silica gel, aluminium oxide and acticarbon, X zeolite usually is selected as CO with its higher adsorption capacity and selectivity 2Adsorbent.In order further to improve its adsorption capacity to improve CO 2Separate and reclaim and the efficient of purifying and the energy consumption of the process of reduction, US3885927, US4477267 and US4775396 propose to adopt Ba respectively 2+, Ca 2+, Zn 2+Be used for CO with the X type zeolite of cation exchange such as rare earth metal 2Absorption; CN99803798.2 disclose with Si/Al than be the low silicon X zeolite (LSX) of 1-1.15 but mix with the kaolin of zeolitization, soak and the high CO of sodium exchange preparation through moulding, sodium hydroxide solution 2The method of adsorption capacity adsorbent; The concentration that CN98116154.5 points out to be used to soak the sodium hydroxide solution of LSX zeolite and binder mixtures is at least 0.5M.Zhonglin Zhao etc. has reported that the sodium hydroxide solution with 1.0-1.2M carries out modification to containing 20% kaolinic type body 13X zeolite adsorbents, thereby has improved in the adsorbent content of effective and to CO 2Adsorbance (Journal of greenhouse gas control, 2007,1 (3), 355-359).
Summary of the invention
A kind of purpose that improves the method for adsorption quantity of high zeolite carbon dioxide of the present invention provides a kind of mixing dilute alkaline soln with sodium carbonate and NaOH type body 13X zeolite powdery or that contain binding agent is handled, and improves 13X zeolite CO 2The technical scheme of the method for adsorbance.
A kind of method that improves adsorption quantity of high zeolite carbon dioxide of the present invention, it is characterized in that it being that a kind of mixing dilute alkaline soln with sodium carbonate and NaOH is handled type body 13X zeolite powdery or that contain binding agent, wherein the pH value of mixed solution is regulated by concentration sodium hydroxide and addition, by improving the degree of crystallinity and the specific area of 13X zeolite, improve the 13X zeolite to CO 2The method of adsorbance, the concrete operations step is: the Na of preparation 0.5-1.0mol/L 2CO 3With the NaOH solution of 0.2-0.6mol/L, get Na 2CO 3Solution adds NaOH solution and regulates Na 2CO 3The pH value of/NaOH mixed solution is to 11.5-13.8; Add the 13X zeolite sample to this Na by liquid-solid ratio 3-40ml/g 2CO 3In/NaOH the solution, under constantly stirring, be heated to 70-100 ℃, kept 3-10 hour, liquid is poured out in cooling, adds the Na of fresh identical pH value with the front and equivalent once more 2CO 3/ NaOH solution is handled once more to the 13X zeolite under the same conditions, and then, Separation of Solid and Liquid washes zeolite sample with water under 70-90 ℃, 100-120 ℃ of drying.
According to above-described a kind of raising 13X zeolite CO 2The method of adsorbance is characterized in that described zeolite 13X is that Si/Al compares for the powdery 13X zeolite of 1.15-1.30 or the type body 13X zeolite that is formed by this 13X zeolite powder adding 15-25% kaolin or concavo-convex excellent binding agent, for powdery 13X zeolite, and its Na 2CO 3The preferred pH value scope of/NaOH treatment fluid is 11.5-13.2; For the type body 13X zeolite that includes binding agent, its Na 2CO 3The preferred pH value scope of/NaOH treatment fluid is 13.0-13.8.
A kind of method that improves adsorption quantity of high zeolite carbon dioxide of the present invention, what provided passes through Na 2CO 3/ NaOH mixed solution is handled to improve its CO the 13X zeolite 2The advantage of the method for adsorbance is: can significantly improve 13X zeolite CO 2Adsorption capacity, the adsorption capacity of treated 13X zeolite can improve 1-35% before handling.Method is simple, expends cheap.The 13X zeolite of handling through this method can be used as adsorbent and is used for transformation (alternating temperature) CO absorption 2Capture reclaim and contain CO 2Gas cleaning, thus CO improved 2Separate the efficient of recovery and purification process, and reduce its energy consumption.
Four, the specific embodiment
Embodiment 1:
Regulate 0.8mol/L Na with 0.2mol/L NaOH solution 2CO 3The pH to 12.6 of solution gets wherein 150ml to flask, adds the former powder of 5.0g zeolite 13X, under constantly stirring, heats this solidliquid mixture to 80 ℃ and keeps 5 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, and Separation of Solid and Liquid is washed and drying the zeolite after handling then.It is 102% with respect to the relative crystallinity of the former powder of 13X that X-ray diffraction records this sample, and the BET specific area is by the 556m of the former powder of 13X before handling 2/ g brings up to 580m 2/ g; Use weight adsorption, after 320 ℃ of vacuum activate 4 hours, at 25 ℃ and P CO2=10 2Measure the CO of this sample and the former powder of 13X under the kPa condition 2Adsorption capacity, its value is 135ml/g and 124ml/g respectively.
Embodiment 2:
Regulate 1.0mol/LNa with 0.3mol/LNaOH solution 2CO 3The pH to 13.1 of solution gets wherein 150ml to flask, adds the former powder of 5.0g zeolite 13X, adopts the processing mode identical with embodiment 1 that the former powder of 13X is handled.The relative crystallinity that records sample is 103%, and the BET specific area is 600m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is 137ml/g.
Embodiment 3:
Regulate 0.5mol/L Na with 0.2mol/L NaOH solution 2CO 3The pH to 11.6 of solution gets wherein 50ml to flask, adds the former powder of 5.0g zeolite 13X, adopts the processing mode identical with embodiment 1 that the former powder of 13X is handled.The relative crystallinity that records sample is 101%, and the BET specific area is 565m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is 128ml/g.
Embodiment 4:
With content by weight is that 25% powdery kaolin mixes with the former powder of 13X, adds the water moulding, 120 ℃ of oven dry; 600 ℃ of roastings 4 hours, obtain including kaolinic type body 13X zeolite then.Get wherein 5g type body zeolite and put into flask, add prior adjusted pH value and be 13.1 Na 2CO 3/ NaOH solution 90ml under constantly stirring, heats this solidliquid mixture to 90 ℃ and kept 5 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, washs solid and dry then.After measured, the relative crystallinity before and after this type body zeolite treatment is respectively 75% and 89%, and the BET specific area is respectively 433m 2/ g and 452m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is distinguished 88ml/g and is 105ml/g.
Embodiment 5:
Press embodiment 3 preparation type body 13X zeolites, get wherein 5g type body zeolite and put into flask, add prior adjusted pH value and be 13.6 Na 2CO 3/ NaOH solution 150ml under constantly stirring, heats this solidliquid mixture to 90 ℃ and kept 5 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, washs solid and dry then.The relative crystallinity of handling the back sample is respectively 95%, and the BET specific area is 505m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is 122ml/g.
Embodiment 6:
With content by weight is that 20% powdery kaolin mixes with the former powder of 13X, adds the water moulding, 120 ℃ of oven dry; 600 ℃ of roastings 4 hours, obtain including kaolinic type body 13X zeolite then.Get wherein 5g type body zeolite and put into flask, add prior adjusted pH value and be 13.6 Na 2CO 3/ NaOH solution 50ml under constantly stirring, heats this solidliquid mixture to 90 ℃ and kept 6 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, washs solid and dry then.After measured, the relative crystallinity before and after this type body zeolite treatment is respectively 80% and 96%, and the BET specific area is respectively 445m 2/ g and 462m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is distinguished 92ml/g and is 125ml/g.
Embodiment 7:
With content by weight is that 20% powdery attapulgite mixes with the former powder of 13X, adds the water moulding, 120 ℃ of oven dry; 550 ℃ of roastings 4 hours, obtain including concavo-convex excellent type body 13X zeolite then.Get wherein 5g type body zeolite and put into flask, add prior adjusted pH value and be 13.4 Na 2CO 3/ NaOH solution 150ml under constantly stirring, heats this solidliquid mixture to 90 ℃ and kept 5 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, washs solid and dry then.After measured, the relative crystallinity before and after this type body zeolite treatment is respectively 80% and 85%, and the BET specific area is respectively 488m 2/ g and 500m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is distinguished 108ml/g and is 117ml/g.
Embodiment 8:
Press embodiment 7 preparation type body 13X zeolites, get wherein 5g type body zeolite and put into flask, add prior adjusted pH value and be 13.8 Na 2CO 3/ NaOH solution 150ml under constantly stirring, heats this solidliquid mixture to 80 ℃ and kept 3 hours, pours out solution; The above-mentioned Na that adds equivalent again 2CO 3/ NaOH solution repeats said process, washs solid and dry then.The relative crystallinity of handling the back sample is respectively 83%, and the BET specific area is 495m 2/ g is at 25 ℃ and P CO2=10 2CO under the kPa condition 2Adsorption capacity is 114ml/g.

Claims (2)

1, a kind of method that improves adsorption quantity of high zeolite carbon dioxide, it is characterized in that it being that a kind of mixing dilute alkaline soln with sodium carbonate and NaOH is handled type body 13X zeolite powdery or that contain binding agent, wherein the pH value of mixed solution is regulated by concentration sodium hydroxide and addition, by improving the degree of crystallinity and the specific area of 13X zeolite, improve the 13X zeolite to CO 2The method of adsorbance, the concrete operations step is: the Na of preparation 0.5-1.0mol/L 2CO 3With the NaOH solution of 0.2-0.6mol/L, get Na 2CO 3Solution adds NaOH solution and regulates Na 2CO 3The pH value of/NaOH mixed solution is to 11.5-13.8; Add the 13X zeolite sample to this Na by liquid-solid ratio 3-40ml/g 2CO 3In/NaOH the solution, under constantly stirring, be heated to 70-100 ℃, kept 3-10 hour, liquid is poured out in cooling, adds the Na of fresh identical pH value with the front and equivalent once more 2CO 3/ NaOH solution is handled once more to the 13X zeolite under the same conditions, and then, Separation of Solid and Liquid washes zeolite sample with water under 70-90 ℃, 100-120 ℃ of drying.
2, according to the described a kind of raising 13X zeolite CO of claim 1 2The method of adsorbance is characterized in that described zeolite 13X is that Si/Al compares for the powdery 13X zeolite of 1.15-1.30 or the type body 13X zeolite that is formed by this 13X zeolite powder adding 15-25% kaolin or concavo-convex excellent binding agent, for powdery 13X zeolite, and its Na 2CO 3The preferred pH value scope of/NaOH treatment fluid is 11.5-13.2; For the type body 13X zeolite that includes binding agent, its Na 2CO 3The preferred pH value scope of/NaOH treatment fluid is 13.0-13.8.
CN2009100740310A 2009-03-25 2009-03-25 Method for improving adsorption quantity of high zeolite carbon dioxide Expired - Fee Related CN101543761B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102205972A (en) * 2011-04-19 2011-10-05 兰州大学 Modification method of attapulgite
CN106040166A (en) * 2016-06-23 2016-10-26 江西科帕克环保化工有限责任公司 Preparation method of air separation molecular sieve capable of efficiently desorbing
CN106925235A (en) * 2017-03-27 2017-07-07 东北大学 One kind can efficiently separate CO in moisture2Adsorbent and preparation method thereof
CN115417422A (en) * 2022-08-05 2022-12-02 中国石油大学(华东) Preparation method of FAU type molecular sieve adsorbent and carbon dioxide adsorption performance thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102205972A (en) * 2011-04-19 2011-10-05 兰州大学 Modification method of attapulgite
CN102205972B (en) * 2011-04-19 2013-03-20 兰州大学 Modification method of attapulgite
CN106040166A (en) * 2016-06-23 2016-10-26 江西科帕克环保化工有限责任公司 Preparation method of air separation molecular sieve capable of efficiently desorbing
CN106925235A (en) * 2017-03-27 2017-07-07 东北大学 One kind can efficiently separate CO in moisture2Adsorbent and preparation method thereof
CN106925235B (en) * 2017-03-27 2019-10-08 东北大学 One kind can efficiently separate CO in moisture2Adsorbent and preparation method thereof
CN115417422A (en) * 2022-08-05 2022-12-02 中国石油大学(华东) Preparation method of FAU type molecular sieve adsorbent and carbon dioxide adsorption performance thereof

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