CN104117343A - Preparation method of renewable low concentration CO2 high efficient absorption material - Google Patents
Preparation method of renewable low concentration CO2 high efficient absorption material Download PDFInfo
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Abstract
The invention discloses a preparation method of a renewable low concentration CO2 high efficient absorption material, and aims to provide a preparation method of a renewable low concentration CO2 high efficient absorption material which has the advantages of low energy consumption, good absorption selectivity, and large absorption quantity of low partial pressure CO2. The technical scheme comprises the following steps: preparing silica sol and an amino siloxane solution, evenly mixing the silica sol and the amino siloxane solution, then mixing the mixed sol with dimethyl silicone oil, stirring to form suspension liquid, stirring at the same temperature of the sol until gel is formed; then heating the mixture to a temperature of 40 to 60 DEG C, allowing the mixture to stand still for aging for 1 to 9 days at a temperature of 40 to 60 DEG C, filtering to obtain the spherical gel; and finally putting the spherical gel and ethanol into supercritical drying equipment to dry the gel. The prepared renewable low concentration CO2 high efficient absorption material has the advantages of good uniformity, high nitrogen content, high specific surface area, large pore volume, and large CO2 absorption capacity.
Description
Technical field
The present invention relates to a kind of CO
2the preparation method of sorbing material, relates in particular to a kind of renewable low concentration CO
2the preparation method of efficient adsorption material.
Technical background
Carbon dioxide (CO
2) be one of constituent of nature atmosphere, the content in atmosphere very low (being about 0.03%), can not exert an influence to mankind's activity.But in the confined spaces such as submarine, space station, manned deep-sea vehicle, underground national defence fortification, because personnel breathe, (in tranquil situation, exhalation 20-25LCO per hour is grown up
2) etc. reason CO
2concentration constantly raises.Research is found, is worked as CO
2when concentration is greater than 1% (the about 1KPa of dividing potential drop), personnel just there will be feel dizzy, the CO such as thought slowness
2poisoning symptom.Therefore must remove unnecessary CO
2to guarantee personnel health.
Solid amine refers to a kind of weak-base anion-exchange resin of high porosity traditionally, is pore-forming in the styrene-divinylbenzene copolymer of certain molecular weight, certain degree of cross linking, then introduces the solid-state copolymer that amido forms.Now various to take compared with bigger serface solid be matrix, introduces the sorbing material that amido obtains be referred to as solid amine by overlap joint, modification, impregnating method.Solid amine has abundant amido, can with CO
2chemical reaction occurs to be realized CO
2selective absorption, under the condition of step-down or heating, can make again reaction carry out in the other direction, realize CO
2desorption, there is selectively good, the feature such as energy consumption is low, easy regeneration, be CO
2one of the emphasis of sorbing material research and focus.
At present, the preparation method of solid amine mainly contains grafting and floods two kinds.Wherein, method that infusion process is mainly flooded by physics is introduced amido, and the amido total amount that the solid amine that this method obtains can be introduced is larger, and adsorbance is higher, but there is no being connected of chemical bond, less stable between amido and matrix; And grafting is mainly introduced amido on matrix by chemical reaction, the solid amine amido that this method obtains is mainly connected with matrix by chemical bond, and heat endurance is higher, and simultaneously its amido high degree of dispersion is at carrier surface, easily and CO
2effect, the rate of adsorption and unit amido adsorbance are all higher than infusion process, but the amido total amount that grafting is introduced is limited, and adsorbance is lower.
The Chinese patent that application number is [201010102582.6] has been announced a kind of absorption method and has been removed CO in gas
2method, the method is carried out amination with the resin of swelling and is prepared amine resin, and amine resin is activated, the amine resin activating of take is that adsorbent is removed CO
2.But its adsorbance is lower, and CO
2pressure is higher, at CO
2when dividing potential drop is 6%, adsorbance is 1.45mmol/g (63.7mg/g), as for the CO under low-pressure more
2in adsorbance document, do not provide.
The Chinese patent that application number is [201010118752.X] has been announced a kind of CO absorption
2with porous carbon composite material and its preparation method and application, the method adopts infusion process to prepare sorbing material, first makes porous charcoal, then floods polymine and prepares porous carbon composite material.Preparation material at 50 ℃～110 ℃ to pure CO
2adsorbance can reach 3.64mmol/g (160mg/g) more than, but its CO
2pressure is very high and adsorption temp is higher, is unsuitable for the environment (CO of confined space
2pressure is no more than 1KPa, and temperature is normal temperature), and in document, do not provide its circulation adsorption desorption performance.
The Chinese patent that application number is [200510012772.8] has been announced a kind of efficient adsorption CO
2organic-amine-porous composite material, the method is with the synthetic former powder direct impregnation organic amine of mesoporous material, utilizes template micella to disperse organic amine synthetic composite material.This material at 75 ℃ to 5% CO
2adsorbance can reach 3.23mmol/g (142mg/g), but its adsorption temp and pressure are all higher, and adsorbance has declined approximately 4.23% after 7 circulation adsorption desorptions.
Document [K.
m.Alnaief, I.Smirnova.Amino functionalised Silica-Aerogels for CO
2-adsorption at lowpartial pressure.Adsorption, 2012,18:163-171] adopt copolycondensation and two kinds of different grafting methods of post-modification to prepare CO
2sorbing material, and contrast, material nitrogen content higher (reaching as high as 5.2wt%) CO prepared by post-modification found
2adsorbance is also taller and bigger (at 22 ℃ to 0.25% CO
2adsorbance is 0.523mmol/g), and material prepared by copolycondensation adsorbance is under the same conditions no more than 0.1mmol/g.But post-modification method need to be passed through long modified solution replacement process, and manufacturing cycle is long, and is difficult to guarantee the uniformity of material.
Document [Cui.et.al, Mesoporous amine-modified SiO
2aerogel:a potential CO
2sorbent.Energy & Environmental Science, 2011] adopt the method for post-modification to prepare amino modified silica aerogel, its nitrogen content is 3.04wt%, at CO
2be respectively in 10% atmosphere its CO with steam volume content
2adsorbance reaches as high as 7mmol/g (25 ℃) and 3.8mmol/g (50 ℃).But, its CO
2all very high with water content, and also exist manufacturing cycle long, be difficult to guarantee the problems such as material homogeneity.
In summary, current solid amine is to low concentration CO
2adsorbance generally less, and exist circulation suctions/desorption adsorbance to decline or the deficiency such as manufacturing cycle length, lack of homogeneity, so all there is certain defect in above method.
Summary of the invention
Object of the present invention is exactly to overcome the defect that above technology exists, and provides that a kind of energy consumption is low, adsorptive selectivity good, low dividing potential drop CO
2adsorbance is large, suction/desorption rate is fast, desorption conditions is gentle, the renewable low concentration CO of circulation adsorption desorption stable performance
2efficient adsorption material.
The object of the invention is to be achieved through the following technical solutions, mainly comprise configuration colloidal sol, balling-up, aging, dry four steps, concrete steps are as follows:
The first step, preparation colloidal sol: difference prepare silicon colloidal sol and amino silicone solution, siloxanes, water, ethanol (technical pure), acidic catalyst are mixed according to mol ratio 1:0～4:3～20:0.0018, standing approximately 2 hours, add the base catalyst with acidic catalyst equimolar amounts, after mixing, according to siloxanes: water mol ratio is that water is supplied in 1:6～8, mix and temperature is adjusted to 5～-25 ℃, obtaining Ludox; By amino silicone (0.35～0.65 times that mole is siloxanes) and ethanol according to the siloxanes mixed in molar ratio identical with ethanol evenly (being that ethanol is 3～20 times of amino silicone), and be adjusted to the temperature identical with Ludox, obtain amino silicone solution;
Described siloxanes is ethyl orthosilicate (analyzing pure), methyl silicate (analyzing pure) or its mixture;
Described amino silicone is one or more the mixture in aminopropyl triethoxysilane (analyzing pure), aminopropyl trimethoxysilane (analyzing pure), aminoethyl aminopropyl triethoxysilane (analyzing pure), methyl aminopropyl diethoxy silane (analyzing pure);
Described acidic catalyst is hydrochloric acid (analyzing pure), nitric acid (analyzing pure) or acetic acid (analyzing pure);
Described base catalyst is ammoniacal liquor (analyzing pure), NaOH or sodium carbonate;
Second step, balling-up: the Ludox that the first step is obtained and amino silicone solution mix, and obtain mixed sols.Dimethicone (technical pure) is adjusted to the temperature identical with mixed sols, under the condition constantly stirring, mixed sols and dimethicone are joined in dimethicone for 1:3～20 by volume, obtain mixed sols suspension, keep identical mixing speed, until mixed sols generation gel obtains spherical gel suspension;
Described stirring is mechanical agitation or magnetic agitation;
Described mixing speed is 40～1000r/min;
The 3rd step, aging: the spherical gel suspension that second step is obtained continues to stir 10～50min, is warming up to 40～60 ℃, at this temperature standing aging 1～9 day, then with screen filtration, obtain spherical gel;
The 4th step, dry: the spherical gel that the 3rd step is obtained and ethanol (technical pure) are together placed in supercritical drying equipment, the nitrogen of preliminary filling 0.5～2.5Mpa, speed with 1～3 ℃/min is warming up to 270 ℃, be incubated 2 hours, again with the speed release pressure of 100KPa/min, finally, with nitrogen blowing 30 minutes, with stove is cooling, can obtain renewable low concentration CO
2efficient adsorption material.
Adopt the present invention can reach following technique effect:
(1) first step of the present invention and second step all adopt liquid mode of mixing, and can make raw material mix on molecular level, thereby avoid preparation discontinuity of material, the renewable low concentration CO of preparation
2efficient adsorption material homogeneity is good;
(2) the present invention changes the hydrolysis ratio of alkoxyl on siloxanes by the mol ratio of adjusting water and siloxanes in the first step, in the 3rd step, by adjusting aging temperature and ageing time, change the degree of carrying out of graft reaction, process of grafting is controlled in acting in conjunction by two steps, improved the nitrogen content of material, the renewable low concentration CO of preparation
2efficient adsorption material nitrogen content is high, and nitrogen silicon mol ratio can reach 0.28;
(3) the present invention prepares material by sol-gel process, by low temperature gel, reduces gel time, has improved the uniformity of structure, the renewable low concentration CO of preparation when strengthening process operability
2efficient adsorption material specific area is high, can reach 800m
2/ g, pore volume is large, can reach 5.29cm
3/ g, specific heat capacity is little, is 1.23 ± 0.03J/gK;
(4) the renewable low concentration CO that prepared by the present invention
2efficient adsorption material nitrogen content is high, specific area is large, so its low dividing potential drop CO
2adsorbance is large, at CO
2dividing potential drop is 0.5KPa, and temperature is 25 ℃, and relative humidity is the CO under 60% condition
2adsorbance can reach 1.85mmol/g;
(5) the present invention is usingd amino silicone and is originated as amido, thereby it can make amido be connected to equably gel skeleton surface by chemical bond with siloxanes generation hydrolysis condensation reaction, therefore the renewable low concentration CO of preparation
2efficient adsorption material circulation adsorption desorption stability is high, does not consider adsorption desorption for the first time, and after 9 circulations, declining does not appear in adsorbance;
(6) the present invention can change the character such as its structure, specific area, aperture, nitrogen content by regulating the factors such as raw material proportioning, preparation technology, thereby makes the renewable low concentration CO of preparation
2efficient adsorption material meets the needs of specific environment;
(7) with respect to post-modification method, the present invention has saved the time of modified solution displacement, and manufacturing cycle is short, and speed of production is fast;
(8) second step of the present invention can be prepared spherical renewable low concentration CO by suspension balling-up technology
2efficient adsorption material, due to spherical renewable low concentration CO
2therefore efficient adsorption material does not have corner angle, uses more conveniently, and is difficult for producing dust.
The specific embodiment
The invention will be further described below to use embodiment, but these embodiment do not produce any restriction to protection scope of the present invention.
Embodiment 1
(1) by the 1:1:5:0.0018 mixing in molar ratio of ethyl orthosilicate, water, ethanol, hydrochloric acid, after standing 2 hours, add the ammoniacal liquor with amount of substances such as hydrochloric acid, and be that 1:7 supplies water by ethyl orthosilicate and water mol ratio, adjust temperature to-15 ℃, obtain Ludox; By aminopropyl triethoxysilane (0.65 times that amount of substance is ethyl orthosilicate) and ethanol in molar ratio 1:5 mix, and adjust temperature to-15 ℃, obtain amino silicone solution;
(2) Ludox and amino silicone solution are mixed, obtain mixed sols.Dimethicone is adjusted to-15 ℃, low whipping speed is under the mechanical agitation condition of 200r/min, by mixed sols and dimethicone by volume 1:5 join in dimethicone, obtain mixed sols suspension, keep mixing speed until mixed sols generation gel obtains spherical gel suspension;
(3) spherical gel suspension is continued to stir 20min, be warming up to 50 ℃ aging 2 days, filter and obtain spherical gel;
(4), after aging completing, spherical gel and ethanol are placed in supercritical drying still to the nitrogen of preliminary filling 2MPa, speed with 2 ℃/min is warming up to 270 ℃, is incubated 2 hours, with the speed release pressure of 100KPa/min, nitrogen blowing 30 minutes, obtains renewable low concentration CO after cooling with stove
2efficient adsorption material.
Adopt digital camera to the renewable low concentration CO on graph paper
2efficient adsorption material is taken pictures, and statistics shows, renewable low concentration CO
2the average diameter of efficient adsorption material microballoon is 1.86mm, and sphericity is better.
Adopt the avatar360 infrared spectrometer of U.S. Nicolet company to test renewable low concentration CO
2the infrared spectrum of efficient adsorption material and pure silica aeroge.From FT-IR spectrogram, can find out renewable low concentration CO
2the absworption peak explanation amido that has occurred N-H and Si-C key on the spectral line of efficient adsorption material has been connected on aeroge skeleton, and through Kjeldahl's method and the test of silicon molybdenum blue AAS, its nitrogen content is 3.89wt% (nitrogen silicon ratio is 0.28).
Adopt ESCALAB250Xi type x-ray photoelectron spectroscopy to obtain renewable low concentration CO
2the photoelectron spectroscopy figure on efficient adsorption material (interior) surface, its surface nitrogen content is 7.44wt% (surface nitrogen silicon ratio is 0.43) by analysis.
Adopt the SDTQ600 type thermogravimetric analyzer of U.S. TA company to measure renewable low concentration CO
2the TG-DSC curve of efficient adsorption material.From TG-DSC spectrogram, can find out water, CO due to its absorption
2deng desorption, the process that material has a weight sharply to decline 105 ℃ of front and back; Meanwhile, material can stable existence in being less than the air atmosphere of 210 ℃, and this has guaranteed normally carrying out of material regeneration.
Adopt the renewable low concentration CO of Dynamic Adsorption testing of equipment
2the CO of efficient adsorption material
2dynamic adsorption, test condition is: the pressure of adsorbed gas is an atmospheric pressure, consists of 0.5% CO
2, 20.69% O
2, all the other are N
2, relative humidity is 60%, and gas flow rate is 50ml/min, and adsorption temp is 25 ℃.The renewable low concentration CO of embodiment 1 preparation
2the saturated extent of adsorption of efficient adsorption material is 1.85mmol/g, and penetrating adsorbance is 1.09mmol/g.From renewable low concentration CO
2the CO of efficient adsorption material
2in adsorption breakthrough curve figure, can find out that curve is very large at ascent stage slope, illustrate that the rate of adsorption is very fast.At CO
2dividing potential drop is that under the dry atmosphere of 1KPa, its adsorbance is 1.28mmol/g (25 ℃).
Adopt the SDTQ600 type thermogravimetric analyzer of U.S. TA company to measure renewable low concentration CO
2the circulation adsorption desorption performance of efficient adsorption material, desorption atmosphere is nitrogen, and the time is 30min, and temperature is 100 ℃.From renewable low concentration CO
2the CO of efficient adsorption material
2in circulation absorption amount column diagram, can find out, not consider to circulate for the first time, renewable low concentration CO
2declining does not appear in efficient adsorption material adsorbance after 9 circulations; Difference as for circulation for the first time with follow-up circulation, is mainly because there are some unsettled group and particles in freshly prepd material, and after once circulating, these destabilizing factors are eliminated, and therefore follow-up circulation performance is comparatively stable.
Adopt the autosorb-1 type Full-automatic physical adsorption instrument of U.S. Kang Ta company to test renewable low concentration CO
2the specific area of efficient adsorption material and pore volume.The renewable low concentration CO that after tested prepared by embodiment 1
2the specific area of efficient adsorption material is 336.95m
2/ g, pore volume is 1.86cm
3/ g.
Embodiment 2～24
The technological parameter that embodiment 2～24 adopts is as shown in table 1, because affect renewable low concentration CO
2the technological parameter of efficient adsorption material main performance is mainly the mol ratio of mol ratio, amino silicone and siloxanes of mol ratio, ethanol and the siloxanes of water and siloxanes in Ludox, 5 parameters such as the kind of amino silicone and gelling temps, and the time of acid, the kind of base catalyst and the kind major effect gel of consumption and siloxanes, little on its main performance impact, so main these 5 technological parameters that change of embodiment 2～24 are further to explain the present invention.In table, write technological parameter, all the other technological parameters are identical with embodiment 1.
In table 1, the technological parameter of embodiment 2～17 adopts the thought and method of orthogonal design that (that is, amino silicone selection aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, methyl aminopropyl diethoxy silane are set; Water and siloxanes mol ratio select 0,2,3,4; Ethanol and siloxanes mol ratio select 3,5,10,20; Amino silicone and siloxanes mol ratio select 0.35,0.5,0.6,0.65; Gelling temp is selected 5 ℃ ,-5 ℃ ,-15 ℃ ,-25 ℃.According to orthogonal table L
16(4
5) arrange to test), according to document [department of mathematics of Institutes Of Technology Of Taiyuan. Probability Theory and Math Statistics. Beijing: the .2009:185-190. of Science Press] and [Zhao voter. test design method. Beijing: the .2006:62-118 of Science Press], the effect that these embodiment obtain with carry out comprehensive test (4
5=1024 times) effect that obtains is similar, by data analysis and process, can show that each factor is for renewable low concentration CO
2efficient adsorption material main performance affect rule.
The renewable low concentration CO of table 1
2the preparation technology parameter of efficient adsorption material and partial properties
Claims (9)
1. a renewable low concentration CO
2the preparation method of efficient adsorption material, is characterized in that comprising the following steps:
The first step, preparation colloidal sol: difference prepare silicon colloidal sol and amino silicone solution, siloxanes, water, ethanol, acidic catalyst are mixed according to mol ratio 1:0～4:3～20:0.0018, standing 2 hours, add the base catalyst with acidic catalyst equimolar amounts, after mixing, according to siloxanes: water mol ratio is that water is supplied in 1:6～8, mix and temperature is adjusted to 5～-25 ℃, obtaining Ludox; The amino silicone of 0.35～0.65 times that is siloxanes by mole is even according to the siloxanes mixed in molar ratio identical with ethanol with ethanol, and is adjusted to the temperature identical with Ludox, obtains amino silicone solution;
Second step, balling-up: the Ludox that the first step is obtained and amino silicone solution mix, and obtain mixed sols; Dimethicone is adjusted to the temperature identical with mixed sols, under the condition constantly stirring, mixed sols and dimethicone are joined in dimethicone for 1:3～20 by volume, obtain mixed sols suspension, keep identical mixing speed, until mixed sols generation gel obtains spherical gel suspension;
The 3rd step, aging: the spherical gel suspension that second step is obtained continues to stir 10～50min, is warming up to 40～60 ℃, at this temperature standing aging 1～9 day, then with screen filtration, obtain spherical gel;
The 4th step, dry: spherical gel and ethanol that the 3rd step is obtained are together placed in supercritical drying equipment, the nitrogen of preliminary filling 0.5～2.5Mpa, speed with 1～3 ℃/min is warming up to 250～290 ℃, be incubated 2 hours, again with the speed release pressure of 100KPa/min, finally with nitrogen blowing 30 minutes, with stove is cooling, obtain renewable low concentration CO
2efficient adsorption material.
2. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described siloxanes is ethyl orthosilicate, methyl silicate or its mixture, and it is pure that ethyl orthosilicate and methyl silicate are analysis.
3. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described amino silicone is one or more the mixture in aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, methyl aminopropyl diethoxy silane; It is pure that aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, methyl aminopropyl diethoxy silane are analysis.
4. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described acidic catalyst is hydrochloric acid, nitric acid or acetic acid, and it is pure that hydrochloric acid, nitric acid or acetic acid are analysis.
5. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described base catalyst is ammoniacal liquor, NaOH or sodium carbonate; Ammoniacal liquor is pure for analyzing.
6. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described ethanol is technical pure.
7. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described dimethicone is technical pure.
8. a kind of renewable low concentration CO as claimed in claim 1
2the preparation method of efficient adsorption material, is characterized in that described agitating mode is mechanical agitation or magnetic agitation.
9. a kind of renewable low concentration CO as claimed in claim 8
2the preparation method of efficient adsorption material, is characterized in that described mixing speed is 40～1000 turn/min.
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