CN109201007A - A kind of carbon dioxide absorber and its preparation method and application - Google Patents

A kind of carbon dioxide absorber and its preparation method and application Download PDF

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CN109201007A
CN109201007A CN201811128447.1A CN201811128447A CN109201007A CN 109201007 A CN109201007 A CN 109201007A CN 201811128447 A CN201811128447 A CN 201811128447A CN 109201007 A CN109201007 A CN 109201007A
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carbon dioxide
adsorbent
nitrogen
ionic liquid
carbon
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CN109201007B (en
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赵培玉
张国杰
徐英
孙映晖
张永发
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Taiyuan University of Technology
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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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • 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
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

The invention discloses a kind of carbon dioxide absorbers and its preparation method and application, belong to carbon dioxide absorber technical field.Adsorbent is combined by organic amine, ionic liquid and biomass carbon；Wherein biomass carbon accounts for 40 ~ 60%, and organic amine accounts for 30 ~ 50%, and ionic liquid accounts for 5 ~ 10%.Preparation method are as follows: dipping is stirred at room temperature 5 ~ 8 hours in the mixed aqueous solution of biomass carbon and organic amine, ionic liquid, then it is ultrasonically treated 2 ~ 3 hours in ultrasonator, gained mixture is freezed 20 ~ 30 minutes in -196 DEG C of liquid nitrogen, then mixture is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 ~ 48 hours, obtain collecting carbonic anhydride adsorbent.Organic amine and the preferable dispersibility of ionic liquid and stability make adsorbent have the characteristics that adsorption capacity is strong, cyclical stability is high and at low cost in the invention, can efficiently trap to carbon dioxide.

Description

A kind of carbon dioxide absorber and its preparation method and application
Technical field
The present invention relates to a kind of preparation methods of the carbon dioxide absorber of efficient stable, belong to carbon dioxide absorber system Standby technical field.
Background technique
With the development of economy and society, CO2 emissions artificial in atmosphere are continuously increased.Carbon dioxide is in atmosphere In accumulation will lead to many weathers and environmental disaster.For example, global warming, sea level rise and land desertification etc..Meanwhile Carbon dioxide has a wide range of applications as potential carbon resource in chemistry and agriculture field.Therefore, the capture of carbon dioxide It is the optimal selection for mitigating current greenhouse gas emission and recycling this potential carbon resource with separation.Especially from large-scale flue gas Trapping and separation carbon dioxide are most important to CO2 emission is reduced in source (such as coal-fired power plant and cement plant).Existing In some collecting carbonic anhydride methods, solid amine absorption method has extensively because of selectivity with higher and lower regeneration energy consumption General application prospect.
The preparation of solid amine absorption agent is the key that solid amine absorption method.In the prior art generally by physical impregnation method Organic amine is distributed in carrier duct, is prepared with the adsorbent compared with high adsorption capacity.This adsorbent almost without corrosion, And amine content with higher.But such adsorbent, after multiple adsorption desorption circulation, amine loss of active component is serious, causes Adsorbent stability is poor.Also, in the preparation process of solid amine absorption agent, it is generally used the preparation absorption of heat drying method Agent, this method both consumed energy, and easily caused amine loss and collapse of pore structure again during heating.Such as Chinese patent CN201110147916.6 discloses a kind of mesoporous silica/organic matter compound carbon dioxide absorber, with infusion process by organic amine It is supported on silica-base material surface, haves the shortcomings that stability is poor.Also, because CO2Have when entering adsorbent deep layer duct Very big diffusional resistance, causes in CO2The utilization rate of organic amine is lower during trapping.Therefore, people pass through optimization carrier Porous structure or introduce non-reacted additive, make adsorbent that there is good diffusivity, and then solve adsorbent diffusion The problem that rate is slow and amine utilization rate is low,
Compared with the porous structure of optimization carrier, this method of non-reacted additive is introduced in adsorbent from practical application From the perspective of be easier realize.Since additive can generate additional carbon dioxide diffusion path in adsorbent, make simultaneously In adsorbent, more adsorption sites are exposed, so the amine efficiency of adsorbent is significantly increased.But it is non-due to additive Reactivity so that the raising of adsorbent adsorbance is limited, and if the amount of the additive used is higher, can make total dioxy Changing carbon adsorption amount reduces.Meanwhile it being added the modified adsorbent of agent there are still the problems of stability difference.
In the past few decades, the appearance of ionic liquid provides new machine to solve engineers facing challenges Meeting.Ionic liquid is a kind of most advanced solvent with many peculiar properties, is widely used in CO in recent years2Trapping.With biography The organic amine absorbent of system is compared, and ionic liquid is as CO2Absorbent overcomes the shortcomings of traditional organic amine.For example, Ionic liquid almost without vapour pressure, decomposition temperature is high, stability is good, the service life is long.Now studies have shown that conventional ionic liquid exists CO under normal pressure2Trapping ability is weaker, and the amino functional ionic liquid developed thereafter is in trapping CO2Though being mentioned in terms of ability Height, but its viscosity is with CO2The increase of amount of collected and increase, and finally influence carbon dioxide absorption and desorption.To understand The problem that certainly viscosity of il is big and adsorption-desorption rate is low, people, on porous carrier, make ion ionic liquid loaded Liquid is preferably dispersed in carrier, increases ionic liquid and carbon dioxide exposure face, and then improve the suction of ionic liquid Attached parsing rate.Although this method can reduce viscosity of il, the stability and absorption parsing rate of adsorbent are improved, But there are still at high cost and CO for the adsorbent of this method preparation2The low problem of adsorbance.Cheng et al. (CO2 Adsorption Performance of Ionic Liquid [P66614][2-Op] Loaded onto Molecular Sieve MCM-41 Compared to Pure Ionic Liquid in Biohythane/Pure CO2 Atmospheres, Energy Fuels, 30,3251 3256,2016) by ionic liquid loaded in mesoporous silicon oxide For CO2Absorption finds CO in the short time2The rate of adsorption is obviously improved, but adsorbance is not above liquid ionic liquid Itself, and ionic liquid loaded amount is larger, cost is also higher.Therefore, develop that a kind of stability is good, the rate of adsorption is fast, adsorbance High, low-cost CO2Adsorbent is most important to collecting carbonic anhydride.
Summary of the invention
The present invention is intended to provide the carbon dioxide absorber that a kind of adsorbance height, good cycling stability, the rate of adsorption are fast.This Invention additionally provides the preparation method and application of the adsorbent.
Adsorbent provided by the invention is one kind using biomass carbon as carrier, using organic amine and ionic liquid as active matter The load type adsorbing agent of matter.By walnut shell and pine the sawdust mixing that will be carbonized, crush, the ultrasonic spoke in ultrasonator It penetrates, peels off the irregular graphite linings in biomass carbon, generate new or open blocked hole, to enhance biomass carbon Porosity and permeability；It is modified again by flowing back in the solution of modifying agent, obtains a kind of novel powder biomass carbon.Biomass Charcoal is handled by ultrasonic radiation, and obtained flourishing pore structure can effectively improve the load capacity and dispersion of organic amine and ionic liquid Property.Biomass carbon obtains more rich surface functional group, surface functional group abundant in pore surface by reflux modification It can be in conjunction with the organic amine of load, so that organic amine is fixed in adsorbent by stronger, to improve the stabilization of adsorbent Property.Biomass carbon carrier is immersed at room temperature in the mixed aqueous solution of organic amine, ionic liquid, by freeze-drying 20 ~ After 48 hours, a kind of collecting carbonic anhydride adsorbent is obtained.Adsorbent is prepared by freeze-drying, not only reduces energy Consumption, and new gap will form in organic amine layer of load due to the removal of water in freezing dry process, further promote Into the exposure of titanium dioxide Carbon diffusion and organic amine active sites, and then significantly improve the adsorbance of carbon dioxide.
The present invention provides a kind of carbon dioxide absorber, adsorbent is made by freeze-drying；By organic amine, ionic liquid Body is combined with biomass carbon；The weight percent of each component are as follows: biomass carbon accounts for 40 ~ 60%, and organic amine accounts for 30 ~ 50%, from Sub- liquid accounts for 5 ~ 10%.
The biomass carbon is the two proportion made of being mixed with as walnut shell and pine sawdust carbonized material are as follows:
Walnut shell carbonized material 30 ~ 70%
Pine sawdust carbonized material 30 ~ 70%.
The organic amine be tetraethylenepentamine, polyethyleneimine, diethylenetriamine it is any.
The ionic liquid is functional form ionic liquid；Functional form ionic liquid includes 1- amine propyl -3- methylimidazole Inferior amine salt, 1- amine propyl -3- methylimidazole hexafluorophosphate, 1- amine propyl -3- methyl imidazolium tetrafluoroborate, 1- amine ethyl - Any one of 3- methylimidazole bromide.
The present invention provides the preparation methods of above-mentioned collecting carbonic anhydride adsorbent, comprising the following steps:
(1) walnut shell washed, 100 DEG C of dryings, carbonize, be crushed to 200 ~ 300 mesh, obtain walnut shell carbonized material A；
Carbonization condition is vacuum, and temperature is 600 ~ 800 DEG C；
(2) by the washing of pine sawdust, 100 DEG C of dryings, charing, 200 ~ 300 mesh is crushed to, pine sawdust carbonized material B is obtained；
Carbonization condition is vacuum, and temperature is 500 ~ 600 DEG C；
(3) A is mixed in proportion with B, is subsequently placed in ultrasonic radiation 10 ~ 20 minutes in the ultrasonator equipped with deionized water, It filters, dry C；
(4) C is placed in the modifier solution that concentration is 1 ~ 2.5mol/L and be heated to reflux 8 ~ 10 hours modified, suction filtration, Obtain biomass carbon D within dry 10 ~ 12 hours at 100 DEG C；
(5) dipping is stirred at room temperature in the mixed aqueous solution of biomass carbon D and organic amine, ionic liquid, dip time is 5 ~ 8 Hour, then it is ultrasonically treated 2 ~ 3 hours in ultrasonator again, gained mixture freezes to 20 in -196 DEG C of liquid nitrogen ~ 30 minutes, then mixture is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 ~ 48 hours, obtained carbon dioxide and catch Collect adsorbent.
Further, in step (3) active carbon ultrasonic radiation condition are as follows: temperature be 30 ~ 50 DEG C, supersonic frequency be 20 ~ 30KHz。
Further, the modifying agent in step (4) be 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and I-hydroxybenzotriazole any or two kinds of mixture.
Further, the concentration of modifier solution is 1 ~ 2.5mol/L in step (4)；Biomass carbon and modifier solution Solid-to-liquid ratio is the ml of 1g/50 ~ 100, i.e., every g biomass carbon needs the modifier solution of 50 ~ 100 ml, and being heated to reflux temperature is 100 ~120℃。
Further, the proportion of the biomass carbon in step (5), organic amine and ionic liquid are as follows: 40 ~ 60:30 ~ 50:5 ~ 10。
Further, biomass carbon and deionized water solid-to-liquid ratio are 1g/5-10ml in step (5), i.e., every g biomass carbon needs Want 5-10ml deionized water.
The present invention provides application of the above-mentioned collecting carbonic anhydride adsorbent in adsorbing and trapping carbon dioxide.Described catches Collection adsorbent can be applied to air, the trapping in flue gas to carbon dioxide.
In above-mentioned application, the adsorption temp is 50 ~ 80 DEG C, and adsorptive pressure is 0.01 ~ 0.1 MPa.
Beneficial effects of the present invention:
(1) compared with using mesoporous synthetic material, the present invention uses modified powder biomass carbon for carrier, and makes the life The raw material of substance high-area carbon is discarded walnut shell and pine sawdust, and raw material is cheap and easy to get, realizes waste utilization.
(2) present invention uses Freeze Drying Technique in adsorbent preparation process, does immersion solvent with deionized water, with Traditional heating drying is made solvent with dehydrated alcohol and is compared, not only energy saving, but also saves reagent.And in freezing dry process by In the removal of water, new gap will form in organic amine layer of load, titanium dioxide Carbon diffusion and organic amine can be promoted living Property position exposure, improve carbon dioxide adsorption performance.
(3) it by combining organic amine in adsorbent preparation process with ionic liquid, provides a kind of based on ion Liquid promotes the new method of solid amine absorption agent dynamics diffusion, to improve the carbon dioxide adsorption performance of solid amine absorber.
(4) compared with non-reacted additive, ionic liquid not only can produce additional diffusion way as additive Diameter can also increase adsorption reaction site, and then improve the carbon dioxide adsorption and adsorption desorption rate of adsorbent.And from Sub- liquid stability is preferable, and after adding ionic liquid, organic amine and ionic liquid are combined, and improve the stability of adsorbent.
(5) compared with using ionic liquid trapping carbon dioxide merely, since the adsorbent uses more organic amine, from Sub- liquid consumption is less (5 ~ 10%), therefore not only increases adsorbance and also reduce adsorbing and trapping cost.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
(1) preparation of biomass carbon:
30g walnut shell is washed, is dried, the vacuum carbonized at 600 DEG C crushes, is sieved into 250 mesh powder (A)；By 30g pine Sawdust washing, dry, the vacuum carbonized at 500 DEG C, crushing are sieved into 250 mesh powder (B)；(A) and (B) is pressed into 30%:70% Ratio mixing, be subsequently placed in ultrasonic radiation 10 minutes, supersonic frequency in the ultrasonator equipped with 30 DEG C of deionized water 20KHz is filtered, dry C；C is placed in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide hydrochloride that concentration is 1mol/L 8 hours modified, suction filtration is heated to reflux in salting liquid at 100 DEG C, obtains 17g biomass carbon within dry 10 hours at 100 DEG C.
(2) preparation of load type adsorbing agent:
It weighs 0.8g organic amine and 0.2g ionic liquid is put into 5ml deionized water, be stirred at room temperature 30 minutes, then weigh Biomass carbon 1g is put into the mixed solution of organic amine, ionic liquid and water, continues dipping to be stirred at room temperature 8 hours, so It is ultrasonically treated 2 hours in ultrasonator afterwards, gained mixture is freezed 20 minutes in -196 DEG C of liquid nitrogen, then will be mixed Conjunction object, which is placed in -65 DEG C of freeze-dryer, to be freeze-dried 24 hours, and collecting carbonic anhydride adsorbent is obtained.
(3) performance test of adsorbent:
By 1g absorbent filling 10mm it is tubular fixed-bed in, temperature is risen to 75 DEG C, temperature-rise period by both ends silica wool beyond the Great Wall In be passed through nitrogen, after temperature is stablized, nitrogen is switched into the mixed of carbon dioxide that carbon dioxide volume solubility is 15% and nitrogen It closes gas and carries out adsorption reaction, gaseous mixture gas flow rate is 60ml/min.Adsorbent adsorbance is 4.12mmol/g with this condition.
10 temp.-changing adsorption parsing tests are carried out to adsorbent using above-mentioned fixed bed reactors, adsorption process is at 75 DEG C Under, it is carried out under carbon dioxide and nitrogen mixture atmosphere that gas concentration lwevel is 15%, resolving is the nitrogen at 100 DEG C Atmosphere encloses lower progress.By 1g absorbent filling in fixed bed, nitrogen is passed through with the gas flow rate degree of 100ml/min, and will Temperature is increased to 100 DEG C, keeps 90min at 100 DEG C.75 DEG C are reduced the temperature to later, and nitrogen is switched into carbon dioxide The gaseous mixture of carbon dioxide and nitrogen that volumetric concentration is 15% carries out adsorption reaction, and gaseous mixture gas flow rate is 60ml/min.It inhales Gaseous mixture is switched to pure nitrogen gas, nitrogen flow 100ml/min again after attached process, and temperature is increased to 100 DEG C, is allowed Adsorbent desorbs 60min at 100 DEG C.It reduces the temperature to 75 DEG C again later, and nitrogen is switched into carbon dioxide volumetric concentration For 15% carbon dioxide and the gaseous mixture of nitrogen, adsorption reaction is carried out again, and the above process is repeated 10 times.With this condition, into After 10 absorption of row/de-adsorption cycle process, the adsorbance of adsorbent remains to reach 3.9mmol/g, and adsorbance only declines 5.3%.It says Bright adsorbent has preferable cyclical stability.
Embodiment 2:
(1) preparation of biomass carbon:
40g walnut shell is washed, is dried, the vacuum carbonized at 600 DEG C crushes, is sieved into 250 mesh powder (A)；By 35g pine Sawdust washing, dry, the vacuum carbonized at 500 DEG C, crushing are sieved into 250 mesh powder (B)；(A) and (B) is pressed into 40%:60% Ratio mixing, be subsequently placed in ultrasonic radiation 15 minutes, supersonic frequency in the ultrasonator equipped with 40 DEG C of deionized water 25KHz is filtered, dry C；C is placed in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide hydrochloride that concentration is 2mol/L 8 hours modified, suction filtration is heated to reflux in salting liquid at 100 DEG C, obtains 20g biomass carbon within dry 10 hours at 100 DEG C.
(2) preparation of load type adsorbing agent:
It weighs 1g organic amine and 0.2g ionic liquid is put into 5ml deionized water, be stirred at room temperature 30 minutes, then weigh life Substance charcoal 1g, is put into the mixed solution of organic amine, ionic liquid and water, continues dipping to be stirred at room temperature 8 hours, then It is ultrasonically treated 2 hours in ultrasonator, gained mixture is freezed 20 minutes in -196 DEG C of liquid nitrogen, it then will mixing Object is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 hours, obtains collecting carbonic anhydride adsorbent.
(3) performance test of adsorbent:
By 1g absorbent filling 10mm it is tubular fixed-bed in, temperature is risen to 75 DEG C, temperature-rise period by both ends silica wool beyond the Great Wall In be passed through nitrogen, after temperature is stablized, nitrogen is switched into the mixed of carbon dioxide that carbon dioxide volume solubility is 15% and nitrogen It closes gas and carries out adsorption reaction, gaseous mixture gas flow rate is 60ml/min.Adsorbent adsorbance is 4.48mmol/g with this condition.
10 temp.-changing adsorption parsing tests are carried out to adsorbent using above-mentioned fixed bed reactors, adsorption process is at 75 DEG C Under, it is carried out under carbon dioxide and nitrogen mixture atmosphere that gas concentration lwevel is 15%, resolving is the nitrogen at 100 DEG C Atmosphere encloses lower progress.By 1g absorbent filling in fixed bed, nitrogen is passed through with the gas flow rate degree of 100ml/min, and will Temperature is increased to 100 DEG C, keeps 90min at 100 DEG C.75 DEG C are reduced the temperature to later, and nitrogen is switched into carbon dioxide The gaseous mixture of carbon dioxide and nitrogen that volumetric concentration is 15% carries out adsorption reaction, and gaseous mixture gas flow rate is 60ml/min.It inhales Gaseous mixture is switched to pure nitrogen gas, nitrogen flow 100ml/min again after attached process, and temperature is increased to 100 DEG C, is allowed Adsorbent desorbs 60min at 100 DEG C.It reduces the temperature to 75 DEG C again later, and nitrogen is switched into carbon dioxide volumetric concentration For 15% carbon dioxide and the gaseous mixture of nitrogen, adsorption reaction is carried out again, and the above process is repeated 10 times.With this condition, into After 10 absorption of row/de-adsorption cycle process, the adsorbance of adsorbent remains to reach 4.26mmol/g, and adsorbance only declines 5%.It says Bright adsorbent has preferable cyclical stability.
Embodiment 3:
(1) preparation of biomass carbon:
35g walnut shell is washed, is dried, the vacuum carbonized at 600 DEG C crushes, is sieved into 250 mesh powder (A)；By 50g pine Sawdust washing, dry, the vacuum carbonized at 500 DEG C, crushing are sieved into 250 mesh powder (B)；(A) and (B) is pressed into 45%:55% Ratio mixing, be subsequently placed in ultrasonic radiation 15 minutes, supersonic frequency in the ultrasonator equipped with 50 DEG C of deionized water 25KHz is filtered, dry C；C is placed in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide that concentration is 2.2 mol/L 8 hours modified, suction filtration is heated to reflux in HCI solution at 100 DEG C, obtains 22g biomass carbon within dry 10 hours at 100 DEG C.
(2) preparation of load type adsorbing agent:
It weighs 1.02g organic amine and 0.18g ionic liquid is put into 5ml deionized water, be stirred at room temperature 30 minutes, then claim Biomass carbon 1g is taken, is put into the mixed solution of organic amine, ionic liquid and water, continues dipping to be stirred at room temperature 8 hours, Then it is ultrasonically treated 2 hours in ultrasonator, gained mixture is freezed 20 minutes in -196 DEG C of liquid nitrogen, then will Mixture is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 hours, obtains collecting carbonic anhydride adsorbent.
(3) performance test of adsorbent:
By 1g absorbent filling 10mm it is tubular fixed-bed in, temperature is risen to 75 DEG C, temperature-rise period by both ends silica wool beyond the Great Wall In be passed through nitrogen, after temperature is stablized, nitrogen is switched into the mixed of carbon dioxide that carbon dioxide volume solubility is 15% and nitrogen It closes gas and carries out adsorption reaction, gaseous mixture gas flow rate is 60ml/min.Adsorbent adsorbance is 4.61mmol/g with this condition.
10 temp.-changing adsorption parsing tests are carried out to adsorbent using above-mentioned fixed bed reactors, adsorption process is at 75 DEG C Under, it is carried out under carbon dioxide and nitrogen mixture atmosphere that gas concentration lwevel is 15%, resolving is the nitrogen at 100 DEG C Atmosphere encloses lower progress.By 1g absorbent filling in fixed bed, nitrogen is passed through with the gas flow rate degree of 100ml/min, and will Temperature is increased to 100 DEG C, keeps 90min at 100 DEG C.75 DEG C are reduced the temperature to later, and nitrogen is switched into carbon dioxide The gaseous mixture of carbon dioxide and nitrogen that volumetric concentration is 15% carries out adsorption reaction, and gaseous mixture gas flow rate is 60ml/min.It inhales Gaseous mixture is switched to pure nitrogen gas, nitrogen flow 100ml/min again after attached process, and temperature is increased to 100 DEG C, is allowed Adsorbent desorbs 60min at 100 DEG C.It reduces the temperature to 75 DEG C again later, and nitrogen is switched into carbon dioxide volumetric concentration For 15% carbon dioxide and the gaseous mixture of nitrogen, adsorption reaction is carried out again, and the above process is repeated 10 times.With this condition, into After 10 absorption of row/de-adsorption cycle process, the adsorbance of adsorbent remains to reach 4.38mmol/g, and adsorbance only declines 4.9%. Illustrate that adsorbent has preferable cyclical stability.
Embodiment 4:
(1) preparation of biomass carbon:
40g walnut shell is washed, is dried, the vacuum carbonized at 600 DEG C crushes, is sieved into 250 mesh powder (A)；By 50g pine Sawdust washing, dry, the vacuum carbonized at 500 DEG C, crushing are sieved into 250 mesh powder (B)；(A) and (B) is pressed into 50%:50% Ratio mixing, be subsequently placed in ultrasonic radiation 20 minutes, supersonic frequency in the ultrasonator equipped with 50 DEG C of deionized water 30KHz is filtered, dry C；C is placed in 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt that concentration is 2.5mol/L 8 hours modified, suction filtration is heated to reflux in acid salt solution at 100 DEG C, obtains 24g biomass carbon within dry 10 hours at 100 DEG C.
(2) preparation of load type adsorbing agent:
It weighs 1.12g organic amine and 0.12g ionic liquid is put into 5ml deionized water, be stirred at room temperature 30 minutes, then claim Biomass carbon 1g is taken, is put into the mixed solution of organic amine, ionic liquid and water, continues dipping to be stirred at room temperature 8 hours, Then it is ultrasonically treated 2 hours in ultrasonator, gained mixture is freezed 20 minutes in -196 DEG C of liquid nitrogen, then will Mixture is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 hours, obtains collecting carbonic anhydride adsorbent.
(3) performance test of adsorbent:
By 1g absorbent filling 10mm it is tubular fixed-bed in, temperature is risen to 75 DEG C, temperature-rise period by both ends silica wool beyond the Great Wall In be passed through nitrogen, after temperature is stablized, nitrogen is switched into the mixed of carbon dioxide that carbon dioxide volume solubility is 15% and nitrogen It closes gas and carries out adsorption reaction, gaseous mixture gas flow rate is 60ml/min.Adsorbent adsorbance is 4.75mmol/g with this condition.
10 temp.-changing adsorption parsing tests are carried out to adsorbent using above-mentioned fixed bed reactors, adsorption process is at 75 DEG C Under, it is carried out under carbon dioxide and nitrogen mixture atmosphere that gas concentration lwevel is 15%, resolving is the nitrogen at 100 DEG C Atmosphere encloses lower progress.By 1g absorbent filling in fixed bed, nitrogen is passed through with the gas flow rate degree of 100ml/min, and will Temperature is increased to 100 DEG C, keeps 90min at 100 DEG C.75 DEG C are reduced the temperature to later, and nitrogen is switched into carbon dioxide The gaseous mixture of carbon dioxide and nitrogen that volumetric concentration is 15% carries out adsorption reaction, and gaseous mixture gas flow rate is 60ml/min.It inhales Gaseous mixture is switched to pure nitrogen gas, nitrogen flow 100ml/min again after attached process, and temperature is increased to 100 DEG C, is allowed Adsorbent desorbs 60min at 100 DEG C.It reduces the temperature to 75 DEG C again later, and nitrogen is switched into carbon dioxide volumetric concentration For 15% carbon dioxide and the gaseous mixture of nitrogen, adsorption reaction is carried out again, and the above process is repeated 10 times.With this condition, into After 10 absorption of row/de-adsorption cycle process, the adsorbance of adsorbent remains to reach 4.56mmol/g, and adsorbance only declines 4%.It says Bright adsorbent has preferable cyclical stability.

Claims (10)

1. a kind of carbon dioxide absorber, it is characterised in that: adsorbent is made by freeze-drying；By organic amine, ionic liquid It is combined with biomass carbon；The weight percent of each component are as follows: biomass carbon accounts for 40 ~ 60%, and organic amine accounts for 30 ~ 50%, ion Liquid accounts for 5 ~ 10%.
2. carbon dioxide absorber according to claim 1, it is characterised in that: the biomass carbon is by walnut shell and pine Made of sawdust carbonized material is mixed with, the weight percent of the two are as follows:
Walnut shell carbonized material 30 ~ 70%,
Pine sawdust carbonized material 30 ~ 70%.
3. carbon dioxide absorber according to claim 1, it is characterised in that: the organic amine be tetraethylenepentamine, Polyethyleneimine, diethylenetriamine it is any；The ionic liquid includes 1- amine propyl -3- methylimidazole inferior amine salt, 1- Amine propyl -3- methylimidazole hexafluorophosphate, 1- amine propyl -3- methyl imidazolium tetrafluoroborate, 1- amine ethyl-3-methylimidazole Any one of bromide.
4. a kind of preparation method of the described in any item carbon dioxide absorbers of claim 1 ~ 3, it is characterised in that including following Step:
(1) walnut shell washed, dry, carbonize, be crushed to 200 ~ 300 mesh, obtain walnut shell carbonized material A；
Carbonization condition is vacuum, and temperature is 600 ~ 800 DEG C；
(2) by the washing of pine sawdust, drying, charing is crushed to 200 ~ 300 mesh, obtains pine sawdust carbonized material B；
Carbonization condition is vacuum, and temperature is 500 ~ 600 DEG C；
(3) A is mixed in proportion with B, is subsequently placed in ultrasonic radiation 10 ~ 20 minutes in the ultrasonator equipped with deionized water, It filters, dry C；
(4) C is placed in modifier solution and be heated to reflux 8 ~ 10 hours modified, suction filtration, it is 10 ~ 12 hours dry at 100 DEG C Obtain biomass carbon D；
(5) dipping is stirred at room temperature in the mixed aqueous solution of biomass carbon D and organic amine, ionic liquid, dip time is 5 ~ 8 Hour, it is then 2 ~ 3 hours ultrasonic in ultrasonator again, gained mixture is freezed 20 ~ 30 points in -196 DEG C of liquid nitrogen Then mixture is placed in -65 DEG C of freeze-dryer and is freeze-dried 24 ~ 48 hours by clock, obtain collecting carbonic anhydride suction Attached dose.
5. the preparation method of carbon dioxide absorber according to claim 4, it is characterised in that: biomass in step (3) The ultrasonic radiation condition of charcoal are as follows: temperature is 30 ~ 50 DEG C, and supersonic frequency is 20 ~ 30KHz.
6. the preparation method of carbon dioxide absorber according to claim 4, it is characterised in that: the modification in step (4) Agent is 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and I-hydroxybenzotriazole any or two kinds Mixture；
The concentration of modifier solution is 1 ~ 2.5mol/L；The solid-to-liquid ratio of biomass carbon and modifier solution is 1g/50 ~ 100 ml, Being heated to reflux temperature is 100 ~ 120 DEG C.
7. the preparation method of carbon dioxide absorber according to claim 4, it is characterised in that: biomass in step (5) Charcoal and deionized water solid-to-liquid ratio are 1g/5-10ml.
8. a kind of application of described in any item carbon dioxide absorbers of claim 1 ~ 3 in trapping carbon dioxide.
9. application according to claim 8, it is characterised in that: the adsorbent can apply to air, right in flue gas The absorption of carbon dioxide.
10. application according to claim 9, it is characterised in that: the adsorption temp is 50 ~ 80 DEG C, and adsorptive pressure is 0.01~0.1 MPa；
By 1g absorbent filling 10mm it is tubular fixed-bed in, temperature is risen to 50 ~ 80 DEG C, heating by both ends silica wool beyond the Great Wall It is passed through nitrogen in the process, after temperature is stablized, nitrogen is switched into the carbon dioxide and nitrogen that carbon dioxide volume solubility is 15% Gaseous mixture carry out adsorption reaction, gaseous mixture gas flow rate be 60ml/min；Adsorbent adsorbance can reach with this condition 4.12mmol/g~4.75mmol/g。
CN201811128447.1A 2018-09-27 2018-09-27 Carbon dioxide adsorbent and preparation method and application thereof Expired - Fee Related CN109201007B (en)

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