CN1657156A - Multiamine absorbed fiber and its preparation method and use - Google Patents
Multiamine absorbed fiber and its preparation method and use Download PDFInfo
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- CN1657156A CN1657156A CN 200410052592 CN200410052592A CN1657156A CN 1657156 A CN1657156 A CN 1657156A CN 200410052592 CN200410052592 CN 200410052592 CN 200410052592 A CN200410052592 A CN 200410052592A CN 1657156 A CN1657156 A CN 1657156A
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Abstract
An adsorptive polyamine fibre for adsorbing CO2 from fume is composed of glass fibre and polyamine-type high-molecular layer coated on the surface of glass fibre. It is prepared through immersing glass fibres in the solution of high-molecular polyamine compound and cross-linking agent.
Description
Technical field
The present invention relates to the purposes that polyamine species adsorbing fiber and preparation method thereof and this polyamines adsorbing fiber are used for the adsorption and enrichment carbon dioxide.
Background technology
Fossil fuel such as coal and oil accounts for more than 85% of the energy that consumes in the world at present.In this century, this class A fuel A still occupies leading status.Yet, the burning of fossil fuel but to airborne release a large amount of CO
2, and may cause the variation of weather, promptly so-called greenhouse effects.Therefore, must develop the discharging of otherwise effective technique with the control greenhouse gases.And to CO
2The exploitation of the adsorbent of high selectivity and high-adsorption-capacity, the key of this class technology beyond doubt.
The method that is used for the carbon dioxide adsorbing separation at present mainly comprises based on dissolving or the absorption process of neutralization reaction, absorption method, low temperature distillation method and the membrane separation process etc. of high-specific surface area solid absorbent.The two kinds of methods in back are mainly used in from mist CO
2Separate.
CO commonly used
2Sorbing material such as zeolite, active carbon etc. at low temperatures carbon dioxide is had higher adsorption capacity; But when other gas existed, they were then poor to the selectivity of carbon dioxide, and when temperature was higher than 30 ℃, its adsorption capacity to carbon dioxide just sharply descended, and the adsorbance to carbon dioxide in the time of 200 ℃ almost can be ignored.
Chemical absorbing demonstrates high selectivity to carbon dioxide and absorbs.Solvent commonly used is monoethanolamine, potash etc.But these class methods are owing to carry out in liquid phase, and the corrosivity of solvent is big, thereby big to requirement height, the regeneration expense of reaction tower, and the loss of absorption liquid takes place easily, not only increases expense, also brings problem of environmental pollution.
At present the solid phase adsorption material of report all is no more than 18wt% to the high-adsorption-capacity of carbon dioxide.
Summary of the invention
The object of the present invention is to provide polyamine species adsorbing fiber and preparation method thereof and this polyamines adsorbing fiber to be used for the purposes of adsorption and enrichment carbon dioxide.
The present invention is coated on the glass fibre by the macromolecule that will contain alkaline amido, and the advantage of comprehensive solid-phase adsorbent and alkaline lyosoption makes the fibrous adsorbent that amido is enriched in solid-state containing.This polyamines adsorbing fiber is a kind of carbon dioxide to be had high selectivity, high-adsorption-capacity, and the solid phase adsorption material of low volatility, can be used for the adsorption and enrichment carbon dioxide, is particularly useful for the adsorption and enrichment of carbon dioxide in the flue gas.
Polyamines adsorbing fiber of the present invention is made of the outer field polyamine family macromolecule layer of glass fibre and coating glass fibre, and polyamine family macromolecule layer weight accounts for 15～85% of adsorbing fiber gross weight; Polyamine family macromolecule layer is made of polyamine family macromolecule compound and crosslinking agent, and crosslinking agent weight is 5%～50% of polyamine family macromolecule weight.
Described polyamine family macromolecule compound is generally polyvinylamine, poly-Ethylenimine or triethylenetetramine.The molecular weight of polyamine family macromolecule is 5000-60000.
Described crosslinking agent is generally benzene three acyl chlorides, glutaraldehyde, pentaerythrite or epoxy resin.
Described glass fibre can be glass fiber or glass fabric.Glass fiber typically have a diameter from 1 μ m～50 μ m.
The polyamines adsorbing fiber of the invention described above can prepare by the following method: polyamine family macromolecule compound and crosslinking agent are made into the Polymer Solution that contains the polyamines base, solvent for use is water, methyl alcohol, acetone or dimethyl formamide, the concentration of polyamine family macromolecule is 0.25～50wt% in this Polymer Solution, and the consumption of crosslinking agent is 5%～50% of a polyamine family macromolecule compound weight; Glass fibre soaked in this contain 10～120min in the Polymer Solution of polyamines base, the glass fibre drying that will wrap up polyamine family macromolecule layer then promptly obtains required polyamines adsorbing fiber.
Polyamines adsorbing fiber of the present invention has high selectivity and high-adsorption-capacity to carbon dioxide, can be used for the adsorption and enrichment carbon dioxide.
When polyamines adsorbing fiber of the present invention is used for the adsorption and enrichment carbon dioxide, as long as it is contacted with carbonated gas.Normally the polyamines adsorbing fiber is contacted 0.1～2 hour with carbon dioxide containing gas under the humidity more than 60%.
Polyamines adsorbing fiber of the present invention especially is suitable for the extensive enrichment of carbon dioxide in the flue gas.
Polyamines adsorbing fiber of the present invention can reach 30wt% to the adsorption capacity of carbon dioxide.
The polyamines adsorbing fiber carries out under dynamic condition the mensuration of the adsorption capacity of carbon dioxide.The carbon dioxide that makes certain humidity is by the polyamines adsorbing fiber, and under steady temperature, the rate of body weight gain of polyamines adsorbing fiber is estimated the adsorption capacity (capacity) of polyamines adsorbing fiber to carbon dioxide.
Description of drawings
Fig. 1 is the aerial thermal weight loss situation of polyamines adsorbing fiber.Be presented at before 100 ℃, slight weightlessness is arranged, this is the desorption of adsorbed water on the polyamines adsorbing fiber.The weight kept stable of polyamines adsorbing fiber afterwards is until the just obviously aggravation of weight loss of 250 ℃ of left and right sides polyamines adsorbing fibers.Illustrate that polyamine family macromolecule chain warp is appropriately crosslinked on the polyamines adsorbing fiber, it is thermally-stabilised to about 250 ℃ that gained polyamines adsorbing fiber can keep.In other words, when this adsorbing fiber uses, the obvious loss of adsorbent can not take place yet under 200 ℃ of temperature.
Fig. 2 shows that the relative scale of weight of the weight of polyamine family macromolecule in the polyamines adsorbing fiber skin and crosslinking agent is to the influence of this adsorbing fiber absorbing carbon dioxide capacity.As seen, along with the percentage of the weight of the weight of polyamine family macromolecule and crosslinking agent was increased to from 50: 50 90: 10 o'clock, adsorbing fiber is increased to more than the 20wt% from 3wt% the adsorption capacity of carbon dioxide.Show that the content of amido plays conclusive effect to the absorption of carbon dioxide in the polyamine family macromolecule layer of adsorbing fiber.
The specific embodiment
Embodiment 1
Compound concentration is poly-Ethylenimine (molecular weight 60000) acetone soln (Polymer Solution that contains the polyamines base) of 10～30wt%, and 10% of the poly-Ethylenimine weight of adding epoxy resin mixes then.With diameter is that the glass fiber of 6 μ m is soaked in 30min in the above-mentioned solution, takes out the glass fibre that has wrapped up this polyamine family macromolecule compound, and 60 ℃ dry down, promptly obtains the polyamines adsorbing fiber.By the difference of control Polymer Solution concentration, obtain the polyamines adsorbing fiber of different coating thickness (different polyamine family macromolecule layer content).The percent by weight of polyamine family macromolecule layer and as shown in table 1 in these adsorbing fibers to the adsorption capacity of carbon dioxide.
Table 1
| Sample number into spectrum | Polyamine family macromolecule layer content (wt%) | CO 2Adsorbance (wt%) |
| ????1 | ????56.7 | ????18.2 |
| ????2 | ????77.3 | ????28.1 |
| ????3 | ????81.7 | ????28.3 |
| ????4 | ????84.4 | ????31.0 |
Table 1 shows the raising that accounts for the percentage of adsorbing fiber gross weight with polyamine family macromolecule layer weight, the also corresponding increase of its adsorbance to carbon dioxide.Wherein account for 84.4% when above of gross weight of adsorbing fiber when the weight of polyamine family macromolecule layer, adsorbing fiber has reached more than 30% the adsorbance of carbon dioxide.
With concentration is poly-Ethylenimine (molecular weight 15000) dimethyl formamide solution of 20wt%, mix with 5% the epoxy resin of weight for poly-Ethylenimine weight, then glass fabric is soaked in 30min in the above-mentioned solution, the taking-up fiber is also dry under 65 ℃, obtains the polyamines adsorbing fiber.Adsorbing fiber is that 75% o'clock adsorbance to carbon dioxide is 32wt% in relative humidity.
Embodiment 3
The dimethyl formamide solution of polyvinylamine is mixed with epoxy resin, and the percentage by weight of polyvinylamine and epoxy resin is 90: 10, and polyvinylamine concentration is 30wt%; Glass fabric is soaked in 30min in this solution, takes out fiber, 65 ℃ dry down, obtains the polyamines adsorbing fiber.Under 25 ℃, be 60% air-flow by humidity, the balance water absorption that records adsorbing fiber is 45wt%; Feed carbon dioxide subsequently, the humidity of control gas is 60% also, records under this humidity, and adsorbing fiber is 15.6wt% to the adsorption capacity of carbon dioxide.
Embodiment 4
With the pentaerythrite is crosslinking agent, to gather Ethylenimine mixes with pentaerythrite, the percentage by weight of poly-Ethylenimine and pentaerythrite is 90: 10, being made into poly-Ethylenimine concentration is the methanol solution of 30wt%, glass fibre is immersed 60min in this solution, take out fiber, 65 ℃ dry down, obtains the polyamines adsorbing fiber.Under 25 ℃, relative humidity is 75% o'clock, and recording adsorbing fiber is 29wt% to the equilibrium adsorption capacity of carbon dioxide.
Triethylenetetramine is mixed with epoxy resin, and the percentage by weight of triethylenetetramine and epoxy resin is 70: 30, and dilution is for containing the acetone soln of 5wt% triethylenetetramine, glass fibre is soaked in this solution, take out fiber, 65 ℃ dry down, obtains the polyamines adsorbing fiber.Under 25 ℃, relative humidity is 75% o'clock, and recording adsorbing fiber is 17wt% to the equilibrium adsorption capacity of carbon dioxide.Be heated to 140 ℃, make the fiber desorption and regeneration.5 times so repeatedly, under 25 ℃, relative humidity is 75% o'clock again, and recording this sorbing material is 18wt% to the equilibrium adsorption capacity of carbon dioxide.The proof adsorbing fiber is after 140 ℃ of heating, and its adsorption capacity can access recovers (regeneration) completely, and this adsorbing fiber can use repeatedly.
Claims (8)
1. a polyamine species adsorbing fiber is characterized in that this adsorbing fiber is made of the outer field polyamine family macromolecule layer of glass fibre and coating glass fibre, and polyamine family macromolecule layer weight accounts for 15～85% of adsorbing fiber gross weight; Polyamine family macromolecule layer is made of polyamine family macromolecule compound and crosslinking agent, and crosslinking agent weight is 5%～50% of polyamine family macromolecule weight.
2. an adsorbing fiber as claimed in claim 1 is characterized in that described polyamine family macromolecule compound is polyvinylamine, poly-Ethylenimine or triethylenetetramine, and the molecular weight of polyamine family macromolecule is 5000-60000; Described crosslinking agent is benzene three acyl chlorides, glutaraldehyde, pentaerythrite or epoxy resin.
3. an adsorbing fiber as claimed in claim 1 or 2 is characterized in that described glass fibre is glass fiber or glass fabric.
4. adsorbing fiber as claimed in claim 3, the diameter that it is characterized in that described glass fiber is 1 μ m～50 μ m.
5. the preparation method of the described polyamines adsorbing fiber of one of claim 1～4, it is characterized in that polyamine family macromolecule compound and crosslinking agent are made into the Polymer Solution that contains the polyamines base, solvent for use is water, methyl alcohol, acetone or dimethyl formamide, the concentration of polyamine family macromolecule is 0.25～50wt% in this Polymer Solution, and the consumption of crosslinking agent is 5%～50% of a polyamine family macromolecule compound weight; Glass fibre soaked in this contain 10～120min in the Polymer Solution of polyamines base, the glass fibre drying that will wrap up polyamine family macromolecule layer then promptly obtains required polyamines adsorbing fiber.
6. the described adsorbing fiber of one of claim 1～4 is used for the adsorption and enrichment carbon dioxide.
7. according to the described application of claim 6, it is characterized in that described adsorbing fiber is contacted 0.1～2.0 hour with carbonated gas.
8. according to the described application of claim 6, it is characterized in that described adsorbing fiber is contacted 0.1～2 hour with carbonated gas under the humidity more than 60%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703676A (en) * | 2012-08-29 | 2015-06-10 | Ccm研究有限公司 | Method and compositions for capturing carbon dioxide |
| CN105133183A (en) * | 2015-10-15 | 2015-12-09 | 五邑大学 | Preparation method and application of micro-nano fiber membrane containing high-density amido and centrifugal spun yarns of micro-nano fiber membrane |
| CN109078623A (en) * | 2018-10-16 | 2018-12-25 | 齐鲁工业大学 | A kind of magnetic response type both sexes nano adsorption material and preparation method thereof |
| CN112337448A (en) * | 2020-11-20 | 2021-02-09 | 天津工业大学 | Solid amine hollow fiber for removing low-concentration carbon dioxide in closed room and preparation method thereof |
| CN114011385A (en) * | 2021-11-01 | 2022-02-08 | 中国船舶重工集团公司第七一八研究所 | Preparation method of high-amino-content solid amine fiber cloth |
| CN115650663A (en) * | 2022-10-18 | 2023-01-31 | 北京交通大学 | Preparation method of ultrahigh-performance concrete with carbon dioxide as internal curing agent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2708724B1 (en) * | 1993-07-29 | 1995-10-13 | Boye Sa Manuf Vetements Paul | Production of cold by adsorption / desorption of carbon dioxide with the use of activated carbon fibers or activated carbon as adsorbent material. |
| CN1043130C (en) * | 1995-12-22 | 1999-04-28 | 吉林大学 | Solid carbon dioxide adsorbent and preparation method thereof |
| KR100388630B1 (en) * | 2000-12-04 | 2003-06-25 | 한국에너지기술연구원 | Manufacturing Method for Glass Fiber Reinforced Activated Carbon/Zeolite Composite Adsorbent with Waste Water Treatment Using Mixture of Zeolite and Phenolic Resin |
| JP2004251304A (en) * | 2003-02-18 | 2004-09-09 | Matsushita Electric Ind Co Ltd | Manufacturing method for vacuum insulator, vacuum insulator, insulating box body and insulation appliance using the vacuum insulator |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104703676A (en) * | 2012-08-29 | 2015-06-10 | Ccm研究有限公司 | Method and compositions for capturing carbon dioxide |
| CN104703676B (en) * | 2012-08-29 | 2018-01-19 | Ccm研究有限公司 | For catching the method and composition of carbon dioxide |
| CN105133183A (en) * | 2015-10-15 | 2015-12-09 | 五邑大学 | Preparation method and application of micro-nano fiber membrane containing high-density amido and centrifugal spun yarns of micro-nano fiber membrane |
| CN105133183B (en) * | 2015-10-15 | 2019-03-22 | 五邑大学 | A kind of the micro nanometer fiber film and its centrifugal spinning preparation method and application of the amido containing high density |
| CN109078623A (en) * | 2018-10-16 | 2018-12-25 | 齐鲁工业大学 | A kind of magnetic response type both sexes nano adsorption material and preparation method thereof |
| CN112337448A (en) * | 2020-11-20 | 2021-02-09 | 天津工业大学 | Solid amine hollow fiber for removing low-concentration carbon dioxide in closed room and preparation method thereof |
| CN112337448B (en) * | 2020-11-20 | 2024-03-26 | 天津工业大学 | Solid amine hollow fiber for removing low-concentration carbon dioxide in closed chamber and preparation method thereof |
| CN114011385A (en) * | 2021-11-01 | 2022-02-08 | 中国船舶重工集团公司第七一八研究所 | Preparation method of high-amino-content solid amine fiber cloth |
| CN115650663A (en) * | 2022-10-18 | 2023-01-31 | 北京交通大学 | Preparation method of ultrahigh-performance concrete with carbon dioxide as internal curing agent |
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| CN1314482C (en) | 2007-05-09 |
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Granted publication date: 20070509 Termination date: 20131209 |