CN1724141A - Process for preparing adsorbent of molecular sieve with high adsorption value fluorite - Google Patents
Process for preparing adsorbent of molecular sieve with high adsorption value fluorite Download PDFInfo
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- CN1724141A CN1724141A CNA2005100125506A CN200510012550A CN1724141A CN 1724141 A CN1724141 A CN 1724141A CN A2005100125506 A CNA2005100125506 A CN A2005100125506A CN 200510012550 A CN200510012550 A CN 200510012550A CN 1724141 A CN1724141 A CN 1724141A
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Abstract
An adsorbent of zeolite molecular sieve with high adsorbent to CO is prepared through ion exchange between non-adhesive 4A molecular sieve and calcium chloride solution, water washing, baking to obtain 5A molecular sieve, immersing it in the diluted solution of sodium hydroxide or water glass, baking and activating.
Description
One, technical field
The preparation method of adsorbent of molecular sieve with high adsorption value fluorite of the present invention belongs to the technical field of the preparation and the modification of zeolite molecular sieve.Specifically, be preparation method about the high modification 5A adsorbent of molecular sieve of a kind of carbon monoxide adsorbance.
Two, technical background
Along with C
1Developing rapidly of chemistry, carbon monoxide is increasingly extensive in the developing application of chemical industry, and synthesizing of compounds such as many chemical products such as formic acid, acetic acid, oxalic acid, dimethylformamide, phosgene, polycarbonate, polyamine fat all needs pure carbon monoxide; Simultaneously, in synthetic ammonia, toluene di-isocyanate(TDI) industry such as (TDI), the existence of micro CO will cause some catalyst for reaction poisonings in the gas, it must be removed; In addition, the industrial waste gas that contains carbon monoxide is a lot, as blast furnace gas, converter gas and the oven gas of steel mill, and the calcium carbide furnace gas in chemical plant etc., needs general impurity removals such as carbon monoxide wherein are to obtain pure gas.
The mid-80 PSA (transformation absorption) technology is come out, because its device is simple, the automaticity height, easy to operate, operating cost is low, unstripped gas wide accommodation, product purity advantages of higher, become gas and separate and the one preferred technique that purifies, and seek to carbon monoxide have than high adsorption capacity and optionally adsorbent be the key of raising PSA technical efficiency.CN86102838 and US5922640 disclose Cu (I)-zeolite molecular sieve and Cu (I)-acticarbon respectively, and the copper-loaded adsorbent of this class utilizes the complexing absorption principle to adsorb, so their carbon monoxide adsorbance is higher.But the desorption of carbon monoxide is difficulty comparatively, the desorption temperature of Cu (I)-zeolite adsorbent is more than 200 ℃, and the desorption temperature of Cu (I)-acticarbon also will be more than 120 ℃, method with general transformation desorption is difficult to make adsorbent reactivation, must adopt heating or high vacuum desorption and regeneration, so not only energy consumption is big, operation inconvenience, and also the carbon monoxide yield is low.
CN98113363 and CN03115743 disclose the preparation technology of binder free 5A molecular sieve respectively, its method is done the binding agent moulding with the 4A molecular sieve with clay, handle (crystallization process) through alkali lye, binding agent partly is converted into the 4A molecular sieve, obtain binder free 4A molecular sieve, through the calcium chloride solution exchange, obtain the 5A adsorbent of molecular sieve of binder free again.The 5A molecular sieve that comprises binding agent with tradition is compared, because binding agent partly transforms into effective ingredient, has eliminated the obstruction in duct between sieve particle simultaneously, and the adsorbance and the rate of adsorption of this type of adsorbent all are greatly increased.
Three, summary of the invention
The preparation method of adsorbent of molecular sieve with high adsorption value fluorite of the present invention, purpose are to provide a kind of existing binder free 5A adsorbent of molecular sieve are carried out modification, thereby reach the method for its carbon monoxide adsorbance of further raising.
The preparation method of adsorbent of molecular sieve with high adsorption value fluorite of the present invention, it is characterized in that it being the preparation method of the high zeolite adsorbent of a kind of carbon monoxide adsorbance, this method is: after binder free 4A molecular sieve and calcium chloride solution are carried out ion-exchange and reach balance, through washing, oven dry, obtain the 5A molecular sieve, then the 5A molecular sieve is mixed with certain density dipping solution with certain solid-to-liquid ratio, after flooding certain hour at a certain temperature solution is poured out, oven dry, roasting promptly obtains the 5A adsorbent of molecular sieve of modification.Wherein said dipping solution is the weak solution of NaOH or waterglass, and the concentration of maceration extract sodium hydroxide solution is 0.01mol/L-0.10mol/L, and selectable range is 0.05mol/L-0.10mol/L; The modulus of maceration extract water glass solution is 1.5-2.0, and wherein concentration of silicon dioxide is 0.05mol/L-0.30mol/L, and selectable range is 0.10mol/L-0.20mol/L.Described dipping temperature is 20 ℃-90 ℃, and selectable range is 35 ℃-90 ℃.Described dip time is 10min-5h, and selectable range is 1h-3h.Described solid-to-liquid ratio is 1: 1-5, selectable range is 1: 2-4.
Provided by the present inventionly the method that the 5A molecular sieve carries out modification is had the following advantages by alkaline solution dipping:
1. the absorption property of 5A adsorbent of molecular sieve can be significantly improved, before the adsorption capacity of the adsorbent of modification is than modification, 1%-15% can be improved carbon monoxide; And when calcium chloride exchange solution was acidity, the effect of this method was more obvious.
2. method is simple, expends cheap.
3. adopt the complete desorption of carbon monoxide that the mode of the normal temperature degassing can be adsorbed with the 5A molecular sieve, be applicable to the use of transformation absorption.
Four, the specific embodiment
Embodiment 1
Binder free 4A molecular sieve and pH=5.86, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 22.6ml/g.Another part 35 ℃ under floods 1h with the sodium hydroxide solution of 0.02mol/L with solid-to-liquid ratio at 1: 2, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 23.1ml/g.Absorption once more behind the desorption, the carbon monoxide adsorbance is 23.0ml/g.
Embodiment 2:
Dipping solution concentration in the embodiment 1 is become 0.05mol/L, and dipping temperature becomes 60 ℃, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 3, and other condition is constant, and the carbon monoxide adsorbance is 24.6ml/g.
Embodiment 3:
Dipping solution concentration in the embodiment 1 is become 0.10mol/L, and dipping temperature becomes 90 ℃, and dip time becomes 3h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 25.3ml/g.
Embodiment 4:
Binder free 4A molecular sieve and pH=6.49, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 23.7ml/g.Another part 90 ℃ under floods 1h with the sodium hydroxide solution of 0.01mol/L with solid-to-liquid ratio at 1: 2, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 24.2ml/g.Absorption once more behind the desorption, the carbon monoxide adsorbance is 24.1ml/g.
Embodiment 5:
Dipping solution concentration in the embodiment 4 is become 0.05mol/L, and dipping temperature becomes 35 ℃, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 3, and other condition is constant, and the carbon monoxide adsorbance is 25.0ml/g.
Embodiment 6:
Dipping solution concentration in the embodiment 4 is become 0.10mol/L, and dipping temperature becomes 60 ℃, and dip time becomes 4h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 25.5ml/g.
Embodiment 7:
Binder free 4A molecular sieve and pH=6.98, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 24.0ml/g.Another part 35 ℃ under floods 0.5h with the sodium hydroxide solution of 0.02mol/L with solid-to-liquid ratio at 1: 2, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 24.6ml/g.Absorption once more behind the desorption, the carbon monoxide adsorbance is 24.4ml/g.
Embodiment 8:
Dipping solution concentration in the example 7 is become 0.05mol/L, and dipping temperature becomes 60 ℃, and dip time becomes 4h, and the dipping solid-to-liquid ratio becomes 1: 3, and other condition is constant, and the carbon monoxide adsorbance is 25.4ml/g.
Embodiment 9:
Dipping solution concentration in the embodiment 7 is become 0.05mol/L, and dipping temperature becomes 90 ℃, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 25.7ml/g.
Embodiment: 10
Binder free 4A molecular sieve and pH=7.36, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 24.6ml/g.Another part 35 ℃ under floods 0.5h with the sodium hydroxide solution of 0.02mol/L with solid-to-liquid ratio at 1: 2, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 25.0ml/g.Absorption once more behind the desorption, the carbon monoxide adsorbance is 24.8ml/g.
Embodiment 11:
Dipping solution concentration in the example 10 is become 0.05mol/L, and dipping temperature becomes 60 ℃, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 3, and other condition is constant, and the carbon monoxide adsorbance is 25.4ml/g.
Embodiment 12:
Dipping solution concentration in the example 10 is become 0.05mol/L, and dipping temperature becomes 90 ℃, and dip time becomes 3h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 258ml/g.
Embodiment 13:
Binder free 4A molecular sieve and pH=8.12, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 25.2ml/g.Another part 35 ℃ under floods 0.5h with the sodium hydroxide solution of 0.01mol/L with solid-to-liquid ratio at 1: 2, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 25.4ml/g.Absorption once more behind the desorption, the carbon monoxide adsorbance is 25.1ml/g.
Embodiment 14:
Dipping solution concentration in the embodiment 13 is become 0.05mol/L, and dipping temperature becomes 60 ℃, and dip time becomes 4h, and the dipping solid-to-liquid ratio becomes 1: 3, and other condition is constant, and the carbon monoxide adsorbance is 25.7ml/g.
Embodiment 15:
Dipping solution concentration in the embodiment 13 is become 0.10mol/L, and dipping temperature becomes 90 ℃, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 26.4ml/g.
Embodiment 16:
Binder free 4A molecular sieve and pH=6.98, concentration is that the calcium chloride solution of 0.60mol/L mixes with solid-to-liquid ratio at 1: 3, after 90 ℃ exchange reaches balance down, obtain the 5A molecular sieve, after washing, oven dry, be divided into two parts, get a copy of it after 550 ℃ of activation, adopt weight adsorption, 101.325 * 10 at 25 ℃
3Recording its carbon monoxide adsorbance under the Pa is 24.0ml/g.Another part is 1.52 with modulus, and silica concentration is that the water glass solution of 0.10mol/L 35 ℃ under floods 1h with solid-to-liquid ratio at 1: 3, oven dry, and recording the carbon monoxide adsorbance after the activation under the same conditions is 25.30ml/g.
Embodiment 17:
Dipping solution modulus in the embodiment 16 is become 1.96, and solution concentration becomes 0.18mol/L, and dip time becomes 2h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 25.6ml/g.
Embodiment 18:
Dipping solution concentration in the embodiment 16 is become 0.18mol/L, and dipping temperature becomes 90 ℃, and dip time becomes 3h, and the dipping solid-to-liquid ratio becomes 1: 4, and other condition is constant, and the carbon monoxide adsorbance is 26.3ml/g.
Claims (7)
1, a kind of preparation method of adsorbent of molecular sieve with high adsorption value fluorite, it is characterized in that it being the preparation method of the high zeolite adsorbent of a kind of carbon monoxide adsorbance, this method is: after at first binder free type body 4A molecular sieve and calcium chloride solution being carried out ion-exchange and reaching balance, through washing, oven dry, make the 5A molecular sieve, with the alkaline solution dipping, after the oven dry activation, can obtain the high modification 5A adsorbent of molecular sieve of carbon monoxide adsorbance then.
2, described by claim 1 with alkaline solution dipping 5A molecular sieve, it is characterized in that described alkaline dipping solution is the solution of NaOH or waterglass.
3, the described NaOH dipping solution of claim 2, the concentration that it is characterized in that sodium hydroxide solution is 0.01mol/L-0.10mol/L, selectable range is 0.05mol/L-0.10mol/L.
4, the described waterglass dipping solution of claim 2, the modulus that it is characterized in that waterglass is 1.50-2.00, and wherein concentration of silicon dioxide is 0.05mol/L-0.30mol/L, and selectable range is 0.10mol/L-0.20mol/L.
5, it is characterized in that with alkaline solution dipping 5A molecular sieve dipping temperature is 20 ℃-90 ℃ by claim 1 is described, selectable range is 35 ℃-90 ℃.
6, it is characterized in that with alkaline solution dipping 5A molecular sieve dip time is 10min-5h by claim 1 is described, selectable range is 1h-3h.
7, described with alkaline solution dipping 5A molecular sieve by claim 1, solid-to-liquid ratio is 1 when it is characterized in that flooding: 1-5, selectable range is 1: 2-4.
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| CN100377776C (en) * | 2006-10-17 | 2008-04-02 | 太原理工大学 | Method for preparing molecular sieve absorbent with high adsorption capacity |
| CN100431689C (en) * | 2006-12-21 | 2008-11-12 | 北京工业大学 | Preparation method of compound absorbent for removing nitrogen oxide |
| CN101890332A (en) * | 2010-07-30 | 2010-11-24 | 成都华西气体化工有限责任公司 | Preparation method of special high-performance 5A molecular sieve for pressure swing adsorption |
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| US4381256A (en) * | 1981-01-14 | 1983-04-26 | W. R. Grace & Co. | Method of producing binderless zeolite extrudates |
| CN1042021C (en) * | 1992-11-17 | 1999-02-10 | 中国科学院大连化学物理研究所 | Process for preparing adsorbent of non-adhesive dewaxed 5A molecular sieve |
| CN1113828A (en) * | 1994-05-31 | 1995-12-27 | 中国科学院大连化学物理研究所 | high efficiency carbon monoxide adsorbent |
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- 2005-05-25 CN CNB2005100125506A patent/CN100471555C/en not_active Expired - Fee Related
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| CN100431689C (en) * | 2006-12-21 | 2008-11-12 | 北京工业大学 | Preparation method of compound absorbent for removing nitrogen oxide |
| CN101890332A (en) * | 2010-07-30 | 2010-11-24 | 成都华西气体化工有限责任公司 | Preparation method of special high-performance 5A molecular sieve for pressure swing adsorption |
| CN101890332B (en) * | 2010-07-30 | 2012-07-18 | 成都华西气体化工有限责任公司 | Preparation method of special high-performance 5A molecular sieve for pressure swing adsorption |
| CN105749859A (en) * | 2014-12-17 | 2016-07-13 | 中国石油天然气股份有限公司 | Method for preparing adsorbent for deacidification of methyl methacrylate |
| CN105749859B (en) * | 2014-12-17 | 2018-05-04 | 中国石油天然气股份有限公司 | Preparation method for methyl methacrylate deacidification adsorbent |
| CN111097373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Porous adsorption material, oxygen-carrying and adsorption composite functional material and application thereof |
| CN111097374A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院生态环境研究中心 | Preparation method of oxygen-carrying and adsorption composite functional material and application of oxygen-carrying and adsorption composite functional material in water body remediation |
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| CN111097368A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Adsorbing material and preparation method and application thereof |
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| CN114682237A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of 5A molecular sieve adsorbent |
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| CN113000026A (en) * | 2021-03-04 | 2021-06-22 | 上海绿强新材料有限公司 | Modified composite molecular sieve and preparation and application thereof |
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