CN100377776C - Method for preparing molecular sieve absorbent with high adsorption capacity - Google Patents
Method for preparing molecular sieve absorbent with high adsorption capacity Download PDFInfo
- Publication number
- CN100377776C CN100377776C CNB2006101020455A CN200610102045A CN100377776C CN 100377776 C CN100377776 C CN 100377776C CN B2006101020455 A CNB2006101020455 A CN B2006101020455A CN 200610102045 A CN200610102045 A CN 200610102045A CN 100377776 C CN100377776 C CN 100377776C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- calcium
- adsorption capacity
- preparation
- high adsorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for preparing the absorber of molecule screen, wherein it is characterized in that: it improves the calcium content to prepare the absorber with high adsorption on nitrogen, carbon oxide, oxygen, water, etc. And said method mixes 4A molecule screen with calcium compound, uses caoline as adhesive, compresses, bakes, treats with alkali, exchanges with calcii chloridum solution and activates. The nitrogen adsorption of product can reach 11.5ml/g, and the carbon oxide adsorption can reach 34ml/g, and the skellysolve B adsorption can reach 16%.
Description
One, technical field
The preparation method of molecular sieve absorbent with high adsorption capacity of the present invention belongs to the preparation of zeolite molecular sieve and to having the technical field of Adhesive-free Molecular Sieve 5A process modification now, is the preparation method of the 5A adsorbent of molecular sieve of macroion exchange and high adsorption capacity.
Two, technical background
Carbon monoxide, nitrogen, methane etc. all are important raw material of industry gas, and with industrial expansion, the demand of these unstripped gas also constantly increases.So these gases that separate, purify have important industrial significance.
Transformation absorption PSA technology is in recent years at the gas separation of industrial new emergence, it utilizes the difference of gas component characterization of adsorption on solid material and adsorbance with the characteristic of change in pressure, realizes the separation and the purification of gas by periodic pressure conversion process.And adsorbent is the basis of PSA gas separation, and the performance of adsorbent directly influences final separating effect, even influences the complexity of processing step and the service life of PSA.Therefore, the used adsorbent of PSA has high adsorption capacity and separation selectivity to purpose gas, then all is of great importance for the separating effect and the saving energy.Chinese patent 86102838 discloses a kind of molecular sieve of copper modification, utilize carbon monoxide to adsorb with monovalence copper on it or cupric generation complexing, so carbon monoxide is had high adsorption capacity and high selection absorption property, but the carbon monoxide desorption of its absorption is comparatively difficult.
One of molecular sieve modified technology is ion-exchange, and salts such as 4A and calcium chloride carry out ion-exchange, thereby the sodium ion that calcium ion replaces among the 4A makes the aperture change make 5A greatly, and the absorption property that improves adsorbent is had great role.More general method is at present: powder 4A and binding agent kaolin mixed-forming, through high-temperature roasting kaolin is converted into metakaolin, crystallization is converted into molecular sieve 4A with metakaolin in the sodium hydroxide solution of 1-1.5mol/L again, the binder free type body molecular sieve 4A liquid phase calcium that makes exchange and make type body molecular sieve 5A, this method calcium exchange capacity can reach 80%, improves but to be difficult to again.CA2125314 discloses a kind of method that improves ion-exchange capacity, be to exchange with calcium chloride solution again after handling sample 3-4 time with the sodium carbonate liquor that NaOH is regulated pH=8-9, can improve the calcium exchange capacity, but its operation is many and it is effective to the powder exchange to be.
Three, summary of the invention
The preparation method of a kind of molecular sieve absorbent with high adsorption capacity of the present invention, purpose are to improve the calcium exchange capacity and the adsorption capacity of existing binder free 5A molecular sieve, thereby a kind of method for preparing molecular sieve absorbent with high adsorption capacity is provided.
The preparation method of a kind of molecular sieve absorbent with high adsorption capacity of the present invention, it is characterized in that it being a kind of preparation method who is used for the molecular sieve absorbent with high adsorption capacity of pressure swing adsorption technique, this method mixes 4A molecular sieve and calcium containing compound, and described calcium containing compound is calcium oxide, calcium hydroxide, calcium salt calcium chloride, calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate or calcium oxalate; With kaolin is binding agent, extrusion modling, make adsorbent of molecular sieve through roasting, alkali treatment, calcium chloride solution exchange and activation, the molecular sieve absorbent with high adsorption capacity of preparation can reach to the nitrogen adsorption amount that 11.5ml/g, carbon monoxide adsorbance reach more than the 34ml/g, the adsorbance of n-hexane reaches more than 16% (percentage by weight).
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that described calcium containing compound is a calcium chloride.
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that the described calcium containing compound and the content ratio of 4A molecular sieve are 0.1-50mmol Ca
++/ 100g molecular sieve.
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that the described calcium chloride and the content ratio of 4A molecular sieve are 40-50mmol Ca
++/ 100g molecular sieve.
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that described roasting, and its sintering temperature is 550-680 ℃, roasting time 2-4h.
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that described roasting, and its sintering temperature scope also can be 550-650 ℃.
The preparation method of above-mentioned a kind of molecular sieve absorbent with high adsorption capacity is characterized in that the kaolin and the content ratio of 4A molecular sieve are 1: 4.
The preparation method's of a kind of molecular sieve absorbent with high adsorption capacity of the present invention advantage is:
1, high calcium exchange degree can improve the adsorbance to each adsorbate, can reach to the nitrogen adsorption amount that 11.5ml/g, carbon monoxide adsorbance reach more than the 34ml/g, the adsorbance of n-hexane reaches more than 16% (weight).
2, process is simple, the calcium utilization height.
3, now be mainly used in pressure swing adsorption technique, so industry use, saving cost and the energy are had very big meaning.
Four, the specific embodiment
Embodiment 1
80g4A powder, 20g kaolin, 0.05mol calcium chloride mix, through extruding slivering, oven dry, roasting 2h in 650 ℃ of Muffle furnaces, again in 300ml, 90 ℃ of crystallization 6h in the 1.5mol/L sodium hydroxide solution, through being washed to pH=8, again with this sample in 300ml, 90 ℃ exchange 2h in the calcium chloride of 0.97mol/L, the exchange secondary, the sample that has exchanged, wash a night for 90 ℃, oven dry activates 2h in 450 ℃ of Muffle furnaces again.Record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 33.00ml/g, and the adsorbance of nitrogen is 10.06ml/g; 0.25atm under 25 ℃, recording n-hexane with gravimetric method is 16.16%.
Embodiment 2
The calcium chloride that adds is 0.035mol, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 30.73ml/g, and the adsorbance of nitrogen is 9.14ml/g; 0.25atm under 25 ℃, the n-hexane adsorbance is 13.30%.
Embodiment 3
The calcium chloride that adds is 0.044mol, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 31.30ml/g, and the adsorbance of nitrogen is 9.73ml/g; 0.25atm under 25 ℃, the n-hexane adsorbance is 14.70%.
Embodiment 4
The calcium chloride that adds is 0mol, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 29.99ml/g, and the adsorbance of nitrogen is 8.35ml/g; 0.25atm under 25 ℃, the adsorbance of n-hexane is 12.86%.
Embodiment 5
Identical with example 1, sintering temperature is 580 ℃, and 2h records with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 34.33ml/g, and the adsorbance of nitrogen is 11.6ml/g; 0.25atm under 25 ℃, the n-hexane adsorbance is 13.47%.
Embodiment 6
Identical with example 1, sintering temperature is 680 ℃, and 2h records with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 31.88ml/g, and nitrogen is 9.13ml/g; 0.25atm under 25 ℃, n-hexane is 12.3%.
Embodiment 7
Identical with example 4, sintering temperature is 580 ℃, 2h, and the 5A that the method that all the other conditions are identical makes records with gravimetric method: the adsorbance of its carbon monoxide is 28.74ml/g, nitrogen is 9.35ml/g; 0.25atm under 25 ℃, the n-hexane adsorbance is 13.22%.
Embodiment 8
Identical with example 4, sintering temperature is 680 ℃, and 2h, this sample be at 1atm, and under 25 ℃, record with gravimetric method: the adsorbance of carbon monoxide is 26.23ml/g, and nitrogen is 7.29ml/g; 0.25atm under 25 ℃, recording n-hexane with gravimetric method is 11.56%.
Embodiment 9
The first step adds 0.05mol calcium hydroxide and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 28.95ml/g.
Embodiment 10
The first step adds 0.05mol calcium carbonate and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 26.10ml/g.
Embodiment 11
The first step adds the 0.05mol calcium oxalate and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 9.52ml/g.
Embodiment 12
The first step adds the 0.05mol calcium oxide and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 25.00ml/g.
Embodiment 13
The first step adds 0.05mol calcium nitrate and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 29.00ml/g.
Embodiment 14
The first step adds 0.05mol calcium sulfate and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 26.00ml/g.
Embodiment 15
The first step adds the 0.05mol calcium bicarbonate and mixes, and all the other steps are identical with example 1, record with gravimetric method: this sample is at 1atm, and under 25 ℃, the adsorbance of carbon monoxide is 28.05ml/g.
Claims (7)
1. the preparation method of a molecular sieve absorbent with high adsorption capacity, it is characterized in that it being a kind of preparation method who is used for the molecular sieve absorbent with high adsorption capacity of pressure swing adsorption technique, this method mixes 4A molecular sieve and calcium containing compound, and described calcium containing compound is calcium oxide, calcium hydroxide, calcium salt calcium chloride, calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate or calcium oxalate; With kaolin is binding agent, extrusion modling, make adsorbent of molecular sieve through roasting, alkali treatment, calcium chloride solution exchange and activation, the molecular sieve absorbent with high adsorption capacity of preparation can reach to the nitrogen adsorption amount that 11.5ml/g, carbon monoxide adsorbance reach more than the 34ml/g, the adsorbance of n-hexane reaches more than 16% (percentage by weight).
2. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 1 is characterized in that described calcium containing compound is a calcium chloride.
3. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 1 is characterized in that the described calcium containing compound and the content ratio of 4A molecular sieve are 0.1-50mmol Ca
++/ 100g molecular sieve.
4. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 2 is characterized in that the described calcium chloride and the content ratio of 4A molecular sieve are 40-50mmol Ca
++/ 100g molecular sieve.
5. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 1 is characterized in that described roasting, and its sintering temperature is 550-680 ℃, roasting time 2-4h.
6. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 1 is characterized in that described roasting, and its sintering temperature scope also can be 550-650 ℃.
7. the preparation method of a kind of molecular sieve absorbent with high adsorption capacity according to claim 1 is characterized in that the kaolin and the content ratio of 4A molecular sieve are 1: 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101020455A CN100377776C (en) | 2006-10-17 | 2006-10-17 | Method for preparing molecular sieve absorbent with high adsorption capacity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101020455A CN100377776C (en) | 2006-10-17 | 2006-10-17 | Method for preparing molecular sieve absorbent with high adsorption capacity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962047A CN1962047A (en) | 2007-05-16 |
| CN100377776C true CN100377776C (en) | 2008-04-02 |
Family
ID=38081372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101020455A Expired - Fee Related CN100377776C (en) | 2006-10-17 | 2006-10-17 | Method for preparing molecular sieve absorbent with high adsorption capacity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100377776C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475049A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of 5A adsorbent of molecular sieve |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884905B (en) * | 2009-05-13 | 2012-08-01 | 中国石油化工股份有限公司 | Solid adsorbent and preparation method thereof |
| CN102451664B (en) * | 2010-10-21 | 2013-09-18 | 中国石油化工股份有限公司 | Preparation method of adsorbent used for whole naphtha adsorption separation process |
| CN102059092A (en) * | 2010-11-29 | 2011-05-18 | 广州市香港科大霍英东研究院 | Refrigerating composite absorbent and preparation method thereof |
| CN102275950B (en) * | 2011-07-21 | 2013-02-13 | 中国地质大学（武汉） | Method for preparing 5A zeolite molecular sieve |
| CN102513058B (en) * | 2011-12-08 | 2014-01-08 | 复旦大学 | Modified natural stilbite used as methane adsorbent, and preparation method thereof |
| CN102912677B (en) * | 2012-09-20 | 2015-12-02 | 安徽凤凰滤清器股份有限公司 | A kind of filter of automobile engine air paper and preparation method thereof |
| CN103923345B (en) * | 2014-04-01 | 2015-12-09 | 桐乡市隆诚矿石材料有限公司 | Environment protection type multifunctional reodorant and preparation method thereof |
| CN104437443B (en) * | 2014-10-10 | 2016-08-17 | 宁夏宝塔石化科技实业发展有限公司 | A kind of activation method improving adsorbing material storage natural gas performance |
| CN105749859B (en) * | 2014-12-17 | 2018-05-04 | 中国石油天然气股份有限公司 | Preparation method of methyl methacrylate deacidification adsorbent |
| CN106315614A (en) * | 2016-08-29 | 2017-01-11 | 霍普科技（天津）股份有限公司 | Preparation method of modified Y-type molecular sieve |
| CN106215866B (en) * | 2016-08-31 | 2018-09-25 | 太原理工大学 | The method that steam assistant metal displacement prepares bimetallic MOFs materials |
| CN106434593B (en) * | 2016-09-21 | 2020-01-07 | 武汉中科志康生物科技有限公司 | Microsphere material for storing DNA polymerase at normal temperature, preparation method and application thereof |
| CN107936973B (en) * | 2017-11-05 | 2020-07-24 | 江西环保股份有限公司 | Heavy metal contaminated soil CaCO3Preparation method of/C repairing agent |
| CN109289764B (en) * | 2018-11-02 | 2021-04-06 | 太原理工大学 | Synthesis method of TUT-5A and application thereof in efficient separation of propyne propylene |
| CN115155519A (en) * | 2022-08-01 | 2022-10-11 | 中科洁力（福州）环保技术有限公司 | Preparation method of molecular sieve with strong adsorbability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2125314A1 (en) * | 1994-06-07 | 1995-12-08 | Raymond Le Van Mao | Zeolite materials with enhanced ion exchange capacity |
| CN1724141A (en) * | 2005-05-25 | 2006-01-25 | 太原理工大学 | Process for preparing adsorbent of molecular sieve with high adsorption value fluorite |
-
2006
- 2006-10-17 CN CNB2006101020455A patent/CN100377776C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2125314A1 (en) * | 1994-06-07 | 1995-12-08 | Raymond Le Van Mao | Zeolite materials with enhanced ion exchange capacity |
| CN1724141A (en) * | 2005-05-25 | 2006-01-25 | 太原理工大学 | Process for preparing adsorbent of molecular sieve with high adsorption value fluorite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106475049A (en) * | 2015-08-28 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of 5A adsorbent of molecular sieve |
| CN106475049B (en) * | 2015-08-28 | 2019-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of 5A adsorbent of molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1962047A (en) | 2007-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100377776C (en) | Method for preparing molecular sieve absorbent with high adsorption capacity | |
| CN108704609A (en) | Monolayer CuCl/ acticarbon preparation methods for CO adsorbing separations | |
| CN103566869B (en) | A kind of cupric adsorbent of molecular sieve and preparation method thereof | |
| CN103394367B (en) | Utilize coal ash for manufacturing for the method for ZSM-5 molecular sieve nucleocapsid double-layer catalyst | |
| CN102784617A (en) | Adsorbent containing silver molecular sieve as well as preparation method and application of adsorbent | |
| CN101733070A (en) | X-type zeolite separation material and preparation method thereof | |
| CN104226256A (en) | Spherical forming Cu base metal organic skeleton-graphene oxide composite material and preparation method of spherical forming Cu base metal organic skeleton-graphene oxide composite material | |
| CN113351157A (en) | Modified lithium low-silicon zeolite molecular sieve and preparation method thereof | |
| Zhang et al. | A new honeycomb MOF for C 2 H 4 purification and C 3 H 6 enrichment by separating methanol to olefin products | |
| CN113371730A (en) | Modified calcium low-silicon zeolite molecular sieve and preparation method thereof | |
| CN115536857B (en) | Zinc-organic framework material capable of selectively adsorbing carbon dioxide and synthesis method | |
| CN100369666C (en) | High temperature carbon dioxide adsorbent containing silicon nano calcium oxide, its preparation process and application in hydrogen production process | |
| CN101890332B (en) | Preparation method of special high-performance 5A molecular sieve for pressure swing adsorption | |
| CN100471555C (en) | Process for preparing adsorbent of molecular sieve with high adsorption value fluorite | |
| CN102688742A (en) | A carbon dioxide adsorbent preparation method | |
| KR100803771B1 (en) | Process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air | |
| CN103408032A (en) | Method for supercritical hydrothermal synthesis of flyash zeolite | |
| CN115090265B (en) | Preparation method of refinery dry gas ethylene efficient adsorbent | |
| CN113117639B (en) | Modified molecular sieve adsorbent and preparation method and application thereof | |
| CN110589849A (en) | Preparation method of medium-silicon ZSM-5 type molecular sieve and application of medium-silicon ZSM-5 type molecular sieve as high-selectivity acid gas adsorbent | |
| CN103933928B (en) | Dehumidifying adsorbent and preparation method thereof | |
| CN102059092A (en) | Refrigerating composite absorbent and preparation method thereof | |
| CN108905959A (en) | The method that microwave in-situ one-step method prepares ZnO/MCM-41 desulfurizing agent | |
| CN103933933A (en) | Ce-LiX high-performance oxygen adsorption material and preparation method thereof | |
| CN111889063B (en) | BiOCl adsorbent, preparation method and application thereof in room temperature desulfurization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |