CN103506070A - Preparation method of copper loaded activated carbon adsorbent - Google Patents
Preparation method of copper loaded activated carbon adsorbent Download PDFInfo
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- CN103506070A CN103506070A CN201210202195.9A CN201210202195A CN103506070A CN 103506070 A CN103506070 A CN 103506070A CN 201210202195 A CN201210202195 A CN 201210202195A CN 103506070 A CN103506070 A CN 103506070A
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- adsorbent
- active carbon
- dipping
- gas absorption
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Abstract
The invention provides a preparation method of an adsorbent for gas adsorbing separation. The adsorbent is used for the gas separation through pressure swing adsorption or temperature swing adsorption. The preparation method which treats activated carbon as a carrier comprises the following steps: dipping a copper salt and/or other assistants onto the active carbon carrier, placing the above obtained dipped activated carbon in a drying tower, and galvanizing the dipped activated carbon for heating the activated carbon in order to complete the drying process of the preparation of the adsorbent. The copper salt in the obtained adsorbent has a large load capacity and uniform dispersion on the surface of the activated carbon, so the adsorbent has a higher adsorption capability than traditional drying methods.
Description
Technical field
The invention provides the separated preparation method with copper activity carbon adsorbent of a kind of gas absorption, for pressure-variable adsorption or Temp .-changing adsorption divided gas flow.
Background technology
The pressure-variable adsorption of gas or Temp .-changing adsorption separation and purification process, because energy consumption is low, can move at normal temperatures, automaticity is high, flow process is simple, it is changeable to install, are therefore widely used.1985, Kawasaki, Japan Inland Steel processed and U.S. combinating carbide company built up the device of the Pressure Swing Adsorption CO of 410Nm/h in Japan.C-1 chemistry industry and in petrochemical industry large-scale CO pressure-variable adsorption production capacity separated with hydrogen pressure-variable adsorption and the single covering device of purification reached the scale of tens thousand of cubic metres of aerogenesis per hour.
Current industrial hydrogen generally be take active carbon, molecular sieve, silica or aluminium oxide as carrier with the adsorbent of the separated employing of CO pressure-variable adsorption, and load monovalence copper is as adsorbent.
The people such as Guan Yingfu (" gas chemical industry: C1 chemistry and chemical industry, 2010,35 (6): 49～52) investigated a kind of Cu (I)/active carbon CO adsorbent, its first adsorption capacity reached 46ml/g.Can separation obtain highly purified CO gas, and can operate at normal temperatures.
The people such as Liu Zhijun (" gas chemical industry: C1 chemistry and chemical industry, 2007,32 (1): 14) investigated a kind of Cu (I)/active carbon CO adsorbent, also obtained highly purified CO gas.But above two pieces of documents all do not relate to the preparation problem of Cu (I)/acticarbon.
The people such as Yi Honghong (environmental science, 2004,25 (5): 24～29) adopt the PU1 adsorbent of Peking University, obtained high the CO rate of recovery and purity, this adsorbent is Cu (I)/molecular sieve.
The NaY type adsorbent that NKK adopts, by the Na in Y zeolite
+with Cu
2+exchange, then through processes such as reduction, process the about 60ml/g of CO adsorbance of 25 ℃.
Wang Zong such as says at (gas chemical industry, 1991,16 (2): 8～13) studied Cu (I)/acticarbon.Its preparation method is impregnated into mantoquita on active carbon with infusion process, with forced air drying, dries.Different from method of directly drying to active carbon energising of the present invention.
(SCI, 2011,32 (8): 1794～1798) with method of glucose reduction, prepared CuCl/NaY adsorbent of molecular sieve such as Sun Si.At 25 ℃, during CO dividing potential drop 100kPa, adsorption capacity has reached 59ml/g.
Chinese patent CN1050403 discloses a kind of Cu/ active carbon CO adsorbent, and its dry run is with inert gas or vacuum drying, different from drying means of the present invention.
Chinese patent CN1085114C discloses adsorbent prepared by a kind of copper chloride, active carbon, rare earth and attapulgite, but it does not illustrate the impact of drying mode and drying mode.
Representative Chinese patent CN101890332A discloses the adsorbent of molecular sieve that a kind of pressure-variable adsorption is used, different from copper/acticarbon of the present invention.
In sum, in existing adsorbent document, there is no to find similarly to prepare with the present invention the method for adsorbent.
Summary of the invention
The object of this invention is to provide the separated preparation method with adsorbent of a kind of gas absorption.
Know-why of the present invention is by improving the drying mode in absorbent preparation process, suppress mantoquita and/or auxiliary agent in crystallization or reunion behavior in activated carbon granule surface and micropore inside, in restrain adsorption agent dry run, mantoquita and/or auxiliary agent are to migration and the enrichment on activated carbon granule surface, thereby effectively improve mantoquita and/or auxiliary agent in the distribution situation of carried by active carbon surface, make the adsorbent in equal mantoquita and/or auxiliary agent load capacity situation there is higher adsorption capacity and longer life-span; Also can be in the situation that significantly improve the load capacity of mantoquita on active carbon and/or auxiliary agent, keep mantoquita and/or auxiliary agent in activated carbon surface distribution situation comparatively uniformly.Method of the present invention also can be so that there is further to decompose oxidation or reduction process in the mantoquita and/or the auxiliary agent that load on absorbent charcoal carrier.And decomposing, after oxidation or reduction process, repeated impregnations, dry again, and further decomposition, oxidation or reduction process.
The present invention is achieved through the following technical solutions:
Scheme 1: the method be take active carbon as carrier, its preparation process is for being prepared into mantoquita and/or auxiliary agent the solution of the aqueous solution or other solvent, then active carbon is immersed in this solution, active carbon after dipping is placed in drying tower, upper and lower from drying tower, by the active carbon close contact after the both positive and negative polarity of desiccant power supply and dipping, switch on power, thereby make electric current flow through active carbon and make active carbon heating itself, by between heating activated carbon to 50～1500 ℃, water or other solvent seasoning evaporation are removed and mantoquita is reduced into monovalence copper and obtains adsorbent finished product.The preferred material of the active carbon after this programme drying tower contact dipping is nonmetallic materials.In this programme, electrode also can arrange in drying tower side; Power supply can be AC power, can be also dc source.
Scheme 2: the method be take active carbon as carrier, its preparation process is for being prepared into mantoquita and/or auxiliary agent the solution of the aqueous solution or other solvent, then active carbon is immersed in this solution, active carbon after dipping is placed in drying tower, drying tower is placed in electric induction furnace coil inside, in the coil of electric induction furnace by the alternating current of certain frequency, active carbon in drying tower can produce corresponding induced-current, thereby this induced-current flows through active carbon makes active carbon heating itself, by between heating activated carbon to 50～1500 ℃, water or other solvent seasoning evaporation are removed and mantoquita is reduced into monovalence copper and obtains adsorbent finished product.The preferred material of the active carbon after this programme drying tower contact dipping is nonmetallic materials.
Scheme 3: the method be take active carbon as carrier, its preparation process is for being prepared into heat decomposable mantoquita and/or auxiliary agent the solution of the aqueous solution or other solvent, then active carbon is immersed in this solution, active carbon after dipping is placed in drying tower, upper and lower from drying tower, by the active carbon close contact after the both positive and negative polarity of desiccant power supply and dipping, switch on power, thereby make electric current flow through active carbon and make active carbon heating itself, by between heating activated carbon to 50～400 ℃, water or other solvent seasoning evaporation are removed and mantoquita is reduced into monovalence copper or resolves into Cu oxide.And then the solution impregnation of the aqueous solution being prepared into mantoquita and/or auxiliary agent or other solvent, then the active carbon after this being flooded is again placed in drying tower, upper and lower from drying tower, by the active carbon close contact after the both positive and negative polarity of desiccant power supply and dipping, switch on power, thereby make electric current flow through active carbon and make active carbon heating itself, by between heating activated carbon to 50～1500 ℃, water or other solvent seasoning evaporation are removed and mantoquita is reduced into monovalence copper and obtains adsorbent finished product.The preferred material of the active carbon after this programme drying tower contact dipping is nonmetallic materials.In this programme, electrode also can arrange in drying tower side; Power supply can be AC power, can be also dc source.
Compare with traditional heated air drying adsorbent, the method of the present invention inequality that can keep from heat, uneven drying is even, heated air makes solvent residual in activated carbon granule from the outside start vaporizer of particle, the residual solvent of granule interior is diffused into and in outside process, mantoquita is taken to particle skin or outer surface, cause mantoquita at activated carbon granule inner surface skewness, load capacity cannot improve, the disadvantage that adsorption capacity is lower.
Adsorbent of the present invention is evaluated at ADSORPTION IN A FIXED BED tower, and dry Reduce and adsorption all carries out in ADSORPTION IN A FIXED BED tower, and this tower is the glass tube of the long 50cm of an internal diameter 2cm, CO/H
2, CO/N
2carry out the sign of pressure-variable adsorption separating power with CO/CH4 gas.In gaseous mixture, CO dividing potential drop is all 35kPa, and gaseous mixture stagnation pressure 100kPa carries out after saturated adsorption at ambient temperature, obtains the equilibrium adsorption capacity of CO to pass in and out volume differences-adsorption bed dead volume of adsorption bed gas.Be evacuated down to-90kPa is with reproducing adsorbent.The gas of separating sucking-off during regeneration goes to mid portion 100ml left and right with gas chromatographic analysis CO content.
The specific embodiment
The invention will be further described for embodiment.
Embodiment 1
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～6mm.
Take CuCl
22H
2o (analyze pure, molecular weight 170.48, content 99%) 60g is dissolved in 160ml distilled water and obtains solution A.Take above-mentioned absorbent charcoal carrier 60g in solution A, 90 ℃ of dipping 1h.Then filter, active carbon is packed into and in above-mentioned adsorption tower, forms the active carbon packed column that about 50cm is high, two graphite electrodes are set at activated-charcoal column two ends, insert in the active carbon after dipping one end of each graphite electrode, two other one end of graphite electrode, apply voltage, under nitrogen atmosphere, the heating activated carbon to 200 after dipping ℃ is dried to 20 minutes, cool to room temperature under nitrogen atmosphere.Adsorbent surface is the black of active carbon itself.
Press preceding method test adsorbent equilibrium adsorption capacity, CO is equilibrium adsorption capacity 53ml/g first.Adsorbance 38ml/g for the second time and for the third time.CO content 98% in the gas parsing during regeneration.The non-CO gas of estimating part is that bed space causes.Aforementioned three kinds of gaseous mixtures are little on the equilibrium adsorption capacity impact of CO.
Embodiment 2
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～6mm.
Take CuCl
22H
2o (analyze pure, molecular weight 170.48, content 99%) 60g and glucose 30g are dissolved in 160ml distilled water and obtain solution B.Take above-mentioned absorbent charcoal carrier 60g in solution B, room temperature dipping 3h.Then filter, active carbon is packed into and in above-mentioned adsorption tower, forms the active carbon packed column that about 50cm is high, two graphite electrodes are set at activated-charcoal column two ends, insert in the active carbon after dipping one end of each graphite electrode, two other one end of graphite electrode, apply voltage, under nitrogen atmosphere, the heating activated carbon to 200 after dipping ℃ is dried to 90 minutes, cool to room temperature under nitrogen atmosphere.Adsorbent surface is the black of active carbon itself.
Press preceding method test adsorbent equilibrium adsorption capacity, CO is adsorbance 58ml/g first.Adsorbance 41ml/g for the second time and for the third time.CO content 99% in the gas parsing during regeneration.
Embodiment 3
Carbon carrier: active carbon, bulk density 0.38g/ml, BET specific area 1091m
2/ g, particle diameter 2.5mm, particle length 2～6mm.
Take Cu (NO
3)
23H
2o (analyze pure, molecular weight 241.6, content 99%) 85g is dissolved in 160ml distilled water and obtains solution C.Take above-mentioned absorbent charcoal carrier 60g in solution C, 90 ℃ of dipping 3h.Then filter, active carbon is packed into and in above-mentioned adsorption tower, forms the active carbon packed column that about 50cm is high, two graphite electrodes are set at activated-charcoal column two ends, insert in the active carbon after dipping one end of each graphite electrode, two other one end of graphite electrode, apply voltage, under air atmosphere, by ℃ dry decomposition of the heating activated carbon to 300 after dipping 20 minutes, cool to room temperature under air atmosphere.Adsorbent surface is the black of active carbon itself.
And then according to the method in embodiment 2, with solution B wherein, flood this active carbon, and the dry and reduction according to the method in embodiment 2, adsorbent 106g obtained, stannous chloride load capacity approximately 75% (by quality of activated carbon).
Press preceding method test adsorbent equilibrium adsorption capacity, CO is adsorbance 103ml/g first.Adsorbance 71ml/g for the second time and for the third time.CO content 99.2% in the gas parsing during regeneration.
Claims (8)
1. the separated preparation method with adsorbent of a gas absorption, the method be take active carbon as carrier, mantoquita and/or other auxiliary agent are immersed on absorbent charcoal carrier, active carbon after dipping is dried, decomposes and/or reduces in drying tower, it is characterized in that in described dry, decomposition and/or reduction process, by electric current is passed in the active carbon after dipping, thereby make active carbon generate heat dry run prepared by catalyst;
Described mantoquita is one or more in copper chloride, copper nitrate, copper acetate, copper formate, cupric oxalate, copper sulphate.
2. the separated preparation method with adsorbent of gas absorption according to claim 1, it is characterized in that described method electric current being passed in the active carbon after dipping is by the electrode of power supply being directly connected in to the active carbon after dipping in drying tower, then make electric current flow through the active carbon between electrode and electrode, make active carbon itself heating to complete dry, decomposition and/or the reduction process of adsorbent.
3. the separated preparation method with adsorbent of gas absorption according to claim 1, it is characterized in that described electric current being passed into method in the active carbon after dipping for producing induced-current in the active carbon of the mode by alternating current impression after dipping, thereby electric current is passed in drying tower to the active carbon after dipping, and active carbon heating itself is to complete being dried of adsorbent, decomposition and/or reduction process.
4. the separated preparation method with adsorbent of gas absorption according to claim 2, is characterized in that the voltage of the electric current that passes into is 5～10000V.
5. the separated preparation method with adsorbent of gas absorption according to claim 3, the a-c cycle that it is characterized in that the power supply of alternating current impression is 50Hz～100kHz.
6. according to the separated preparation method with adsorbent of gas absorption described in claim 1～5, it is characterized in that, decomposition dry by completing between heating activated carbon to 50～1500 after dipping ℃ and/or reduction process.
7. according to the separated preparation method with adsorbent of the gas absorption described in claim 1～6, it is characterized in that in dry run, pass into inert gas or adopt vacuum draw to take the solvent being evaporated out of drying tower.
8. according to the separated preparation method with adsorbent of gas absorption described in claim 1～7, it is characterized in that after dry, decomposition for the first time and/or reduction process complete, then repeat one or many dipping and dry, decomposition and/or reduction process.
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| CN201210202195.9A CN103506070A (en) | 2012-06-19 | 2012-06-19 | Preparation method of copper loaded activated carbon adsorbent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801272A (en) * | 2015-04-15 | 2015-07-29 | 南通职业大学 | Preparation method of cobalt-supported activated carbon as well as condition and device for adsorbing methylbenzene with cobalt-supported activated carbon |
| CN104941613A (en) * | 2015-06-15 | 2015-09-30 | 武汉轻工大学 | Preparation method of supported flower-shaped copper oxide and method for deeply removing hydrogen phosphide from yellow phosphorus tail gas |
| CN113351171A (en) * | 2021-07-07 | 2021-09-07 | 全球能源互联网研究院有限公司 | Adsorbent and preparation method and application thereof |
| CN113351159A (en) * | 2020-03-04 | 2021-09-07 | 中国石油化工股份有限公司 | Adsorbent for deeply removing carbon monoxide in hydrogen, preparation method thereof and method for removing carbon monoxide in hydrogen by using adsorbent |
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
| CN113639549A (en) * | 2021-08-13 | 2021-11-12 | 成都中科普瑞净化设备有限公司 | Electric heating dipping drying rotary kiln |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039364A (en) * | 1989-09-07 | 1990-02-07 | 中国市政工程西北设计院 | Active carbon fluid discharge drying method and device |
| CN101695651A (en) * | 2009-10-27 | 2010-04-21 | 昆明理工大学 | Copper and iron-loaded modified activated carbon absorbent and method for preparing same |
-
2012
- 2012-06-19 CN CN201210202195.9A patent/CN103506070A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039364A (en) * | 1989-09-07 | 1990-02-07 | 中国市政工程西北设计院 | Active carbon fluid discharge drying method and device |
| CN101695651A (en) * | 2009-10-27 | 2010-04-21 | 昆明理工大学 | Copper and iron-loaded modified activated carbon absorbent and method for preparing same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801272A (en) * | 2015-04-15 | 2015-07-29 | 南通职业大学 | Preparation method of cobalt-supported activated carbon as well as condition and device for adsorbing methylbenzene with cobalt-supported activated carbon |
| CN104941613A (en) * | 2015-06-15 | 2015-09-30 | 武汉轻工大学 | Preparation method of supported flower-shaped copper oxide and method for deeply removing hydrogen phosphide from yellow phosphorus tail gas |
| CN113351159A (en) * | 2020-03-04 | 2021-09-07 | 中国石油化工股份有限公司 | Adsorbent for deeply removing carbon monoxide in hydrogen, preparation method thereof and method for removing carbon monoxide in hydrogen by using adsorbent |
| CN113351171A (en) * | 2021-07-07 | 2021-09-07 | 全球能源互联网研究院有限公司 | Adsorbent and preparation method and application thereof |
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
| CN113639549A (en) * | 2021-08-13 | 2021-11-12 | 成都中科普瑞净化设备有限公司 | Electric heating dipping drying rotary kiln |
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Application publication date: 20140115 |