CN103736455A - Copper-iron modified metal organic skeleton adsorbent and preparation method thereof - Google Patents
Copper-iron modified metal organic skeleton adsorbent and preparation method thereof Download PDFInfo
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- CN103736455A CN103736455A CN201310686906.9A CN201310686906A CN103736455A CN 103736455 A CN103736455 A CN 103736455A CN 201310686906 A CN201310686906 A CN 201310686906A CN 103736455 A CN103736455 A CN 103736455A
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Abstract
The invention discloses a copper-iron modified metal organic skeleton adsorbent and a preparation method thereof. A metal organic skeleton is taken as the carrier of the adsorbent, and oxides of two transition metals such as copper and iron are loaded as the active compositions. The preparation method of the modified metal organic skeleton adsorbent is simple, the operationality is strong, the purifying efficiency is improved and the purifying cost is reduced.
Description
Technical field
The present invention relates to a kind of technology of preparing of adsorbent, particularly the preparation method of load type adsorbing agent for a kind of low-concentration hydrogen phosphide purification, belongs to adsorption separation technology field.
Background technology
Under hydrogen phosphide normal temperature, be a kind of gas of colourless foul smelling taste, have severe toxicity, its discharge can cause atmosphere pollution, endangers environmental and human health impacts, and affects the recycling of yellow phosphoric tail gas and the calcium carbide stove exhaust of phosphine containing.At present, more to the purification techniques of low-concentration hydrogen phosphide both at home and abroad, mainly contain combustion method, chemical oxidation absorption process, catalytic oxidation and absorption method etc.But these methods all exist that dephosphorization precision is not high, energy consumption is high, efficiency is low, flow process is complicated, investment is large or the defect such as secondary pollution, especially not high to the adsorption capacity of hydrogen phosphide.Use yellow phosphoric tail gas that said method purified to fail to reach a carbonizer requirement, yellow phosphoric tail gas be rich in carbon monoxide source of the gas, but because it contains the comprehensive utilization that hydrogen phosphide impurity has limited yellow phosphoric tail gas.Therefore the adsorbent of developing a series of high-adsorption-capacities is removed hydrogen phosphide impurity and reached good clean-up effect from yellow phosphoric tail gas is a urgent task.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of have high-adsorption-capacity for adsorbent from yellow phosphoric tail gas Adsorption phosphine gas and preparation method thereof, adsorbent provided by the invention does not need to add the promoter such as noble metal (AgO) or high pollution heavy metal (HgO, CdO).
Copper iron modified metal organic backbone adsorbent provided by the invention, using the carrier of metallic organic framework as adsorbent, on this carrier, the oxide of supported copper, two kinds of transition metal of iron is as active component, the composition of modified activated carbon absorbent is counted with % by weight: Cu oxide counts 1.30～1.51% with copper, ferriferous oxide counts 0.057～0.23% with ferro element, and surplus is metallic organic framework; In oxide, the mol ratio of copper and iron is 5～20:1.
Copper iron modified metal organic backbone adsorbent provided by the invention is prepared through following method:
(1) select metallic organic framework MOF-5, specific area is 500～3800m
2/ g.
(2) active carbon of operation (1) being processed immerses in the nitrate aqueous solution of the certain proportioning that contains copper, iron, the concentration of nitrate aqueous solution is 55.11～67.93g/L, wherein the mol ratio of copper and iron is 5～20:1, the metallic organic framework immersing and the solid-liquid of nitrate aqueous solution are than being 1041.67g/L, fully stir, under 30 ℃ of conditions, with ultrasonic immersing 40～60 minutes, take out the metallic organic framework after dipping, at 80～100 ℃ of temperature, be dried 12～24 hours;
(3) will be through the metallic organic framework of operation (2) 200～400 ℃ of roasting temperatures 2～8 hours, take out and be placed in drying basin and be cooled to room temperature, can obtain the copper iron modified metal organic backbone adsorbent of adsorption of Low Concentration phosphine gas.
Compared to the prior art, the present invention has the following advantages or good effect: method is simple, workable, has improved purification efficiency high, reduces and purifies cost; Upon adsorption saturated, can realize waste gas dephosphorization, realize changing waste into resources; Reaction condition is gentle, is easy to realize.
The specific embodiment
With embodiment, the invention will be further described below.
Experiment condition: adsorbent 5g, adsorption column import phosphine concentration is 1000ppm, and nitrogen is carrier gas, and oxygen content is 1%, 80 ℃ of adsorption conditions constant temperature, under condition of normal pressure, air speed 3000/h, total flow 500ml/min.
Embodiment 1
Select metallic organic framework MOF-5, specific area is 3800m
2/ g.Take 1.88g Cu (NO
3)
23H
2o and 0.81g Fe (NO
3)
39H
2o mixes, and makes Cu/Fe=5:1(mol ratio), with 24ml distilled water, dissolve, obtain maceration extract; Above-mentioned metallic organic framework MOF-5 is taken to 27g and immerse in maceration extract, fully stir, under 30 ℃ of conditions, with conventional Ultrasound, flood 60 minutes, be placed in afterwards baking oven, at 100 ℃ of temperature, be dried 12 hours; Finally be placed in Muffle furnace, 400 ℃ of roasting temperatures 8 hours, take out and be placed in drying basin and be cooled to room temperature, can obtain the acticarbon of adsorption of Low Concentration phosphine gas, clean-up effect is in Table 1.
Table 1 clean-up effect
| Time/min | 50 | 100 | 150 | 200 | 250 | 300 | 600 | 900 |
| Purification efficiency/% | 100 | 99.2 | 98.1 | 97.2 | 95.3 | 90.2 | 88.2 | 88.1 |
Embodiment 2
Select metallic organic framework MOF-5, specific area is 2100m
2/ g.Take 7.5g Cu (NO
3)
23H
2o and 0.81g Fe (NO
3)
39H
2o mixes, and makes Cu/Fe=20:1(mol ratio), with 24ml distilled water, dissolve, obtain maceration extract; Above-mentioned metallic organic framework MOF-5 is taken to 23g and immerse in maceration extract, fully stir, under 30 ℃ of conditions, with conventional Ultrasound, flood 30 minutes, be placed in afterwards baking oven, at 100 ℃ of temperature, be dried 20 hours; Finally be placed in Muffle furnace, 400 ℃ of roasting temperatures 4 hours, take out and be placed in drying basin and be cooled to room temperature, can obtain the acticarbon of adsorption of Low Concentration phosphine gas, clean-up effect is in Table 2.
Table 2 clean-up effect
| Time/min | 50 | 100 | 150 | 200 | 250 | 300 | 600 | 900 |
| Purification efficiency/% | 95.2 | 100 | 99.1 | 95.2 | 90.1 | 87.2 | 84.5 | 83.1 |
Embodiment 3
Select metallic organic framework MOF-5, specific area is 1000m
2/ g.Take 3.75g Cu (NO
3)
23H
2o and 0.81g Fe (NO
3)
39H
2o mixes, and makes Cu/Fe=10:1(mol ratio), with 24ml distilled water, dissolve, obtain maceration extract; Above-mentioned metallic organic framework MOF-5 is taken to 25g and immerse in maceration extract, fully stir, under 30 ℃ of conditions, with conventional Ultrasound, flood 40 minutes, be placed in afterwards baking oven, at 100 ℃ of temperature, be dried 24 hours; Finally be placed in Muffle furnace, 400 ℃ of roasting temperatures 4 hours, take out and be placed in drying basin and be cooled to room temperature, can obtain the acticarbon of adsorption of Low Concentration phosphine gas, clean-up effect is in Table 3.
Table 3 clean-up effect
| Time/min | 50 | 100 | 150 | 200 | 250 | 300 | 600 | 900 |
| Purification efficiency/% | 96.4 | 98.9 | 100 | 97.3 | 95.1 | 88.2 | 84.3 | 82.7 |
Claims (2)
1. a copper iron modified metal organic backbone adsorbent, using the carrier of metallic organic framework as adsorbent, it is characterized in that, on this carrier, the oxide of supported copper, two kinds of transition metal of iron is as active component, the composition of described modified metal organic backbone adsorbent is counted with % by weight: Cu oxide counts 1.30～1.51% with copper, ferriferous oxide counts 0.057～0.23% with ferro element, and surplus is metallic organic framework; In described oxide, the mol ratio of copper and iron is 5～20:1.
2. a preparation method for copper iron modified metal organic backbone adsorbent as claimed in claim 1, is characterized in that having following preparation section:
(1) select metallic organic framework MOF-5, specific area is 500～3800m
2/ g.
(2) metallic organic framework is immersed in the nitrate aqueous solution of the certain proportioning that contains copper, iron, the concentration of nitrate aqueous solution is 55.11～67.93g/L, wherein the mol ratio of copper and iron is 5～20:1, the active carbon immersing and the solid-liquid of nitrate aqueous solution are than being 1041.67g/L, fully stir, under 30 ℃ of conditions, with ultrasonic immersing 40～60 minutes, take out the metallic organic framework after dipping, at 80～100 ℃ of temperature, be dried 12～24 hours;
(3) will be through the metallic organic framework of operation (2) 150～400 ℃ of roasting temperatures 2～8 hours, take out and be placed in drying basin and be cooled to room temperature, can obtain the copper iron modified metal organic backbone adsorbent of adsorption of Low Concentration phosphine gas.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105457615A (en) * | 2015-11-24 | 2016-04-06 | 南京工业大学 | Preparation method of Mn modified metal organic framework material adsorbent for super-deep oil and gas recovery |
| CN106732799A (en) * | 2016-12-16 | 2017-05-31 | 大连交通大学 | A kind of new type low temperature denitration MOF catalyst and preparation method thereof |
| CN111992185A (en) * | 2020-09-21 | 2020-11-27 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN113651514A (en) * | 2021-08-20 | 2021-11-16 | 广州和源生态科技发展股份有限公司 | Substrate modifier for submerged ecological restoration and preparation method thereof |
| CN113797896A (en) * | 2021-10-09 | 2021-12-17 | 湖北中烟工业有限责任公司 | Preparation method of metal organic framework adsorbing material and adsorbing material obtained by same |
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| CN101816924A (en) * | 2010-04-13 | 2010-09-01 | 东南大学 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
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| CN101816924A (en) * | 2010-04-13 | 2010-09-01 | 东南大学 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457615A (en) * | 2015-11-24 | 2016-04-06 | 南京工业大学 | Preparation method of Mn modified metal organic framework material adsorbent for super-deep oil and gas recovery |
| CN106732799A (en) * | 2016-12-16 | 2017-05-31 | 大连交通大学 | A kind of new type low temperature denitration MOF catalyst and preparation method thereof |
| CN106732799B (en) * | 2016-12-16 | 2019-01-22 | 大连交通大学 | A kind of new type low temperature denitration MOF catalyst and preparation method thereof |
| CN111992185A (en) * | 2020-09-21 | 2020-11-27 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN111992185B (en) * | 2020-09-21 | 2022-04-29 | 桂林理工大学 | Cu-MOF, modified adsorption material thereof and preparation method |
| CN113651514A (en) * | 2021-08-20 | 2021-11-16 | 广州和源生态科技发展股份有限公司 | Substrate modifier for submerged ecological restoration and preparation method thereof |
| CN113797896A (en) * | 2021-10-09 | 2021-12-17 | 湖北中烟工业有限责任公司 | Preparation method of metal organic framework adsorbing material and adsorbing material obtained by same |
| CN113797896B (en) * | 2021-10-09 | 2023-11-24 | 湖北中烟工业有限责任公司 | Preparation method of metal organic framework adsorption material and adsorption material obtained by preparation method |
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Application publication date: 20140423 |