CN102744034A - High-mechanical strength stored ammonia mixture containing ceramic fiber and preparation method thereof - Google Patents
High-mechanical strength stored ammonia mixture containing ceramic fiber and preparation method thereof Download PDFInfo
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- CN102744034A CN102744034A CN2012102388421A CN201210238842A CN102744034A CN 102744034 A CN102744034 A CN 102744034A CN 2012102388421 A CN2012102388421 A CN 2012102388421A CN 201210238842 A CN201210238842 A CN 201210238842A CN 102744034 A CN102744034 A CN 102744034A
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Abstract
The invention relates to a high-mechanical strength stored ammonia mixture containing a ceramic fiber. The high-mechanical strength stored ammonia mixture contains anhydrous magnesium chloride, the ceramic fiber and industrial clay. The high-mechanical strength stored ammonia mixture is characterized in that the preparation method comprises the steps of: forming mixture by industrial anhydrous magnesium chloride powder, the ceramic fiber, the industrial clay and industrial alcohol; uniformly agitating the mixture by an agitator, forming semi-drying mixture powder; adding the semi-drying mixture powder to an open sealed container to mechanically oscillate, forming a wet sample block, and drying the sample block for 2-3 hours under the condition that the temperature is 60-80 DEG C and the vacuum degree is 1-10pa to 1Kpa. The prepared storage ammonia mixture has super-strong adsorptive capacity, stable structure and high mechanical strength; in a process of preparing the active stored ammonia mixture, proper industrial clay is also added. Clay mineral has plasticity after being humidified by water, and can deform and keep an original shape for a long time under smaller pressure; the specific surface area is large, and the particles have electronegativity, so the high-mechanical strength stored ammonia mixture has good physical adsorbability and surface chemical activity, and the viscosity and adsorbability of the mixture can be further improved.
Description
Technical field
The present invention relates to a kind of high mechanical properties storage ammonia mixture that contains ceramic fibre and preparation method thereof, be applied to the after-treatment system and the new-energy automobile hydrogen fuel cell system of vehicle exhaust.
Background technology
Nowadays, the whole world is being faced with the double challenge of energy crisis and environmental crisis at present.Aspect the technological means selection of the emission compliance of orthodox car, and the fuel of new-energy automobile is supplied with the technical elements people and is still faced many difficult problems.
Orthodox car aspect, SCR after-treatment system are to rely on the accurate supply of carbamide reducing agent and after the front end of catalyst resolves into ammonia, remove the NOX hazardous material, and then realize the purpose of cleaning of off-gas.But; In actual use, this dependence urea decomposition becomes the metered injection of the liquid area of ammonia to have many deficiencies and difficult point, and for example urea liquid could decompose at a certain temperature; And many vehicles of public transit system loiter; Can't reach urea liquid stable decomposition temperature at all, can't the output ammonia, influence is used normally.The new-energy automobile aspect, the hydrogen fuel cell automobile is a very important techniques route by generally acknowledging.But how stable acquisition hydrogen source is a no small difficult problem of restriction this area development.Ammonia is a kind of the highest gas of hydrogen density that contains, very active under the normal temperature, very easily diffusion.Therefore, if can resolve the storage problem of ammonia, just can hew out the hydrogen fuel cell technology path of " storage ammonia-hydrogen manufacturing-Chu Qing " and the SCR post processing reducing agent operation technique route of " storage ammonia-release ammonia " simultaneously.
We know that some slaine can form complex compound with ammonia under given conditions, and then under uniform temperature or pressure, can realize the desorb of ammonia again, and then reach the function of the storage and the utilization of ammonia.For example, 1 magnesium chloride molecule can with 6 NH
3Molecule forms complex compound, realizes highdensity storage ammonia function.
In the national patent Information Network; With " storage ammonia " " slaine " word and search that is the theme; The patent No. is that CN200680005886.2's the high density of the ammonia ' storage ' invention comprises the solid ammonia storage of ammonia absorptions/desorb solid material and carries material, and the said density that has been compacted to is greater than 50% storage of theoretical skeletal density with carry material that the solid ammonia storage medium is provided, and this storage medium is preparation and processing and storage ammonia with very high-density easily; Said storage ammonia discharges under controlled condition easily; Even the porosity of said material is very low still like this, and this storage medium does not need special safety measure for storage with to carry ammonia be safe.This patent is to adopt the direct compression molding of solid material; Adopt binding agent; Only stated it possibly is the silicon dioxide fibre binding agent, do not had the dosage ratio, the solid material of also only stating among other claim item and the embodiment possibly comprise granular materials, porous material, crystalline material, amorphous materials or their bond composition; Do not have thin of clear and definite claim, industry technology personage almost can't implement.
Ceramic fibre is a kind of fibrous light refractory material; Have in light weight, high temperature resistant, Heat stability is good, thermal conductivity is low, specific heat is little and advantage such as anti-mechanical shock, thereby all obtained using widely in industries such as machinery, metallurgy, chemical industry, oil, pottery, glass, electronics.Compare with traditional material, ceramic fibre is a kind of fibrous light heat-insulating material, has in light weight, high temperature resistant, Heat stability is good, thermal conductivity is low, specific heat capacity is little and advantage such as anti-mechanical shock, and product has following advantage:
Bulk density is low: adopt ceramic fibre lightening material structural load greatly, prolong material service life; Thermal capacity is low: reduced the energy loss amount during matrix material controls effectively; Low heat conductivity: insulation effect is remarkable; Anti-thermal shock and mechanical shock function admirable: fiber has good especially resistance to violent temperature fluctuation and mechanical shock; Stable chemical performance: ceramic fibre belongs to neutral slant acidity material, except that reacting with strong acid-base, is not corroded by other weak acid, alkali and water, oil, steam, does not soak into lead, aluminium, copper; Applied widely: domestic ceramic fibre is widely used at electric power, metallurgy, oil, chemical industry, electronics, boats and ships, communications and transportation, building construction and some light industrial segments, and is used for frontiers of science and technology such as aerospace and atomic energy.
Given this, the magnesium chloride powder that the present invention has better adsorption capacity with support, the principle that can carry out the absorption and the desorb of ammonia is under given conditions prepared a kind of active mixture porosu solid appearance piece that can store ammonia.And also having added in this mixture has a certain amount of ceramic fibre, the interpolation of ceramic fibre to reduce the whole weight of mixture porosu solid appearance piece, improves mixture appearance piece heat endurance and mechanical strength, prolongs its service life.
Summary of the invention
The purpose of this invention is to provide a kind of high mechanical properties storage ammonia mixture that contains ceramic fibre and preparation method thereof, the storage ammonia active mixture of its preparation has superpower adsorption capacity, and Stability Analysis of Structures; Mechanical strength is higher, in the process of the active storage of preparation ammonia mixture, has also added the appropriate amount of industrial clay; Owing to have plasticity after the clay mineral water is moistening; Under less pressure, can be out of shape also and can maintain the original state for a long time, and specific area is big, has elecrtonegativity on the particle; Therefore good physical adsorbability and chemical mobility of the surface are arranged, so just can further improve the viscosity and the adsorption capacity of mixture.
Technical scheme of the present invention is achieved in that the high mechanical properties storage ammonia mixture that contains ceramic fibre; Form by anhydrous magnesium chloride, ceramic fibre and industrial clay; It is characterized in that its preparation method: by weight percentage,, stir through mixer with industrial anhydrous chlorides of rase magnesium salts powder 69 ~ 80wt%, ceramic fibre 4 ~ 10wt%, industrial clay 4 ~ 7wt% and industrial alcohol 11 ~ 17wt% composition mixture; Mixing time is 1 ~ 10h, forms the mixed powder of semi-drying; But the mixed powder of this semi-drying adds in the closed container of an open type and carries out mechanical oscillation 30 ~ 60min, forms wet body appearance piece; The appearance piece is at 60 ~ 80 ℃, and vacuum is 1 ~ 10
-1Dry 2 ~ 3h under the condition of Kpa, or under 60 ~ 100 ℃ temperature dry 2 ~ 4h.
Good effect of the present invention is that the storage ammonia active mixture of its preparation has superpower adsorption capacity, and Stability Analysis of Structures, and mechanical strength is higher; In the process of the active storage of preparation ammonia mixture; Also added the appropriate amount of industrial clay,, under less pressure, can be out of shape also and can maintain the original state for a long time because the clay mineral water has plasticity after moistening; And specific area is big; Have elecrtonegativity on the particle, therefore good physical adsorbability and chemical mobility of the surface are arranged, so just can further improve the viscosity and the adsorption capacity of mixture; Be more suitable in the hydrogen fuel cell system of the after-treatment system and the new-energy automobile of orthodox car industry.
Description of drawings
Fig. 1 is the thermogravimetric curve behind the porous active storage ammonia mixture absorbing ammonia for preparing of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further:
Embodiment 1
Industrial alcohol composition mixture with ceramic fibre, 7wt% industry clay and the 17wt% of the industrial anhydrous chlorides of rase magnesium salts powder of 69wt%, 7wt% stirs through mixer, and mixing time is 1h, forms the mixed powder of semi-drying; But the mixed powder of this semi-drying is added in the closed container of an open type and carry out mechanical oscillation 30min, form wet body appearance piece, then at 80 ℃, vacuum is 10
-1Dry 2h under the condition of Kpa gets final product to such an extent that contain the storage ammonia active mixture of 8.4wt% ceramic fibre.
10g is stored up the ammonia active mixture fill ammonia; Under the environment of gravity-flow ventilation, carry out; But in advance will the closed container of open type put into the tank of the enough big cooling water of water yield, connection ammonia steel cylinder is through pressure-reducing valve and drying system; In the pressure limit of 1Mpa slowly fill ammonia, filling the ammonia time is 3h; Fill that this kind piece quality is 19.1g behind the ammonia, i.e. absorbing ammonia 9.1g.And then the appearance piece carried out heat treated under 450 ℃, and the result finds that a heating back appearance piece quality becomes 10.5g, has promptly discharged ammonia 8.6g, desorption efficiency is 95%.Weight-loss curve behind this porosu solid appearance piece absorbing ammonia is as shown in Figure 1, and as can be seen from the figure, mixture porosu solid appearance piece absorbing ammonia percentage by weight is about 45wt%, with theoretical weightless value consistent
.
Embodiment 2
Industrial alcohol composition mixture with ceramic fibre, 4wt% industry clay and the 12wt% of the industrial anhydrous chlorides of rase magnesium salts powder of 80wt%, 4wt% stirs through mixer, and mixing time is 5h, forms the mixed powder of semi-drying; But the mixed powder of this semi-drying is added in the closed container of an open type and carry out mechanical oscillation 60min; Form wet body appearance piece; Then at 60 ℃, vacuum is dry 3h under the condition of 1Kpa, gets final product to such an extent that contain the storage ammonia active mixture
of 4.5wt% ceramic fibre.
10g is stored up the ammonia active mixture fill ammonia; Under the environment of gravity-flow ventilation, carry out; But in advance will the closed container of open type put into the tank of the enough big cooling water of water yield, connection ammonia steel cylinder is through pressure-reducing valve and drying system; In the pressure limit of 0.3Mpa slowly fill ammonia, filling the ammonia time is 5h; Fill that this kind piece quality is 19.9g behind the ammonia, i.e. absorbing ammonia 9.9g.And then the appearance piece carried out heat treated under 450 ℃, and the result finds that a heating back appearance piece quality becomes 10.5g, has promptly discharged ammonia 9.4g, desorption efficiency is 95%.
Embodiment 3
Industrial alcohol composition mixture with ceramic fibre, 4wt% industry clay and the 11wt% of the industrial anhydrous chlorides of rase magnesium salts powder of 75wt%, 10wt% stirs through mixer, and mixing time is 10h, forms the mixed powder of semi-drying; But the mixed powder of this semi-drying is added in the closed container of an open type and carry out mechanical oscillation 45min; Form wet body appearance piece, and then dry 3h gets final product to such an extent that contain the storage ammonia active mixture
of 11.2wt% ceramic fibre under 100 ℃ temperature.
10g is stored up the ammonia active mixture fill ammonia; Under the environment of gravity-flow ventilation, carry out; But in advance will the closed container of open type put into the tank of the enough big cooling water of water yield, connection ammonia steel cylinder is through pressure-reducing valve and drying system; In the pressure limit of 0.2Mpa slowly fill ammonia, filling the ammonia time is 8h; Fill that this kind piece quality is 19.1g behind the ammonia, i.e. absorbing ammonia 9.1g.And then the appearance piece carried out heat treated under 450 ℃, and the result finds that a heating back appearance piece quality becomes 11g, has promptly discharged ammonia 8.1g, desorption efficiency is 89%.
Claims (1)
1. the high mechanical properties storage ammonia mixture that contains ceramic fibre; Form by anhydrous magnesium chloride, ceramic fibre and industrial clay; It is characterized in that its preparation method: by weight percentage,, stir through mixer with industrial anhydrous chlorides of rase magnesium salts powder 69 ~ 80wt%, ceramic fibre 4 ~ 10wt%, industrial clay 4 ~ 7wt% and industrial alcohol 11 ~ 17wt% composition mixture; Mixing time is 1 ~ 10h, forms the mixed powder of semi-drying; But the mixed powder of this semi-drying adds in the closed container of an open type and carries out mechanical oscillation 30 ~ 60min, forms wet body appearance piece; The appearance piece is at 60 ~ 80 ℃, and vacuum is 1 ~ 10
-1Dry 2 ~ 3h under the condition of Kpa, or under 60 ~ 100 ℃ temperature dry 2 ~ 4h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254943A (en) * | 2022-04-08 | 2022-11-01 | 中国科学院地球化学研究所 | Remediation and treatment method for soil in historical mercury pollution leaving site |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899683A (en) * | 2006-07-05 | 2007-01-24 | 南京工业大学 | Attapulgite-based composite adsorbent for ammonia adsorption refrigeration and preparation and application thereof |
| JP2007307558A (en) * | 2007-06-25 | 2007-11-29 | Jfe Engineering Kk | Adsorption/desorption agent, process for separation, and storage method for ammonia using combination of specific metal halides |
| CN101454064A (en) * | 2006-02-27 | 2009-06-10 | 氨合物股份公司 | A method of storing and delivering ammonia and the use of electromagnetic radiation for desorption of ammonia from a chemical complex |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454064A (en) * | 2006-02-27 | 2009-06-10 | 氨合物股份公司 | A method of storing and delivering ammonia and the use of electromagnetic radiation for desorption of ammonia from a chemical complex |
| CN1899683A (en) * | 2006-07-05 | 2007-01-24 | 南京工业大学 | Attapulgite-based composite adsorbent for ammonia adsorption refrigeration and preparation and application thereof |
| JP2007307558A (en) * | 2007-06-25 | 2007-11-29 | Jfe Engineering Kk | Adsorption/desorption agent, process for separation, and storage method for ammonia using combination of specific metal halides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254943A (en) * | 2022-04-08 | 2022-11-01 | 中国科学院地球化学研究所 | Remediation and treatment method for soil in historical mercury pollution leaving site |
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