CN102731054A - Porous solid block sample of ammonia storage mixture containing molecular sieves and method for preparing same - Google Patents
Porous solid block sample of ammonia storage mixture containing molecular sieves and method for preparing same Download PDFInfo
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- CN102731054A CN102731054A CN2012102388402A CN201210238840A CN102731054A CN 102731054 A CN102731054 A CN 102731054A CN 2012102388402 A CN2012102388402 A CN 2012102388402A CN 201210238840 A CN201210238840 A CN 201210238840A CN 102731054 A CN102731054 A CN 102731054A
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Abstract
The invention relates to a porous solid block sample of an ammonia storage mixture containing molecular sieves and a method for preparing the same. The porous solid block sample of the ammonia storage mixture containing the molecular sieves is composed of anhydrous strontium chloride (SrCl2), the molecular sieves and industrial silica sol; and the method for preparing the porous solid block sample comprises the following specific steps of: blending the powder of industrial anhydrous strontium chloride salt with the industrial silica sol, the molecular sieves and industrial spirit to form a mixture; mixing the mixture by a stirrer to form semi-dry mixed powder, and then obtaining the porous solid block sample of the ammonia storage mixture through mechanical oscillation and drying, wherein the ammonia storage property of the metal salt is guaranteed and the richness of microcosmic nanopores is also improved; besides, the number of macro-holes is increased and the mechanical strength of the porous solid block sample of the mixture is improved; in addition, appropriate industrial silica sol is further added, so that the viscosity and the specific surface area of the porous solid block sample of the mixture are effectively improved.
Description
Technical field
The present invention relates to a kind of storage ammonia mixture porosu solid appearance piece that contains molecular sieve and preparation method thereof, be applied to the SCR after-treatment system and the FCEV fuel cell system of vehicle exhaust.
Background technology
Current, the whole world faces the comprehensive challenge of the energy and environment.Aspect the technique means selection of the emission compliance of orthodox car, and the fuel feed technical elements people of new-energy automobile still face many difficult problems.
The SCR after-treatment system is to rely on the accurate supply of carbamide reducing agent and after the front end of catalyzer resolves into ammonia, remove the NOX hazardous material, reaches the purpose of cleaning of off-gas, realizes state 4 or above standard up to standard of vehicle.But in actual use, this dependence urea decomposition becomes the meter injection of the liquid area of ammonia to have many deficiencies and difficult point, and for example, urea soln is icing blocking problem under-11 ℃ of environment, needs extra pipeline heating system to solve; Urea soln could decompose under the temperature environment more than 135 ℃, and many vehicles of public transit system loiter, and can't reach urea soln stable decomposition temperature at all; Can't the output ammonia, can't eliminate predetermined NOX composition, cause the accumulation of liquid area in vapor pipe at last; Produce the polymkeric substance of trimeric cyanamide; Stop up the urea nozzle and the exhaust pipe of engine, cause vehicles produces fault, and influence is used normally.In addition; If the main flow vehicle of state more than 4 uses the SCR system comprehensively; Relate to the whole nation about 150,000 oiling websites innovation and build the problem of liquid area filling Infrastructure; Because investment is huge, do not see still that at present government and enterprise start to improve this Infrastructure, become a huge problem of potential in the SCR use.
For breaking through energy predicament, solve the new-energy automobile development problem of future source of energy problem, hydrogen fuel cell 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.In institute's possible adopted hydrogen source mode, technological line and the hydrogeneous presoma decomposition of other H-N or the technological line of cracking hydrogen production of the technological line of gas cylinder storage hydrogen, the technological line that water electrolysis hydrogen production is arranged, the technological line that high-purity hydro carbons oil fuel cracking hydrogen production is arranged, low mass molecule alcohol class cracking hydrogen production arranged.In the above-mentioned technological line, all there are some problem and shortage, for example, hydrogen production efficiency and cost, hydrogen manufacturing precision and speed also comprise the problem of system aspects.In a word, the source of hydrogen is the bottleneck of fuel-cell vehicle development, needs people's idea to solve.
One of them is the hydrogenous compound of H-N for the presoma of hydrogen, and wherein, what hydrogen-storage density was the highest is ammonia.Ammonia is a kind of modal industrial chemicals, and the ammonia molecule belongs to active polar molecule, and the diameter dimension of molecule is about 3 ~ 4; Therefore, very active under the normal temperature, very easily diffusion; And having toxic, the skin histology that its toxic is embodied in contact all has corrosion and hormesis, can absorb the moisture in the skin histology; Make the tissue protein sex change, and make the tissue fat saponification, destroy membrane structure.Ammonia in water solubleness high, stimulate and corrosive nature so mainly the upper respiratory tract of animal or human's body is had, often be attracted on mucocutaneous and the eye conjunctiva, stimulate and inflammation thereby produce.In addition, ammonia sucks human body with gas form usually, threat to life safety, and therefore, the maximum hidden danger of the use of ammonia is safety-problems.
This shows, resolve in the use of ammonia storing and safety-problems, just can open up the technological line of a new ammonia utilization.
Traditional ammonia storing mode is a gas cylinder, or realizes with the water-soluble formation ammoniacal liquor of high density ammonia.If adopt gas cylinder to store ammonia, there is the potential safety hazard of operating aspect and seal aspect in the industrial application in enormous quantities, if, have serious etching problem again with the mode of high strong aqua.
In the national patent Information Network; Word and search is the theme with " storage ammonia "; The patent No. is that CN201120099229.7's ' a kind of urotropine by using gas phase method tail gas ammonia recovery unit ', the patent No. is that ' be used for freezer machine room join ammonia connection mechanism ' of CN201020677361.7, ' complex function type storage ammonia device ', the patent No. that the patent No. is CN201020269811.9 are CN200520057558.X ' a kind of ammonia steaming device '; Be one type the ammonia nitrogen trade effluent carried out the environment protection treating device that ammonia nitrogen is got rid of processing, also do not relate to the characteristic component among the present invention.Uncorrelated with the present invention.
The patent No. is that CN201010244091.5's ' be used for method and system that the work of SCR catalyzer is tested ' and the patent No. is that this 2 inventions of CN200880104697.X ' operation method of SCR exhaust after treatment system and diagnostic method ' provide a kind of SCR (SCR) catalytic converter and traditional liquid ureaclastic ammonia dispensing module and system of being used for, and does not relate to the characteristic component of compound.
The patent No. is that CN200910197860.8's the invention of ' a kind of preparation method of efficient low-temperature ammonia-storing material ' is applied to the SCR after-treatment system; Characteristic is to place encloses container to the amino borane compound; Vacuumize, under 0 ~ 4 ℃ of temperature, contact with ammonia; Under 0 ~ 4 ℃ of temperature, keep 30 ~ 60min, prepare required product amino borane ammonia complex NH
3BH
3(NH
3) n (n=1 ~ 3); The maximum storage of room temperature ammonia amount can reach 62.4wt.%; About room temperature supply gas pressure 2.0bar; Room temperature supplies ammonia pressure moderate, inhales to put the ammonia completely reversibility, but the costing an arm and a leg of the extraordinary material amino borane of this patent; Have higher explosion hazard and burning grade, be not suitable for applying in enormous quantities of general industry field;
The patent No. is that CN200580026626.9's the invention of ' storage and carry the solid material of ammonia ' relates to storage and carries the solid material of ammonia.The solid material of this storage ammonia comprises that a kind of ammonia absorbs salt, and wherein this ammonia absorption salt is that general formula is M
a(NH
3)
nX
zIonic salt; Wherein M is selected from for example one or more positively charged ions of Mn, Fe, Co, Ni, Cu and/or Zn of earth alkali metal and/or one or more transition metal, and X is one or more negatively charged ion, and a is the positively charged ion number that comprises in each molecules of salt; Z is the negatively charged ion number that comprises in each molecules of salt; N is 2～12 ligancy, and wherein M is Mg, and it is automotive industry that this ammonia absorbs salt provides a kind of safety, lightweight, cheap and fine and close storage with ammonia.This patent is the direct compression molding of solid material, and electric heating heating desorption ammonia more lays particular emphasis on the control strategy of system, does not relate to the modification and the optimization of the whole porosu solid appearance of mixture piece;
The patent No. be CN200580009219.7's ' purposes of ammonia storage device in energy generation ' invention relate to a kind of generator unit, this unit comprises the ammonia storage device of (i) container (2) form, comprising general formula is M
a(NH
3)
NXzAmmonia absorb and discharge salt; Wherein M is one or more positively charged ions, is selected from basic metal, earth alkali metal and transition metal such as Li, K, Mg, Ca, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, and X is one or more negatively charged ion; Be selected from fluorine root, chlorine root, bromine root, iodine root, nitrate radical, thiocyanate ion, sulfate radical, molybdate, phosphate radical and chloranion; A is the positively charged ion number of each molecules of salt, and z is the negatively charged ion number of each molecules of salt, and n is the ligancy of 2-12; (ii) being used to heat said container (2) and ammonia absorbs and discharges the fuel cell that salt with the device (3a) that discharges ammonia and (iiia) is used for ammonia is converted into electric power; Perhaps (iiib1) is used for ammonia is dissociated into the reactor drum (6) of hydrogen and nitrogen; (iiib2) be used for hydrogen is converted into the fuel cell (4) of electric power; This patent is mainly used in fuel cell; Mentioned property material in the claim 4 and be such salt or be positioned on the porous carrier materials, which kind of material statement is not.
The disclosure of the Invention of CN200710156866.1 ' a kind of amido complex compound ' a kind of amido complex compound.The composition of this amido complex compound is MX
m(NH
3)
n, M is one or more among Li, Mg, Al, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Ba, the Sn in the formula; X is F, Cl, Br, NO
3, SO
4In one or more; M decides according to valency, 1≤m≤5; N decides according to ligancy, 1≤n≤15.With the absorption agent of the amido complex compound behind the deamination, put separation, purification, storage and the transportation that ammonia is realized ammonia through low temperature suction ammonia, high temperature as ammonia.This patent only relates to the preparation technology and the process of this amido complex compound itself.
The patent No. is solid ammonia storage and the conveying material that CN200680005886.2's the high-density of the ammonia ' storage ' patent comprises ammonia absorptions/desorb solid material; 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; The storage ammonia that this storage medium prepares and handles and have 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 security measures for storage with to carry ammonia be safe.This patent is to adopt the direct compression molding of solid material; Adopt sticker; Only stated it possibly is the silica fiber sticker, do not had the dosage ratio, the solid material of also only stating among other claim item and the embodiment possibly comprise particulate material, porous material, crystalline material, amorphous material or their binding substances composition; Do not have thin of clear and definite claim, industry technology personage almost can't implement.Produced the present invention therefrom.
Summary of the invention
The purpose of this invention is to provide a kind of storage ammonia mixture porosu solid appearance piece that contains molecular sieve and preparation method thereof; It optionally adds mesopore and the large pore molecular sieve of finger-hole footpath greater than 5 (0.5nm) in activity storage ammonia mixture; The passage in these holes can let ammonia current therein easily; Guaranteed that the storage ammonia characteristic of metal-salt improved the richness of microcosmic nanoporous again, increased the quantity of macroscopic pores, improved the physical strength of mixture porosu solid appearance piece; Also add the appropriate amount of industrial silicon sol, improved the viscosity and the specific surface area of mixture porosu solid appearance piece effectively.
Technical scheme of the present invention is achieved in that a kind of storage ammonia mixture porosu solid appearance piece that contains molecular sieve and preparation method thereof, and the storage ammonia mixture porosu solid appearance piece that contains molecular sieve is by anhydrous strontium chloride (SrCl
2), molecular sieve and industry silicasol form, and it is characterized in that its preparation method, concrete steps are following:
1) adopts the powder of the industrial anhydrous strontium chloride salt of weight percent 70 ~ 85wt%, mix the industrial spirit of industry silicasol, 5 ~ 18wt% molecular sieve and the 1 ~ 3wt% of 5 ~ 10wt%, composition mixture;
2) each component is mixed through stirrer, mixing time 1 ~ 10h, the mixed powder of furnishing semi-drying, but this powder add in the encloses container of an open type and carry out mechanical oscillation 30 ~ 60min, then at 60 ~ 80 ℃, vacuum tightness is 10
-1Dry 1 ~ 3h under the condition of ~ 1KPa, or dry 2 ~ 3h gets final product to such an extent that contain the storage ammonia mixture porosu solid appearance piece of molecular sieve under 90 ~ 100 ℃ temperature.
Positively effect of the present invention is that prepared mixture porosu solid appearance piece microcosmic nano pore enriches, and is used for realizing the efficient absorption and the desorb of ammonia, and mixture porosu solid appearance piece is to concentrate to use, and satisfies the storage of large vol ammonia and the request for utilization of release.
Description of drawings
Fig. 1 is the thermogravimetric curve figure behind the mixture porosu solid appearance piece absorbing ammonia of the present invention.
Embodiment
Through embodiment the present invention is further described below, embodiment is not equal to restriction the present invention for further illustrating characteristics of the present invention,, all should be included within protection scope of the present invention according to the change that the present invention carries out for those skilled in the art.
Embodiment 1
Powder 82 wt%, industry silicasol 9 wt%, molecular sieve 8 wt% and industrial spirit 1 wt% of the anhydrous strontium chloride salt of industry are mixed through stirrer, and mixing time is 1h, and the back that stirs forms the mixed powder of semi-drying; But the mixed powder of this semi-drying is added to the 30min that vibrates in the encloses container of an open type, again at 80 ℃, vacuum tightness is 10
-1Dry 1h gets final product to such an extent that contain the storage ammonia mixture porosu solid appearance piece of 8.1wt% molecular sieve under the condition of KPa.
10g porosu solid appearance piece is filled ammonia; Under the environment of gravity-flow ventilation, carry out; In advance but the closed container of open type is put into the tank of the enough big cooling water of water yield; Connect the ammonia steel cylinder; By pressure-reducing valve and drying system; In the outlet pressure scope of 0.1Mpa slowly fill ammonia, filling the ammonia time is 3h; Fill that this kind piece quality is 14g behind the ammonia, i.e. absorbing ammonia 4g.And then the appearance piece carried out heat treated under 300 ℃, and found that a heating back appearance piece quality becomes 11.2g, has promptly discharged ammonia 3.8g, desorption efficiency is 95%.Fig. 1 is the thermogravimetric curve behind this mixture porosu solid appearance piece absorbing ammonia, and as can be seen from the figure, the whole porosu solid appearance of this mixture piece has good ammonia adsorptive power, carries out desorb under 250 ℃.
Embodiment 2
Powder 85 wt%, industry silicasol 5 wt%, molecular sieve 7 wt% and industrial spirit 3 wt% of the anhydrous strontium chloride salt of industry are mixed through stirrer, and mixing time is 1h, and the back that stirs forms the mixed powder of semi-drying; But the mixed powder of this semi-drying is added to the 35min that vibrates in the encloses container of an open type, again at 60 ℃, vacuum tightness is that dry 3h gets final product to such an extent that contain the storage ammonia activated mixture porosu solid appearance piece of 7.2wt% molecular sieve under the condition of 1KPa.
10g porosu solid appearance piece is filled ammonia; Under the environment of gravity-flow ventilation, carry out; In advance but the closed container of open type is put into the tank of the enough big cooling water of water yield; Connect the ammonia steel cylinder; By pressure-reducing valve and drying system; In the outlet pressure scope of 0.2Mpa slowly fill ammonia, filling the ammonia time is 5h; Fill that this kind piece quality is 14.4g behind the ammonia, i.e. absorbing ammonia 4.4g.And then the appearance piece carried out heat treated under 300 ℃, and found that a heating back appearance piece quality becomes 10.5 g, has promptly discharged ammonia 3.9g, desorption efficiency is 88%.
Embodiment 3
10g porosu solid appearance piece is filled ammonia; Under the environment of gravity-flow ventilation, carry out; In advance but the closed container of open type is put into the tank of the enough big cooling water of water yield; Connect the ammonia steel cylinder; By pressure-reducing valve and drying system; In the outlet pressure scope of 0.2Mpa slowly fill ammonia, filling the ammonia time is 4h; Fill that this kind piece quality is 13.5g behind the ammonia, i.e. absorbing ammonia 3.5g.And then the appearance piece carried out heat treated under 300 ℃, and found that a heating back appearance piece quality becomes 10.2 g, has promptly discharged ammonia 3.3g, desorption efficiency is 94%.
Claims (1)
1. contain storage ammonia mixture porosu solid appearance piece of molecular sieve and preparation method thereof, the storage ammonia mixture porosu solid appearance piece that contains molecular sieve is by anhydrous strontium chloride (SrCl
2), molecular sieve and industry silicasol form, and it is characterized in that its preparation method, concrete steps are following:
1) adopts the powder of the industrial anhydrous strontium chloride salt of weight percent 70 ~ 85wt%, mix the industrial spirit of industry silicasol, 5 ~ 18wt% molecular sieve and the 1 ~ 3wt% of 5 ~ 10wt%, composition mixture;
2) each component is mixed through stirrer, mixing time 1 ~ 10h, the mixed powder of furnishing semi-drying, but this powder add in the encloses container of an open type and carry out mechanical oscillation 30 ~ 60min, then at 60 ~ 80 ℃, vacuum tightness is 10
-1Dry 1 ~ 3h under the condition of ~ 1KPa, or dry 2 ~ 3h gets final product to such an extent that contain the storage ammonia mixture porosu solid appearance piece of molecular sieve under 90 ~ 100 ℃ temperature.
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| CN201210238840.2A CN102731054B (en) | 2012-07-11 | 2012-07-11 | Storage ammonia mixture porosu solid sample block containing molecular sieve and preparation method thereof |
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| CN201210238840.2A CN102731054B (en) | 2012-07-11 | 2012-07-11 | Storage ammonia mixture porosu solid sample block containing molecular sieve and preparation method thereof |
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| CN102731054B CN102731054B (en) | 2015-09-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230197A (en) * | 2014-09-10 | 2014-12-24 | 江苏名和集团有限公司 | Ammonia stabilizer for concrete |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD296901A5 (en) * | 1987-09-02 | 1991-12-19 | Chemiewerk Bad Koestritz Gmbh,De | METHOD FOR THE PRODUCTION OF HIGH-SLIC MOLECULAR SCREENS |
| CN1177307A (en) * | 1994-10-13 | 1998-03-25 | 高级技术材料公司 | Storage and delivery system for gaseous compounds |
| CN101128394A (en) * | 2005-02-03 | 2008-02-20 | 氨合物公司 | High density storage of ammonia |
| CN101982232A (en) * | 2010-10-29 | 2011-03-02 | 烟台大学 | Deaminizing agent and preparation method thereof |
| CN102027211A (en) * | 2008-05-13 | 2011-04-20 | 罗伯特·博世有限公司 | Device, system and method for providing a reducing agent for a system for the selective catalytic reduction of nitrogen oxides |
-
2012
- 2012-07-11 CN CN201210238840.2A patent/CN102731054B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD296901A5 (en) * | 1987-09-02 | 1991-12-19 | Chemiewerk Bad Koestritz Gmbh,De | METHOD FOR THE PRODUCTION OF HIGH-SLIC MOLECULAR SCREENS |
| CN1177307A (en) * | 1994-10-13 | 1998-03-25 | 高级技术材料公司 | Storage and delivery system for gaseous compounds |
| CN101128394A (en) * | 2005-02-03 | 2008-02-20 | 氨合物公司 | High density storage of ammonia |
| CN102027211A (en) * | 2008-05-13 | 2011-04-20 | 罗伯特·博世有限公司 | Device, system and method for providing a reducing agent for a system for the selective catalytic reduction of nitrogen oxides |
| CN101982232A (en) * | 2010-10-29 | 2011-03-02 | 烟台大学 | Deaminizing agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230197A (en) * | 2014-09-10 | 2014-12-24 | 江苏名和集团有限公司 | Ammonia stabilizer for concrete |
| CN104230197B (en) * | 2014-09-10 | 2017-01-18 | 江苏名和集团有限公司 | Ammonia stabilizer for concrete |
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| CN102731054B (en) | 2015-09-16 |
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