CN102728303A - Magnesium-salt porous active ammonia-storage active mixture and preparation thereof - Google Patents
Magnesium-salt porous active ammonia-storage active mixture and preparation thereof Download PDFInfo
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- CN102728303A CN102728303A CN2012102388101A CN201210238810A CN102728303A CN 102728303 A CN102728303 A CN 102728303A CN 2012102388101 A CN2012102388101 A CN 2012102388101A CN 201210238810 A CN201210238810 A CN 201210238810A CN 102728303 A CN102728303 A CN 102728303A
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000003860 storage Methods 0.000 title claims abstract description 41
- 159000000003 magnesium salts Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229940053326 magnesium salt Drugs 0.000 title abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 214
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 230000009514 concussion Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000007751 thermal spraying Methods 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 8
- 238000003795 desorption Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011343 solid material Substances 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 235000011147 magnesium chloride Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- -1 amino borane compound Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910003203 NH3BH3 Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007907 direct compression Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 108010033040 Histones Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 208000002173 dizziness Diseases 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
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- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Exhaust Gas After Treatment (AREA)
Abstract
The invention relates to a magnesium-salt porous active ammonia-storage active mixture and preparation thereof. The invention is characterized in that the preparation method comprises the following steps: doping proper amounts of molecular sieve, silicasol, deionized water and industrial alcohol in industrial anhydrous magnesium chloride powder; mechanically stirring to obtain a semidry evenly-mixed wet material; and filling into a tank body to prepare an integral porous solid block. The solid block contains abundant ammonia gas transmission pores, has a plurality of macropores in a macroscopic view, has quick ammonia charging property and favorable ammonia storage property, can quickly release ammonia gas, can be used repeatedly without breaking, has efficient adsorption and desorption characteristics, is suitable for adsorbing and storing ammonia gas, is applicable to SCR (selective catalytic reduction) and FCEV (fuel cell electric vehicle) systems, and satisfies the application demands for automobile industry in future.
Description
Technical field
The present invention relates to a kind of porous storage ammonia active mixture and preparation of magnesium salts, 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 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.
The SCR after-treatment system is 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; Reach the purpose of cleaning of off-gas; Realize state 4 or above standard up to standard of vehicle; 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, for example; Urea liquid is icing blocking problem under-11 ℃ of environment, needs extra pipeline heating system to solve; Urea liquid could decompose under the temperature environment more than 135 ℃; And many vehicles of public transit system loiter; Can't reach urea liquid stable decomposition temperature at all; Can't the output ammonia; Can't eliminate predetermined NOX composition; Cause the accumulation of liquid area in blast pipe at last; Produce the polymer of melamine; Stop up the urea nozzle and the exhaust pipe of engine; Cause vehicles produces fault; Influence is normal to be used, 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 potential huge problem 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 is originated is a no small difficult problem of restriction this area development, in institute's possible adopted hydrogen source mode; Technology path and the hydrogeneous presoma decomposition of other H-N or the technology path of cracking hydrogen production that the technology path of gas cylinder storage hydrogen, the technology path that water electrolysis hydrogen production is arranged, the technology path that high-purity hydro carbons petroleum fuel cracking hydrogen production is arranged, low mass molecule alcohol class cracking hydrogen production are arranged; In the above-mentioned technology path, 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 hydrogeneous 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 ~ 4A, therefore, very active under the normal temperature, very easily diffusion, and have toxic; The skin histology that its toxic is embodied in contact all has corrosion and spread effect, can absorb the moisture in the skin histology, makes the histone sex change, and makes the tissue fat saponification, destroys membrane structure; Ammonia in water solubility high, stimulate and corrosiveness 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; Ammonia gets into blood through alveolar after being inhaled into lung easily, combines with hemoglobin, destroys fortune oxygen function; Get into IA ammonia; Few part is neutralized by carbon dioxide, and remainder is absorbed into blood, suck in a short time can occur shedding tears behind a large amount of ammonias, pharyngalgia, cough, uncomfortable in chest, expiratory dyspnea, dizziness, vomiting, weak etc.; If the long-term ammonia that sucks is too much, cause ammonia excessive concentration in the blood, will cause heart stop fight and breath stopped threat to life safety; Therefore, the maximum hidden danger of the use of ammonia is safety problem.
This shows, resolve in the use of ammonia storing and safety problem, just can open up the technology path of a new ammonia utilization.
Traditional ammonia storing mode is a gas cylinder, or realizes with the water-soluble formation ammoniacal liquor of high concentration ammonia.If adopt gas cylinder to store ammonia, there is the potential safety hazard of operating aspect and seal aspect in the commercial Application in enormous quantities, if, have serious etching problem again with the mode of high concentrated ammonia liquor.
At China national patent information net; With the storage ammonia word and search that is the theme; 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 bindiny 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 industrial wastewater 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 catalyst 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 control 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 closed container to the amino borane compound; Vacuumize, under 0-4 ℃ of temperature, contact with ammonia; Under 0-4 ℃ of temperature, kept 30-60 minute, prepare required product amino borane ammino-complex NH3BH3 (NH3) 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 danger 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 cations of Mn, Fe, Co, Ni, Cu and/or Zn of alkaline-earth metal and/or one or more transition metal, and X is one or more anion, and a is the cation number that comprises in each molecules of salt; Z is the anion number that comprises in each molecules of salt; N is 2～12 ligancy, and wherein M is Mg, and it is auto 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 ammonia is resolved in the electric heating heating, more lays particular emphasis on the control strategy of system, does not relate to the modification and the optimization of mixture;
The patent No. be CN200580009219.7's ' purposes of ammonia storage device in energy production ' 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 cations, is selected from alkali metal, alkaline-earth 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 anion; Be selected from fluorine root, chlorine root, bromine root, iodine root, nitrate anion, thiocyanate radical, sulfate radical, molybdate, phosphate radical and chloranion; A is the cation number of each molecules of salt, and z is the anion 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 electrical power; Perhaps (iiib1) is used for ammonia is dissociated into the reactor (6) of hydrogen and nitrogen; (iiib2) be used for hydrogen is converted into the fuel cell (4) of electrical 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 chemical valence, 1≤m≤5; N decides according to ligancy, 1≤n≤15.With the absorbent 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 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.Produced the present invention therefrom.
Summary of the invention
The object of the present invention is to provide a kind of porous storage ammonia active mixture preparation of magnesium salts,, increase the ammonia transmission channel in order to improve the hole of storage ammonia active material solid block, weaken or avoid adsorbing repeatedly with desorption process in MgCl
2The caking that takes place and the efflorescence of solid block are broken, and that satisfies industrial occasions repeatedly recycles requirement, possesses efficient absorption and conciliates characterization of adsorption, and the absorption that is fit to ammonia stores, and is used for SCR and FCEV system, satisfies the application demand of following auto industry.
Technical scheme of the present invention is achieved in that a kind of porous storage ammonia active mixture of magnesium salts; It is characterized in that: press the powder of mass fraction 45 ~ 90 parts industrial anhydrous chlorination magnesium salts; Mix 2 ~ 15 parts Ludox, 1 ~ 8 part of molecular sieve, mix with 4 ~ 17 parts deionized water and 3 ~ 15 parts industrial alcohol.
Described preparation process of mixture is following: with the powder of the anhydrous chlorination magnesium salts of industry; Mix an amount of molecular sieve, Ludox, deionized water and industrial alcohol; Become uniform mixture wet feed through mechanical agitation; Be filled in the tank body, addition is no more than 80% of tank body volume, and machinery concussion 5 ~ 10min eliminates the air gap; Whole tank body is put in the vacuum drying oven, and normal pressure is slowly heating down, and temperature is controlled at 65 ~ 160 ℃; Get rid of water and ethanol to mixture constant weight, substep is evacuated to 550mbar, constant temperature and pressure 0.5 ~ 3h; Take out tank body, the sealing charge door is processed the whole porosu solid piece of storage ammonia active mixture; Ammonia fills in the tank body under 0.05 ~ 0.8MPa pressure, and is saturated to the mixture absorbing ammonia.
Described molecular sieve bore diameter scope is at 2 ~ 30nm, and specific area is greater than 300m
2/ g.
Described industrial clay particle diameter is less than 2um, and disperse becomes suspension in water.
Described tank body is the withstand voltage tank body of stainless steel, inner tank wall thermal spraying nylon heat-insulation layer.
Good effect of the present invention is optionally to have added Ludox, and the particle diameter here is at 10 ~ 20nm, and density is at 1.15g/cm
3, dioxide-containing silica 25%, pH value 8 ~ 10, disperse becomes suspension in water, by means of mechanical agitation and MgCl
2Reach other fillers and fully mix, at MgCl
2Bridging between the particle, dry back forms higher " the integrated solid piece " of mechanical strength, can weaken effectively or avoid adsorbing with desorption process in the expansion of solid block to shrink the efflorescence that causes broken; The diffusing MgCl of water that adds and dissolve with ethanol and differential
2And other fillers, improve between the liquid-solid two-phase wetting with sprawl, in addition, water and ethanol are deviate from the hole of process formation, have enriched the transmission channel of ammonia; The molecular sieve that adds has promoted MgCl
2Dispersion; Can weaken or avoid the generation of caking phenomenon effectively, improve the richness of microscopic void, increase the transmission channel of ammonia; Improve the permeance property of ammonia greatly; Promote the formation of ammino magnesium chloride complex compound, the loose structure of molecular sieve itself possesses certain absorption and memory function to ammonia simultaneously; The pore diameter range of here selecting is at 2 ~ 30nm, and specific area is greater than 300m
2/ g; The molecular sieve that adds is dispersed in MgCl
2In the particle, can weaken or eliminate the generation of caking phenomenon effectively, improve the richness of microscopic void, increase the internal transmission passage of ammonia, improve the permeance property of ammonia greatly, promote the formation of ammino magnesium chloride complex compound; In order to guarantee security under elevated pressures, used tank body is the withstand voltage tank body of stainless steel, inner tank wall thermal spraying nylon heat-insulation layer.
To sum up, the molecular sieve of interpolation has improved the richness of microcosmic nano-pore, has increased the quantity of macroscopic pores; Ludox that adds and the phenomenon that molecular sieve weakens or the ammonia adsorption-desorption of having avoided caking, fragmentation etc. to cause attaches; Improve the richness of microscopic void, increased the quantity of macroscopic pores, improved the mechanical strength of composition appearance piece; Have very high practical value, be suitable for the SCR post processing or the FCEV system of automobile industry.
Description of drawings
The thermogravimetric curve of the active mixture of the absorbing ammonia of Fig. 1 embodiment of the invention 1.
The specific 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
Water with 71 parts magnesium chlorides, 3 parts of molecular sieves, 6 parts of Ludox and 12 parts mixes 1h in homogenizer, add 8 parts of ethanol; Continue mechanical agitation 3h, process uniform mixture wet feed, be filled in the tank body; Be added into 80% of tank body volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in the vacuum drying oven, and the heating rate with 2 ℃/min under the normal pressure as shown in Figure 1 rises to 120 ℃, constant temperature 6h; Get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 1h; Take out tank body, the sealing charge door is processed the whole porosu solid piece of storage ammonia active mixture.
Embodiment 2
Water with 2 parts of molecular sieves, 18 parts of Ludox and 15 parts; In homogenizer, mix 1h; The magnesium chloride mixing 1h that adds 55 parts; Add 10 parts of ethanol; Continue mechanical agitation 3h, make uniform mixture wet feed, be filled in the tank body; Be added into 75% of tank body volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in the vacuum drying oven, and the heating rate with 2 ℃/min under the normal pressure rises to 120 ℃, constant temperature 6h; Get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 1h; Take out tank body, the sealing charge door is processed the whole porosu solid piece of storage ammonia active mixture.
Embodiment 3
Water with 4 parts of Ludox and 6 parts; In homogenizer, mix 1h; The magnesium chloride mixing 1h that adds 81 parts; Add 3 parts of molecular sieve mixing 1h, add 6 parts of ethanol, continue mechanical agitation 3h; Make uniform mixture wet feed; Be filled in the tank body, be added into 80% of tank body volume, machinery concussion 10min eliminates the air gap;
Whole tank body is put in the vacuum drying oven, and the heating rate with 5 ℃/min under the normal pressure rises to 100 ℃, constant temperature 8h; Get rid of water and ethanol, substep is evacuated to 550mbar, constant temperature and pressure 2h; Take out tank body, the sealing charge door is processed the whole porosu solid piece of storage ammonia active mixture.
Embodiment 4
The tank body that the storage ammonia active mixture of accomplishing for embodiment 1 installs additional adopts high-purity industrial ammonia bottle through subsequent use pipe valve, in the outlet pressure scope of 0.4Mpa slowly fill ammonia, filling the ammonia time is 3h, fill ammonia before and after the tank body quality increase by 42%;
The tank body that completion is filled behind the ammonia is connected with automobile SCR system, and under the situation of ammonia leakage rate less than 10ppm, quality reduces 38% before and after the test tank body desorption.
Embodiment 5
The tank body that the storage ammonia active mixture of accomplishing for embodiment 2 installs additional adopts high-purity industrial ammonia bottle through subsequent use pipe valve, in the outlet pressure scope of 0.2Mpa slowly fill ammonia, filling the ammonia time is 6h, fill ammonia before and after the tank body quality increase by 37%;
The tank body that completion is filled behind the ammonia is connected with automobile SCR system, and under the situation of ammonia leakage rate less than 10ppm, quality reduces 33% before and after the test tank body desorption.
Embodiment 6
The tank body that the storage ammonia active mixture of accomplishing for embodiment 3 installs additional adopts high-purity industrial ammonia bottle through subsequent use pipe valve, in the outlet pressure scope of 0.5Mpa slowly fill ammonia, filling the ammonia time is 5h, fill ammonia before and after the tank body quality increase by 38%;
The tank body that completion is filled behind the ammonia is connected with automobile SCR system, and under the situation of ammonia leakage rate less than 10ppm, quality reduces 34% before and after the test tank body desorption.
Claims (3)
1. the porous of a magnesium salts is stored up the ammonia active mixture; It is characterized in that: press the powder of mass fraction 45 ~ 90 parts industrial anhydrous chlorination magnesium salts; Mix 2 ~ 15 parts Ludox, 1 ~ 8 part of molecular sieve, mix with 4 ~ 17 parts deionized water and 3 ~ 15 parts industrial alcohol.
2. a kind of high-efficiency multiple storage ammonia active mixture according to claim 1; It is characterized in that described preparation process of mixture is following: with the powder of the anhydrous chlorination magnesium salts of industry; Mix an amount of molecular sieve, Ludox, deionized water and industrial alcohol, become uniform mixture wet feed, be filled in the tank body through mechanical agitation; Addition is no more than 80% of tank body volume, and machinery concussion 5 ~ 10min eliminates the air gap; Whole tank body is put in the vacuum drying oven, and normal pressure is slowly heating down, and temperature is controlled at 65 ~ 160 ℃; Get rid of water and ethanol to mixture constant weight, substep is evacuated to 550mbar, constant temperature and pressure 0.5 ~ 3h; Take out tank body, the sealing charge door is processed the whole porosu solid piece of storage ammonia active mixture; Ammonia fills in the tank body under 0.05 ~ 0.8MPa pressure, and is saturated to the mixture absorbing ammonia.
3. a kind of high-efficiency multiple storage ammonia active mixture according to claim 1 is characterized in that described molecular sieve bore diameter scope at 2 ~ 30nm, and specific area is greater than 300m
2/ g.
A kind of high-efficiency multiple storage ammonia active mixture according to claim 1 is characterized in that described industrial clay particle diameter less than 2um, and disperse becomes suspension in water.
A kind of high-efficiency multiple storage ammonia active mixture according to claim 1 is characterized in that described tank body is the withstand voltage tank body of stainless steel, inner tank wall thermal spraying nylon heat-insulation layer.
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| WO1999059916A1 (en) * | 1998-05-15 | 1999-11-25 | Crosfield Limited | Process for adsorbing a gas |
| JP2003305461A (en) * | 2002-04-16 | 2003-10-28 | Nippon System Products Kk | Element for removing ammonia-nitrogen in liquid and method for manufacturing the same |
| CN101128394A (en) * | 2005-02-03 | 2008-02-20 | 氨合物公司 | High Density Storage of Ammonia |
| CN101584999A (en) * | 2008-05-20 | 2009-11-25 | 揖斐电株式会社 | Honeycomb structure |
| CN101982232A (en) * | 2010-10-29 | 2011-03-02 | 烟台大学 | Deaminizing agent and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999059916A1 (en) * | 1998-05-15 | 1999-11-25 | Crosfield Limited | Process for adsorbing a gas |
| JP2003305461A (en) * | 2002-04-16 | 2003-10-28 | Nippon System Products Kk | Element for removing ammonia-nitrogen in liquid and method for manufacturing the same |
| CN101128394A (en) * | 2005-02-03 | 2008-02-20 | 氨合物公司 | High Density Storage of Ammonia |
| CN101584999A (en) * | 2008-05-20 | 2009-11-25 | 揖斐电株式会社 | Honeycomb structure |
| CN101982232A (en) * | 2010-10-29 | 2011-03-02 | 烟台大学 | Deaminizing agent and preparation method thereof |
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