EP0931019A1 - Adsorption/desorption von ammoniak - Google Patents
Adsorption/desorption von ammoniakInfo
- Publication number
- EP0931019A1 EP0931019A1 EP97918873A EP97918873A EP0931019A1 EP 0931019 A1 EP0931019 A1 EP 0931019A1 EP 97918873 A EP97918873 A EP 97918873A EP 97918873 A EP97918873 A EP 97918873A EP 0931019 A1 EP0931019 A1 EP 0931019A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonia
- salt
- metal
- adsorber
- particular according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 120
- 238000002336 sorption--desorption measurement Methods 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- 239000012159 carrier gas Substances 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract 2
- 238000001179 sorption measurement Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- 238000003795 desorption Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005057 refrigeration Methods 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- -1 transition metal cation Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims 4
- 239000006096 absorbing agent Substances 0.000 claims 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 239000011572 manganese Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000004065 semiconductor Substances 0.000 claims 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000002826 coolant Substances 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 4
- 238000004378 air conditioning Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/047—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for absorption-type refrigeration systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B49/00—Arrangement or mounting of control or safety devices
- F25B49/005—Arrangement or mounting of control or safety devices of safety devices
Definitions
- the present invention relates to a method for absorbing or adsorbing or desorbing ammonia, the use of the method for collecting ammonia, which emerges as a result of a leak from a system operated with ammonia, such as a refrigeration system, an arrangement for collecting and Regeneration of ammonia and a refrigeration system operated by means of absorption or adsorption / sorption of ammonia.
- Ammonia is the first refrigerant used in cold steam engines, and the so-called compressor refrigeration systems were developed by Linde in the last century.
- Ammonia is particularly suitable as a refrigerant because of its large evaporation enthalpy, its low price and its very low flammability and is mainly used in large systems.
- ammonia is very toxic, and it also attacks copper and its alloys, such as brass and gunmetal, even with the lowest water content.
- the disadvantage of these systems is that the working range of the water / lithium bromide pair of materials for absorption refrigeration systems is very narrow.
- a disadvantage is the freezing point of the water, which cannot be undercut.
- lithium bromide salt is not unlimitedly soluble in water and is very aggressive in connection with air / oxygen.
- lithium bromide / water absorption refrigeration systems require a high level of tightness due to the extremely low vacuum.
- ammonia was a well-known alternative as a refrigerant for use in adsorption systems, since ammonia does not cause long-term damage to the environment and is therefore even recommended by environmental protection organizations.
- ammonia therefore presupposes increased safety requirements for technical systems, such as cooling systems, which means that effective protective devices are of greater importance, which either prevent ammonia from escaping from systems or by means of which ammonia escaping can be safely collected.
- Another object of the present invention is to provide a refrigeration system operated with ammonia, which has an improved economic efficiency in comparison to plants operated with the known ammonia.
- the invention is based on the fact that ammonia forms so-called complexes together with 3d transition metal salts.
- the existence of coordination or complex connections has been known for about eighty years. These compounds have the following general formulation:
- M central cation, usually a transition metal cation such as manganese, iron, cobalt, nickel, copper or zinc in differently oxidized states;
- X.,: M anions, the charges of which compensate for the positive charge of the metal cation.
- X F “ , Cl ⁇ , Br ⁇ , I “ , N0 3 " , S0 4 2 ⁇ , P0 4 3” etc.
- amine complexes can be synthesized very easily, but they are unstable, i.e. thermally degradable.
- Scheme I shows the mechanism of the breakdown or buildup of one or more complexes of a metal sulfate. It has been shown that the number of ligands is variable, but is usually stoichiometric, and it is also known that the absorption or adsorption or desorption of ammonia in the metal salt depends on the following factors:
- Scheme II shows the partially reversible breakdown and assembly of amine complexes of nickel sulfate. It is clear, is that at very high temperatures, the metal salt NiS0 4 zer ⁇ sets. As a result, the construction of amine complexes is no longer possible. However, this is not critical for the technical use of the amine complexes, since the decomposition temperature is above 400 ° C, but the absorption and desorption takes place below 100 ° C.
- salts can be, for example, fluorides, chlorides, bromides, iodides, nitrates, sulfates or phosphates.
- Manganese, nickel, copper, cobalt or iron salts have proven to be particularly suitable, nickel sulfate, copper sulfate or manganese sulfate being particularly preferred for the absorption or adsorption or desorption of ammonia. Due to the excellent adsorption at low temperatures as well as at room temperature, it is now possible to collect ammonia, which escapes from a system operated with ammonia in the event of a leak.
- One of the metal salts mentioned is arranged in the region of the expected leakage or this region is coated by means of a material which contains one of the metal salts mentioned, as a result of which any ammonia escaping is immediately adsorbed.
- the leakage of ammonia as a result of leakage from a plant or the adsorption of ammonia by the metal salt arranged for collection can generally be recognized relatively quickly, since the metal salt is discolored. This discoloration is not general, but rather typical of a particular metal salt, which is why this discoloration must be found out by means of tests before the metal salt is arranged. In the case of manganese salts, for example, brown discoloration usually sets in when these salts adsorb ammonia. Other examples of this process are nickel or copper salts.
- ammonia leakage occurs, for example, when filling or emptying systems which are operated with ammonia.
- Ammonia can be adsorbed on the one hand by coating the critical system parts, by arranging adsorber cartridges or by impregnating system parts.
- a system can be completely packed using ammonia-adsorbing material in order to collect ammonia in the event of leaks or system-related.
- This material can be regenerated from time to time, since, as stated above, ammonia can be driven out of the complexes formed at relatively low temperatures, i.e. at temperatures of around 60 ° C.
- the metal salt thus regenerated can be used again for the adsorption of ammonia, which adsorption, as mentioned above, can already take place at normal pressure and normal temperature.
- Fig. 1 schematically using a schematic diagram, the operation of an ammonia cold absorption system
- FIG. 2 schematically shown in perspective, a filter cartridge of the adsorber of the cold sorption system according to Fig. 1 and 3a cutouts or parts of the adsorber according to Fig. Or 3b 2nd
- FIG. 1 schematically shows a schematic diagram of an ammonia cold sorption system, for example used for operating an air conditioning system, a freezer system, etc.
- a condenser 1 pressurized ammonia gas which is introduced via a line 3 is initially cooled to approx. Room temperature liquefied. This liquefaction takes place analogously to the ammonia refrigeration systems known today.
- the liquid ammonia is fed via line 7 and a throttle element 9 and a further line 11 to the cooling heat exchanger or evaporator 13, where the ammonia is further cooled to approximately -40 ° C. as a result of the pressure being reduced and the evaporation associated therewith.
- a cooling medium 15 is guided, which is used for operating the air conditioning system, the freezer, etc. As a rule, the cooling medium can be cooled to below -40 ° C.
- the vaporous ammonia is fed via lines 19 to a two-part, batch-operated adsorber 21 or desorber 21 ', in which, for example, nickel sulfate, manganese sulfate, copper sulfate or another suitable metal salt is arranged, which collects the ammonia via complex formation and absorbed or adsorbed.
- a two-part, batch-operated adsorber 21 or desorber 21 ' in which, for example, nickel sulfate, manganese sulfate, copper sulfate or another suitable metal salt is arranged, which collects the ammonia via complex formation and absorbed or adsorbed.
- Such an ammonia adsorber or desorber is shown schematically in FIG. 2, for example.
- the ammonia trapped or adsorbed in the adsorber 21 is now expelled again by passing a heating medium through the adsorber 21, for example by opening the two valves 28, so that the heating medium can circulate unhindered through the heating line 26.
- the heating medium can be waste heat which is removed from a district heating system and which has a temperature of approximately 60 ° C to 90 ° C. Since the desorption of ammonia from the metal salts mentioned according to the invention starts at lower temperatures, the heating medium supplied can of course also have a temperature of ⁇ 60 ° C.
- the ammonia is now expelled or evaporated, which automatically results in a pressure increase in the adsorber 21 and the ammonia is driven through the line 3 and the valve 23 into the condenser 1.
- the pressure increase can be supported by an external compressor.
- the former desorber 21 is operated as an alternative as an adsorber. This is possible because at the same time as the When the two valves 28 are opened, the two valves 27 are closed, as a result of which no more heating medium flows through the “desorber” 21 ′ and thus the ammonia gas flowing in through the opened valve 22 ′ is massively cooled. Thus, the ammonia gas flowing in through line 19 is now adsorbed in part 21 'until more or less a saturation equilibrium has been established.
- valve 22' is closed again and valve 24 is opened, whereby part 21 'is operated again as a desorber.
- part 21 is operated again as an adsorber, since the ammonia has in the meantime been at least partially expelled and has reached the condenser 1, where the ammonia has largely condensed as a result of cooling and increasing the pressure.
- the circle of the schematically illustrated adsorber system would thus be closed.
- Condensation temperature or pressure should be at least 10K above the evaporation temperature or pressure.
- the separation process for example water
- the cooling medium can be cooled to, for example, -40 ° C. without problems, without the problem of freezing the water.
- a further advantage lies in the adsorption of the ammonia in the metal salts defined according to the invention, starting from -40 ° C., since cooling of the cooling medium 15 to the -40 ° C. mentioned is thus possible. It is thus possible, for example, to operate freezer systems with the adsorber system described according to the invention.
- Another important advantage is that the desorption of the ammonia from the metal salts, depending on the salt used or depending on the structure or surface properties of the salt, already starts at approx. + 20 ° C, and temperature differences between the medium inlet and outlet to to 2OK and more, so that the heating media necessary or used for desorption can be easily obtained.
- the above-mentioned waste heat from district heating or exhaust gas cooling in combined heat and power plants which usually has a temperature of approx. 60 ° C to 90 ° C, as well as solar energy. This means that there is no need to operate an energy-intensive heating system.
- ammonia adsorber system it is also possible to connect the ammonia adsorber system to a normal gas heating system or to use any other heat transfer medium such as water to expel the ammonia.
- the ammonia is 100% recyclable during the process and the adsorber material is not used up.
- the adsorber 21 or 21 ' An essential element of the adsorber system according to the basic scheme in FIG. 1 is the adsorber 21 or 21 ', of which, for example, a possible embodiment variant is shown schematically in perspective in FIG. 2.
- the adsorber 21 shown in FIG. 2 is like a plate heat exchanger, for example having metal exchanger plates 35 through which water flows and having hollow grooves, the metal salts proposed according to the invention being arranged in the spaces 33 between the individual metal plates, for example in granular form or in another permeable packing form.
- the individual metal heat exchanger plates 35 are fed, for example, by means of the heating medium 26, which is preferably exhaust air from a district heating system or heated water. Enveloping outside, a porous or permeable sheath 37 is arranged, either as mechanical protection or to prevent the metal salts from breaking out laterally.
- the thermal energy required for desorbing depends on various factors. On the one hand, it is important in which form the metal salt responsible for the adsorption is present. For example, tests have shown that when very fine powder is present, desorption already begins at approximately 20 ° C, whereas, for example, when granules are present, desorption only begins in a range between approximately 40 and 60 ° C.
- the surface structure of the adsorbing material is also important, whether the surface has large or small pores. To put it simply, it can be said that the larger the adsorber surface area per volume, the greater the adsorption rate, but the earlier the desorption starts again, for example at the above-mentioned approx. 20 ° C.
- the material itself represents, ie which metal salt is the adsorbing or desorbing material. It is particularly important here whether only 4 ligands or 6 ligands are added during the complex formation, as has been explained, for example, in the introduction to the description. With 6 ligands, the adsorption or desorption usually takes place in 3 stages, whereas with only 4 ligands this takes place in 2 stages. In the case of 3-stage adsorption or desorption, the desorption of the third or first stage usually begins at a relatively low temperature, ie already in a range from approximately 20 to 40 ° C. In other words, with 3-stage adsorption or desorption, relatively little energy has to be supplied to the system in order to accomplish the desorption of the first stage.
- the desorption of the second stage already requires a relatively large amount of energy, which is why it is questionable to include the adsorption or desorption of the second stage when operating an ammonia cold sorption system defined according to the invention. But that means that in principle only a third of the possible adsorption and desorption volume would be taken into account.
- the desorption of the first stage requires more energy, ie the metal salt must be heated to a temperature of at least approx. 40 to 60 ° C so that the first stage of the ammonia ligands is desorbed, but the energy requirement always lies even lower than in the event that the second stage is desorbed in a 3-stage system. In this way, however, 50% of the possible ammonia volume in the adsorption or desorption process is taken into account in a 2-stage system, which may have a positive effect on economy.
- FIG. 3a For a better understanding of the functioning of the individual metal heat exchanger plates 35, a section of the adsorber 21 from FIG. 2 is shown in detail in FIG. 3a, while FIG. 3b shows a single metal heat exchanger plate 35 in a top view.
- the individual plates 35 consist of an upper and a lower plate part, which are welded at the edge 43.
- Two through-tubes 26 are arranged in the peripheral area, through which the hot water or the exhaust air is driven.
- grooves 39 and 41 are arranged in the two welded plate parts, in such a way that the hot water 26 flows in parallel in one groove 39, while in the upper grooves 41 Flow between the parallel grooves 39 is made possible.
- the adsorber shown in FIG. 2 is only one possible embodiment, and of course any other suitable embodiment is also conceivable.
- the adsorber material can also be in the form of a ceramic filter.
- the packaging form of the metal salts arranged in the interspaces is also varied; for example, it is possible to arrange the metal salts in granular form, in compacted powder form, solidified together with a binder, etc. It is essential that the packing remains porous in order to enable the best possible adsorption of the ammonia.
- a possible embodiment variant is also to coat the individual metal plates 35 with the metal salts.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH237996 | 1996-09-30 | ||
CH237996 | 1996-09-30 | ||
PCT/CH1997/000364 WO1998014400A1 (de) | 1996-09-30 | 1997-09-26 | Adsorption/desorption von ammoniak |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0931019A1 true EP0931019A1 (de) | 1999-07-28 |
Family
ID=4232409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97918873A Withdrawn EP0931019A1 (de) | 1996-09-30 | 1997-09-26 | Adsorption/desorption von ammoniak |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0931019A1 (de) |
AU (1) | AU4293397A (de) |
WO (1) | WO1998014400A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070057143A (ko) | 2004-08-03 | 2007-06-04 | 아미넥스 에이/에스 | 고체 암모니아 저장 및 수송 물질 |
RU2395335C2 (ru) | 2005-02-03 | 2010-07-27 | Амминекс А/С | Хранение аммиака при его высоком содержании |
GB0613695D0 (en) * | 2006-07-10 | 2006-08-16 | Council Cent Lab Res Councils | Method of producing (nh2(r2) and/or hydrogen |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60227831A (ja) * | 1984-04-26 | 1985-11-13 | Nittetsu Mining Co Ltd | ガス吸着剤 |
US4848994A (en) * | 1987-11-02 | 1989-07-18 | Uwe Rockenfeller | System for low temperature refrigeration and chill storage using ammoniated complex compounds |
DK0462226T3 (da) * | 1989-03-08 | 1995-07-10 | Rocky Research | Fremgangsmåde og apparat til opnåelse af høje reaktionshastigheder i faststof-gas-reaktorsystemer |
DE4102245A1 (de) * | 1991-01-24 | 1992-08-13 | Ilka Maschinenfabrik Halle Gmb | Sicherheitseinrichtung fuer kaelteaggregate mit ammoniak als kaeltemittel |
DE4305781A1 (de) * | 1992-05-22 | 1993-11-25 | Solvay Catalysts Gmbh | Sorption von NH¶3¶ mit dotierten oxidischen Sorbenzien |
US5320817A (en) * | 1992-08-28 | 1994-06-14 | Novapure Corporation | Process for sorption of hazardous waste products from exhaust gas streams |
JPH08170866A (ja) * | 1994-12-15 | 1996-07-02 | Hitachi Ltd | 冷凍機用冷媒の漏洩防止装置及びこれを備えた冷凍機 |
-
1997
- 1997-09-26 AU AU42933/97A patent/AU4293397A/en not_active Abandoned
- 1997-09-26 WO PCT/CH1997/000364 patent/WO1998014400A1/de not_active Application Discontinuation
- 1997-09-26 EP EP97918873A patent/EP0931019A1/de not_active Withdrawn
Non-Patent Citations (1)
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See references of WO9814400A1 * |
Also Published As
Publication number | Publication date |
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WO1998014400A1 (de) | 1998-04-09 |
AU4293397A (en) | 1998-04-24 |
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