CN111011488B - Controlled atmosphere preservation system and application - Google Patents
Controlled atmosphere preservation system and application Download PDFInfo
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- CN111011488B CN111011488B CN201911375343.5A CN201911375343A CN111011488B CN 111011488 B CN111011488 B CN 111011488B CN 201911375343 A CN201911375343 A CN 201911375343A CN 111011488 B CN111011488 B CN 111011488B
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- 238000004321 preservation Methods 0.000 title claims abstract description 26
- 238000004320 controlled atmosphere Methods 0.000 title claims description 6
- 239000007789 gas Substances 0.000 claims abstract description 121
- 239000001257 hydrogen Substances 0.000 claims abstract description 119
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 119
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000002407 reforming Methods 0.000 claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 claims abstract description 46
- 230000003197 catalytic effect Effects 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000003860 storage Methods 0.000 claims abstract description 39
- 239000012298 atmosphere Substances 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 238000004378 air conditioning Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 147
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 25
- 238000001514 detection method Methods 0.000 claims description 24
- 238000002309 gasification Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
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- 239000002245 particle Substances 0.000 claims description 2
- 230000004308 accommodation Effects 0.000 claims 1
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 9
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- 230000002349 favourable effect Effects 0.000 abstract description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 230000001276 controlling effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 241000607479 Yersinia pestis Species 0.000 description 8
- 230000002159 abnormal effect Effects 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 235000012055 fruits and vegetables Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000002000 scavenging effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 241000238631 Hexapoda Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- IHGSAQHSAGRWNI-UHFFFAOYSA-N 1-(4-bromophenyl)-2,2,2-trifluoroethanone Chemical compound FC(F)(F)C(=O)C1=CC=C(Br)C=C1 IHGSAQHSAGRWNI-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- -1 almag Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B9/00—Preservation of edible seeds, e.g. cereals
- A23B9/16—Preserving with chemicals
- A23B9/18—Preserving with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23B9/20—Preserving with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
Abstract
The invention relates to an air-conditioning fresh-keeping system and application thereof; the modified atmosphere preservation system comprises a catalytic deoxidization subsystem and a hydrogen source subsystem; the catalytic oxygen removal subsystem includes: the air extractor extracts the gas in the warehouse body and conveys the gas into the catalytic deoxidizing device; the catalytic deoxidizing device performs catalytic deoxidizing reaction on the inflowing gas to generate a first mixed gas so as to enable the first mixed gas to enter a body; the hydrogen source subsystem provides hydrogen to the library; the hydrogen source subsystem includes: a reforming hydrogen production reaction device and a heat exchange device; the reforming hydrogen production reaction device generates hydrogen-rich mixed gas. Compared with the traditional modified atmosphere storage, the modified atmosphere fresh-keeping system provided by the invention avoids the separation and transportation processes of inert gases, and has lower cost and higher safety. The oxygen content can be reduced to be lower, which is favorable for greatly improving the fresh-keeping effect. The catalytic deoxidization subsystem is adopted, and explosion is avoided through catalytic deoxidization without flame.
Description
Technical Field
The invention relates to the field of grain storage and preservation, in particular to an air-conditioning preservation system and application.
Background
At present, the grain storage technology for research and application in various countries in the world mainly comprises the following steps: an air-conditioning storage method, a low-temperature storage method, a chemical storage method, a radiation storage method and the like, wherein the development of the air-conditioning storage and the low-temperature storage is faster. As an internationally accepted green grain storage technology, the modified atmosphere grain storage technology can effectively prevent and control grain storage pests, inhibit fungi, and is harmless to grain quality, and is widely applied at present.
At present, a three-low storage mode combining low-temperature storage and chemical storage is mainly adopted in China. The proportion of nitrogen, carbon dioxide and oxygen in normal atmosphere is changed by adopting a biological oxygen reduction or artificial air regulation method in the airtight warehouse, so that a gas atmosphere harmful to grain storage pests is generated in the warehouse, and the propagation of mould can be inhibited, and the respiration and basic physiological metabolism of grains can be reduced.
The main methods adopted are as follows:
firstly, the plastic film is used for sealing the grain pile, and oxygen of the grain pile is consumed by the self-respiration of grains, so that the purposes of insect killing and bacteria inhibition are achieved, and the grain pile is also called natural oxygen-reducing grain storage.
And secondly, air is pumped out of the closed grain pile, and nitrogen is filled into the grain pile, which is also called nitrogen filling grain storage. Through verification, the nitrogen atmosphere has the effects of killing insects, preventing insects, inhibiting bacteria and keeping grain quality.
The effect of controlled atmosphere pest control has close relation with the gas concentration and treatment time of grain piles. Compared with the conventional grain storage, the nitrogen gas can effectively prevent and control grain storage pests, solves the problems of single dependence of the conventional grain storage on fumigating chemical aluminum phosphide, enhanced pest resistance and increased dosage and pest control difficulty caused by the single dependence, provides a new method for pest resistance control of the grain storage, but has the pest control effect closely related to gas concentration, grain temperature and exposure time, and the lower the grain temperature is under the effective nitrogen concentration, the longer the exposure time is required to reach 100 percent of insecticidal rate.
The controlled atmosphere storage is a storage mode for regulating the ratio of oxygen to carbon dioxide in a storage environment and inhibiting the respiration intensity of fruits so as to prolong the storage period of fruits and vegetables. Compared with the common storage, the storage period is prolonged by 1 time, so that the fruits and vegetables keep fresh and crisp, and the nutritional ingredients, hardness, color, weight and the like are almost the same as those of the fresh picked fruits and vegetables, and the fruits and vegetables have excellent storage effect. But the cost of the modified atmosphere warehouse is high.
Disclosure of Invention
Based on the defects of the prior art, the invention provides an air-conditioning fresh-keeping system which can be used for a fresh-keeping warehouse. The specific technical scheme is as follows:
an air-conditioning fresh-keeping system, comprising: a catalytic oxygen removal subsystem and a hydrogen source subsystem;
a catalytic oxygen removal subsystem comprising: the air extracting device is used for being connected with the warehouse body and extracting gas in the warehouse body to be conveyed into the catalytic deoxidizing device; the air inlet of the catalytic deaeration device is connected with the air exhaust device and is used for receiving inflow gas; the catalytic deoxidizing device is used for carrying out catalytic deoxidizing reaction on the inflow gas to generate a first mixed gas; the gas outlet of the catalytic deoxidizing device is connected with the warehouse body so that the first mixed gas flows into the warehouse body;
the hydrogen source subsystem is used for being connected with the library body and providing hydrogen to the library body; the hydrogen source subsystem includes: a reforming hydrogen production reaction device and a heat exchange device; wherein:
the reforming hydrogen production reaction device is used for generating reforming hydrogen production reaction by taking a methanol aqueous solution as a raw material to generate hydrogen-rich mixed gas; the reforming hydrogen production reaction device comprises a gasification unit, a methanol reforming unit and a CO oxidation unit, wherein the gasification unit, the methanol reforming unit and the CO oxidation unit are formed by sequentially separating a first sieve plate and a second sieve plate; the gasification unit is used for gasifying the aqueous solution of methanol; the methanol reforming unit is used for reforming the gasified methanol aqueous solution; the CO oxidation unit is used for oxidizing CO generated by reforming; a material inlet is arranged on the gasification unit, and a gas outlet is arranged on the CO oxidation unit;
the heat exchange device comprises a gas channel and a liquid channel, wherein the inlet of the liquid channel is used for receiving methanol aqueous solution, and the outlet of the liquid channel is connected with the material inlet; the inlet of the gas channel is connected with the gas outlet, and the outlet of the gas channel is used for discharging the cooled mixed gas.
Preferably, the modified atmosphere preservation system of the present invention further comprises:
the gas cooling device is used for receiving the hydrogen-rich mixed gas discharged by the reforming hydrogen production reaction device, cooling the entering hydrogen-rich mixed gas and liquefying water vapor in the hydrogen-rich mixed gas;
the water removing device is used for collecting or removing water generated by the gas cooling device; the outlet of the water removing device is used for being connected with the warehouse body.
More preferably, the method further comprises: the material storage device is used for storing methanol aqueous solution and is connected with the inlet of the liquid channel through the feeding pump.
In the modified atmosphere fresh-keeping system, preferably, the first sieve plate and the second sieve plate are positioned between the bottom plate and the top plate of the reforming hydrogen production reaction device, the distance between the first sieve plate and the bottom plate is smaller than the distance between the second sieve plate and the bottom plate, the distance between the second sieve plate and the top plate is smaller than the distance between the first sieve plate and the top plate, the distance between the first sieve plate and the bottom plate is between 10 and 200 units, and the distance between the second sieve plate and the top plate is between 10 and 200 units; the distance between the first sieve plate and the second sieve plate is between 10 and 1400 unit lengths.
In some embodiments of the invention, the reforming hydrogen production reaction device has an inner diameter in the range of 20 to 150 units of length and a height in the range of 400 to 1500 units of length.
In some embodiments of the invention, the heat exchange device is selected from at least one of a double pipe type heat exchanger, a tube type heat exchanger, a coil type heat exchanger, a plate type heat exchanger, and a spiral plate type heat exchanger.
In some embodiments of the invention, further comprising: the first temperature control device is arranged corresponding to the reforming hydrogen production reaction device and is used for controlling the temperature in the methanol reforming unit and the CO oxidation unit to be between 200 and 350 ℃.
The modified atmosphere preservation system of the invention preferably further comprises:
a mildew induction subsystem comprising: a detection device; the detection device is used for being placed in the interior of the warehouse body so as to detect CO in the warehouse body 2 Content parameters and/or temperature parameters.
The detection device described in the present invention may be a device acceptable in the art for detecting gas and/or temperature parameters, such as an electronic nose or thermometer, etc.
The modified atmosphere preservation system of the invention preferably further comprises:
a positioning subsystem, comprising: the positioning device is in communication connection with the positioning electronic equipment and is used for acquiring position information of the position and providing the position information for the positioning electronic equipment.
The positioning subsystem is an aggregation which is formed by mutually correlating and aims at determining the space position; wherein the positioning device may be implemented in a manner acceptable in the art, such as a GPS locator.
The modified atmosphere preservation system of the invention preferably further comprises:
a control subsystem, comprising: a control device; the control device is electrically connected with the hydrogen source subsystem;
a gas detection subsystem, comprising: a gas detection device for detecting a gas composition parameter in the reservoir body to be provided to the control device, wherein the control device is used for controlling the opening or closing of the hydrogen source subsystem according to the gas composition parameter;
preferably, the control device is also in communication connection with the mildew sensing subsystem; in the mildew induction subsystem, the detection device is used for being placed in the warehouse body to detect CO in the warehouse body 2 Content parameters and/or temperature parameters are provided to the control device, which is used for controlling the temperature according to the CO 2 The content parameter and/or the temperature parameter controls the on or off of the hydrogen source subsystem.
The gas detection device of the present invention may be a device acceptable in the art for detecting gas, such as an electronic nose.
The modified atmosphere preservation system of the invention preferably further comprises:
the emergency subsystem is connected with the control subsystem and is used for sending out a prompt in an opening state; the control device is used for controlling the CO 2 Content parameters and/or temperature parameters, or gas composition parameters to control the opening or closing of the emergency subsystem.
Compared with the traditional modified atmosphere warehouse construction, the modified atmosphere preservation system provided by the invention avoids inert gases (CO) 2 /N 2 ) Is less costly and safer to handle. The oxygen content can be reduced to be lower (ppm level), which is favorable for greatly improving the fresh-keeping effectAnd simultaneously, the oxygen content is monitored and treated in real time. By adopting a catalytic deoxidizing subsystem, no flame is generated to avoid explosion through catalytic deoxidization (the catalytic temperature is 40-50 ℃).
The hydrogen is used in the invention, and the hydrogen is also an important plant gas signal molecule, and has the effect of slowing down the internal physiological metabolism of grains. Compared with the hydrogen storage mode of the high-pressure gas cylinder, the hydrogen source subsystem provided by the invention has the advantages that the internal pressure of the hydrogen source subsystem is basically in the micro-positive pressure condition, in actual use, the risk of hydrogen leakage is small, and the safety coefficient is higher. Compared with the method for producing hydrogen by electrolysis of water, the product of the method has oxides and reducers at the same time, and the risk of explosion is high. The product of the hydrogen source subsystem provided by the invention is only hydrogen and inert gas CO 2 The explosion risk is low. Compared with the high-pressure gas cylinder hydrogen storage and electrolysis water hydrogen production, the hydrogen source subsystem of the invention is far lower than the hydrogen supply cost of the two methods.
The control subsystem and the emergency subsystem are additionally arranged to quickly respond to the emergency, so that the expansion or upgrading of the emergency is avoided, the loss caused by the emergency is reduced to the maximum extent, and the risk prevention consciousness and the capability are improved in various aspects. And a positioning subsystem is additionally arranged, so that accurate positioning and identification of personnel and equipment are realized.
The invention also provides an application of the modified atmosphere preservation system for storing seeds.
Of course, it is not necessary for any one product or method of practicing the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a reforming hydrogen production reaction device in an air-conditioning fresh-keeping system provided by the invention;
FIG. 2 is a schematic diagram of a catalytic deoxidizing device in the modified atmosphere preservation system provided by the invention;
fig. 3 is a schematic structural diagram of the modified atmosphere preservation system provided by the invention.
Reference numerals:
100: a hydrogen source subsystem; 200: a catalytic oxygen removal subsystem;
101: a reforming hydrogen production reaction device; 201: a housing;
102: a first screen plate; 202: a receiving chamber;
103: a second screen plate; 203: a porous plate;
104: a gasification unit; 300: a mildew sensing subsystem;
105: a methanol reforming unit; 301: a detection device;
106: a CO oxidation unit; 400: a positioning subsystem;
107: a material inlet; 500: a control subsystem;
108: a gas outlet; 600: a gas detection subsystem;
109: a heat exchange device; 700: an emergency subsystem.
110: a material storage device;
111: a feed pump;
112: a first temperature control device.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-3, this embodiment provides an air-conditioning fresh-keeping system, which includes: catalytic oxygen removal subsystem 200 and hydrogen source subsystem 100;
catalytic oxygen removal subsystem 200 includes: the air extracting device is used for being connected with the warehouse body and extracting gas in the warehouse body to be conveyed into the catalytic deoxidizing device; the air inlet of the catalytic deaeration device is connected with the air exhaust device and is used for receiving inflow gas; the catalytic deoxidizing device is used for carrying out catalytic deoxidizing reaction on the inflow gas to generate a first mixed gas; the gas outlet of the catalytic deoxidizing device is connected with the warehouse body so that the first mixed gas flows into the warehouse body;
a hydrogen source subsystem 100 for connecting with the library and supplying hydrogen gas to the library; the hydrogen source subsystem 100 includes: a reforming hydrogen production reaction device 101 and a heat exchange device 109; wherein:
the reforming hydrogen production reaction device 101 is used for generating reforming hydrogen production reaction by taking a methanol aqueous solution as a raw material to generate hydrogen-rich mixed gas; the reforming hydrogen production reaction device 101 comprises a gasification unit 104, a methanol reforming unit 105 and a CO oxidation unit 106 which are sequentially separated by a first sieve plate 102 and a second sieve plate 103; the gasification unit 104 is used for gasifying the aqueous methanol solution; the methanol reforming unit 105 is used for reforming the gasified methanol aqueous solution; the CO oxidation unit 106 is configured to oxidize CO generated by reforming; a material inlet 107 is arranged on the gasification unit 104, and a gas outlet 108 is arranged on the CO oxidation unit 106;
the heat exchange device 109 comprises a gas channel and a liquid channel, wherein the inlet of the liquid channel is used for receiving the aqueous methanol solution, and the outlet of the liquid channel is connected with the material inlet 107; the inlet of the gas channel is connected to the gas outlet 108, and the outlet of the gas channel is used for discharging the cooled mixed gas.
Therefore, in the operation process of the modified atmosphere fresh-keeping system of this embodiment, the hydrogen source subsystem 100 generates hydrogen and inputs the hydrogen into the warehouse, the air extractor of the catalytic deoxidizing subsystem 200 extracts air from the warehouse, at this time, the gas in the warehouse is a mixture of air and hydrogen, and in the catalytic deoxidizing device, the hydrogen and oxygen in the air undergo oxidation reaction, so that signal gases such as oxygen in the air and ethylene which may exist can be removed, and the mixed gas after removing the oxygen flows into the warehouse from the air outlet of the catalytic deoxidizing device, so as to perform the next circulation process.
Specifically, the catalytic deoxidizing device may be a catalytic deoxidizing device known in the art, preferably, with reference to fig. 2, the catalytic deoxidizing device includes:
a housing 201, wherein an accommodating chamber 202 is formed inside the housing 201;
a porous plate 203 disposed inside the housing 201 to divide the accommodating chamber 202 into a first compartment and a second compartment; the second compartment is used for containing an oxygen removal catalyst;
the shell 201 is provided with an air inlet and an air outlet, the distance between the air inlet and the first separation chamber is smaller than the distance between the air inlet and the second separation chamber, and the distance between the air outlet and the second separation chamber is smaller than the distance between the air outlet and the first separation chamber. The air outlet is used for being connected with the warehouse body so that the first mixed gas flows into the warehouse body.
As an illustration and description, the oxygen scavenging catalyst may be selected from any of the options acceptable in the art, preferably, in this embodiment, the oxygen scavenging catalyst noble metal based catalyst; more preferably, the oxygen scavenging catalyst is a CAS-KR-MF-NT ambient temperature oxygen scavenging catalyst (available from Kernel environmental protection catalysis Co., ltd.).
When the catalytic deoxidizing device is in operation, after gas enters from the gas inlet, the gas passes through the porous plate 203 and contacts with the deoxidizing catalyst to perform deoxidizing reaction, so that oxygen-free mixed gas is generated. And the oxygen-free mixed gas is discharged from the gas outlet.
The "first mixed gas" appearing in the embodiment explains and emphasizes the description, and the first mixed gas refers to a mixed gas from which most or all of oxygen is removed, and does not exclude a trace amount of oxygen.
Illustratively, the hydrogen source subsystem 100 operates as follows:
the aqueous methanol solution flows into the liquid channel of the heat exchange device 109 from the inlet of the liquid channel, and flows to the outlet of the liquid channel, and finally flows into the reforming hydrogen production reaction device 101 from the inlet of the reforming hydrogen production reaction device 101, in the reforming hydrogen production reaction device 101, the aqueous methanol solution firstly enters the gasification unit 104, under the action of the gasification unit 104, the aqueous methanol solution is gasified to generate methanol steam, the methanol steam flows to the methanol reforming unit 105, the methanol reforming reaction in the unit generates hydrogen, meanwhile, part of CO is generated, the mixed gas flows to the CO oxidation unit 106, the CO is oxidized to generate carbon dioxide CO 2 The mixed gas of hydrogen and carbon dioxide flows out from the gas outlet 108 of the reforming hydrogen production reaction device 101, enters the heat exchange device 109 from the gas inlet of the heat exchange device 109, and in the heat exchange device 109, the liquid (methanol water) in the liquid channel and the mixed gas in the gas channel exchange heat, and finally the mixed gas flows out from the gas outlet 108 of the heat exchange device 109.
Therefore, the reforming hydrogen production reaction device 101 integrates the gasification unit 104, the methanol reforming unit 105 and the CO oxidation unit 106, so that the production difficulty of equipment is reduced, and the processing efficiency of the equipment is improved. The heat exchange device 109 is cooperatively arranged, so that the utilization rate of the thermal efficiency of the equipment is improved, and the power consumption and the gas production cost of the equipment are reduced.
The integral reforming hydrogen production reaction device 101 formed by separating the sieve plates is adopted, so that the preparation simplicity of the reforming hydrogen production reaction device 101 is further improved, and the processing efficiency of equipment is improved.
The modified atmosphere preservation system according to the present embodiment preferably further includes: a gas cooling device, configured to receive the hydrogen-rich mixed gas discharged from the reforming hydrogen production reaction device 101, cool the hydrogen-rich mixed gas, and liquefy water vapor therein;
the water removing device is used for collecting or removing water generated by the gas cooling device; the outlet of the water removing device is used for being connected with the warehouse body.
The water removal device described in this embodiment may take any form acceptable in the art, for example, a desiccant may be added to the water removal device to remove condensed water; the drying agent is not particularly limited, and silica gel, calcium oxide, and the like can be used, for example.
The hydrogen source subsystem 100 provided by the invention is used for delivering reformed gas into a grain depot, wherein the hydrogen content is about 75% and the carbon dioxide content is about 25%.
More preferably, the method further comprises: a material storage device 110 and a feed pump 111, wherein the material storage device 110 is used for storing methanol aqueous solution, and the material storage device 110 is connected with the inlet of the liquid channel through the feed pump 111.
The feed pump 111 is not particularly limited, and may be, for example, one of the feed pumps 111 acceptable in the art, such as peristaltic pump, gear pump, centrifugal pump, and the like.
The materials of the feeding pump 111 and the corresponding pipeline can be selected by a person skilled in the art according to actual requirements, and the materials can be at least one of a silica gel hose, a metal hard tube, and the like.
The pipe diameter of the feed pump 111 may be selected from one of phi 3, phi 6 and phi 8.
The flow rate of the feed during operation of this embodiment may be dependent on the actual production scale and requirements, and this embodiment is preferably 1 to 20ml/min.
More preferably, in the aqueous methanol solution, the volume ratio of methanol to water is (0.9-1.5): 1.
in the air-filled packaging system of this embodiment, the number of the holes of the first screen plate 102 is between 6 and 64.
The number of the sieve holes of the second sieve plate 103 is between 6 and 64.
The methanol reforming unit 105 described in this embodiment may be used in the presence of a methanol reforming catalyst such as Cu-Zn-Al 2 O 3 (more for example, using a commercially available SCST-401 type catalyst) a reaction of reforming methanol to produce hydrogen occurs. The reaction equation is as follows:
CH 3 OH→CO+2H 2
H 2 O+CO→CO 2 +H 2
CH 3 OH+H 2 O→CO 2 +3H 2
the reaction of reforming methanol to produce hydrogen can produce hydrogen and simultaneously produce certain CO and CO 2 。
The CO oxidation unit 106 described in this embodiment may be used in the presence of a carbon monoxide low temperature catalyst, such as CuO-ZnO-Al 2 O 3 The oxidation of carbon monoxide is achieved by a low temperature catalytic reaction of carbon monoxide (e.g., using a commercially available SCST-231 type catalyst) as follows:
CO+H 2 O→CO 2 +H 2 +41.19kJ/mol
it will be appreciated by those skilled in the art that the methanol reforming unit 105 and the CO oxidation unit 106 in this embodiment may be filled with catalysts required for the corresponding reactions, and the catalysts may be selected according to actual production requirements, which is not limited in this embodiment. Preferably, the first catalyst includes at least one of copper, zinc, aluminum, palladium, or the like, or an oxide of copper, zinc, aluminum, palladium, or the like. The second catalyst comprises at least one of copper, zinc, aluminum, iron, palladium, and other metals or oxides of copper, zinc, aluminum, iron, palladium, and other metals.
In the inflation packaging system according to this embodiment, as a preferable or another aspect, the heat exchanging device 109 is at least one selected from a double pipe type heat exchanger, a tube type heat exchanger, a coil type heat exchanger, a plate type heat exchanger, and a spiral plate type heat exchanger.
In the gas-filled packaging system according to this embodiment, as a preferable or another technical solution, the material of the reforming hydrogen production reaction device 101 is at least one selected from stainless steel, almag, copper and brass.
In the modified atmosphere fresh-keeping system according to this embodiment, preferably, the first sieve plate 102 and the second sieve plate 103 are located between the bottom plate and the top plate of the reforming hydrogen production reaction device 101, the distance between the first sieve plate 102 and the bottom plate is smaller than the distance between the second sieve plate 103 and the bottom plate, the distance between the second sieve plate 103 and the top plate is smaller than the distance between the first sieve plate 102 and the top plate, the distance between the first sieve plate 102 and the bottom plate is between 10 and 200 units, and the distance between the second sieve plate 103 and the top plate is between 10 and 200 units; the distance between the first screening deck 102 and the second screening deck 103 is between 10 and 200 units of length.
Preferably, the methanol reforming unit 105 can accommodate a first catalyst for catalyzing the hydrogen production by reforming methanol, the CO oxidation unit 106 can accommodate a second catalyst for catalyzing the CO oxidation, and the mesh sizes of the first sieve plate 102 and the second sieve plate 103 are smaller than the minimum particle sizes of the first catalyst and the second catalyst.
Thus, during operation, the methanol water vapor sequentially passes through the gasification unit 104, the methanol reforming unit 105 and the CO oxidation unit 106, and the first catalyst and the second catalyst do not move to other units along with the gas flow, so that the effective catalytic efficiency of the methanol reforming unit 105 and the CO oxidation unit 106 can be ensured.
In the gasification unit 104 described in this embodiment, a gasification device may be included in the gasification unit 104, and the gasification device may select a gasification tank, a gasification plate, etc. according to actual needs by a person skilled in the art; the vaporizing device is provided with a heating element to gasify the aqueous methanol solution flowing into the vaporizing unit 104. Those skilled in the art will appreciate that the components of the gasification unit 104 need to have a certain compressive strength and temperature resistance.
In some implementations of this example, the reforming hydrogen production reaction device 101 has an inner diameter in the range of 20 to 150 units of length and a height in the range of 400 to 1500 units of length.
In some implementations of the present embodiment, further comprising: the first temperature control device 112 is provided corresponding to the reforming hydrogen production reaction device 101, and the first temperature control device 112 is used for controlling the temperature in the methanol reforming unit 105 and the CO oxidation unit 106 to be between 200 and 350 ℃.
Thereby facilitating the occurrence of the methanol reforming hydrogen production reaction.
The modified atmosphere preservation system according to the embodiment preferably further includes:
mildew sensing subsystem 300 includes: a detection device 301; the detection device 301 is configured to be placed inside the warehouse body to detect CO inside the warehouse body 2 Content parameters and/or temperature parameters.
The detection device 301 described in this embodiment may be a device acceptable in the art for detecting gas and/or temperature parameters, such as an electronic nose or thermometer.
The detection device 301 described in this embodiment may be one or more.
During operation, the detection device 301 is placed inside the library. The detecting device 301 detects parameters of surrounding gas (including concentration parameters of gas, such as concentration parameters of hydrogen or concentration parameters of carbon dioxide, etc.) and/or temperature parameters to better monitor whether the food stored in the warehouse is mildewed or not.
The modified atmosphere preservation system according to the embodiment preferably further includes:
positioning subsystem 400 includes: the positioning device is in communication connection with the positioning electronic equipment and is used for acquiring position information of the position and providing the position information for the positioning electronic equipment.
Therefore, in the operation process, the worker can hold the positioning device by hand, and when the worker patrols in the warehouse, abnormal conditions (such as mildew or other abnormal conditions of food) can be found and fed back in real time, and the abnormal conditions can be received by the positioning electronic equipment, so that the monitoring of the mildew conditions is realized in real time.
The modified atmosphere preservation system according to the embodiment preferably further includes:
control subsystem 500, comprising: a control device; the control device is electrically connected with the hydrogen source subsystem 100;
the gas detection subsystem 600 includes: and the gas detection device is used for detecting the gas composition parameter in the warehouse body to be provided for the control device, and the control device is used for controlling the on or off of the hydrogen source subsystem 100 according to the gas composition parameter.
Thus, the gas detection device detects gas component parameters (which may include a hydrogen concentration parameter, a carbon dioxide concentration parameter, an oxygen concentration parameter, etc.) of the library, and controls whether the hydrogen source subsystem 100 delivers hydrogen into the library according to the gas component parameters. So as to better realize the automatic operation of the controlled atmosphere fresh-keeping warehouse system.
Preferably, the control device is also in communication with the mildew sensing subsystem 300; in the mildew sensing subsystem 300, the detection device 301 is configured to be placed inside the warehouse body to detect CO in the warehouse body 2 Content parameters and/or temperature parameters are provided to the control device, which is used for controlling the temperature according to the CO 2 The content parameter and/or the temperature parameter control the turning on or off of the hydrogen source subsystem 100.
Thereby, the detection device 301 of the mildew sensing subsystem 300 detects CO 2 The content parameter and/or the temperature parameter can also be fed back to the control device when abnormal, and the control device is used for controlling the temperature according to the CO 2 The content parameter and/or the temperature parameter control the activation of the hydrogen source subsystem 100. And when CO 2 When the content parameter and/or the temperature parameter are recovered to be normal, the content parameter and/or the temperature parameter are fed back to the control device and are used by the control device for controlling the temperature according to the CO 2 The content parameter and/or the temperature parameter control the shut down of the hydrogen source subsystem 100.
The modified atmosphere preservation system according to the embodiment preferably further includes:
the emergency subsystem 700 is connected with the control subsystem 500, and the emergency subsystem 700 is used for sending out a prompt in an open state; the control device is used for controlling the CO 2 Content parameters and/or temperature parameters, or gas composition parameters to control the opening or closing of the emergency subsystem 700.
Whereby the control device is adapted to control the flow of the gas in accordance with the CO 2 The content parameter and/or the temperature parameter, or the gas composition parameter controls the opening or closing of the emergency subsystem 700 when reaching a preset value, and the emergency subsystem 700 canThe prompt (any form of prompt accepted in the field, such as one or a combination of a plurality of light prompts, sound prompts, picture prompts and the like) is sent out, so that the conditions in the warehouse are abnormal and larger than the processing capacity of the air-conditioning fresh-keeping system, and the air-conditioning fresh-keeping system cannot or is difficult to process by itself and feeds back in time, so that a worker can find abnormal conditions in time and process the abnormal conditions as soon as possible, and the possibility of loss and danger is reduced.
Compared with the traditional modified atmosphere warehouse construction, the modified atmosphere preservation system provided by the embodiment avoids inert gas (CO) 2 /N 2 ) Is less costly and safer to handle. The oxygen content can be reduced to be lower (ppm level), which is favorable for greatly improving the fresh-keeping effect, and simultaneously, the oxygen content is monitored and treated in real time. By adopting a catalytic deoxidizing subsystem, no flame is generated to avoid explosion through catalytic deoxidization (the catalytic temperature is 40-50 ℃).
In this embodiment, hydrogen is used, which is also an important plant gas signal molecule, and has the effect of slowing down the physiological metabolism in grains. Compared with the hydrogen storage mode of the high-pressure gas cylinder, the hydrogen source subsystem provided by the embodiment is basically in the micro-positive pressure condition, and in actual use, the risk of hydrogen leakage is small, and the safety coefficient is higher. Compared with the method for producing hydrogen by electrolysis of water, the product of the method has oxides and reducers at the same time, and the risk of explosion is high. The product of the hydrogen source subsystem provided in this example is only hydrogen and inert gas CO 2 The explosion risk is low. Compared with the hydrogen storage of a high-pressure gas cylinder and the hydrogen production of electrolysis water, the hydrogen source subsystem of the embodiment is far lower than the hydrogen supply cost of the two methods.
The control subsystem and the emergency subsystem are additionally arranged to quickly respond to the emergency, so that the expansion or upgrading of the emergency is avoided, the loss caused by the emergency is reduced to the maximum extent, and the risk prevention consciousness and the capability are improved in various aspects. And a positioning subsystem is additionally arranged, so that accurate positioning and identification of personnel and equipment are realized.
It is noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (9)
1. An air-conditioning fresh-keeping system, characterized by comprising: a catalytic oxygen removal subsystem and a hydrogen source subsystem;
a catalytic oxygen removal subsystem comprising: the air extracting device is used for being connected with the warehouse body and extracting gas in the warehouse body to be conveyed into the catalytic deoxidizing device; the air inlet of the catalytic deaeration device is connected with the air exhaust device and is used for receiving inflow gas; the catalytic deoxidizing device is used for carrying out catalytic deoxidizing reaction on the inflow gas to generate a first mixed gas; the gas outlet of the catalytic deoxidizing device is connected with the warehouse body so that the first mixed gas flows into the warehouse body;
wherein, the catalytic deoxygenation device includes: a housing having an accommodation chamber formed therein; a porous plate disposed inside the housing, dividing the receiving chamber into a first compartment and a second compartment; the second compartment is used for containing an oxygen removal catalyst; the shell is provided with an air inlet and an air outlet, the distance between the air inlet and the first separation cavity is smaller than the distance between the air inlet and the second separation cavity, and the distance between the air outlet and the second separation cavity is smaller than the distance between the air outlet and the first separation cavity;
the hydrogen source subsystem is used for being connected with the library body and providing hydrogen to the library body; the hydrogen source subsystem includes: a reforming hydrogen production reaction device and a heat exchange device; wherein:
the reforming hydrogen production reaction device is used for generating reforming hydrogen production reaction by taking a methanol aqueous solution as a raw material to generate hydrogen-rich mixed gas; the reforming hydrogen production reaction device comprises a gasification unit, a methanol reforming unit and a CO oxidation unit, wherein the gasification unit, the methanol reforming unit and the CO oxidation unit are formed by sequentially separating a first sieve plate and a second sieve plate; the gasification unit is used for gasifying the aqueous solution of methanol; the methanol reforming unit is used for reforming the gasified methanol aqueous solution; the CO oxidation unit is used for oxidizing CO generated by reforming; a material inlet is arranged on the gasification unit, and a gas outlet is arranged on the CO oxidation unit; the methanol reforming unit can contain a first catalyst for catalyzing the hydrogen production by reforming methanol, the CO oxidation unit can contain a second catalyst for catalyzing the CO oxidation, and the mesh pore diameters of the first sieve plate and the second sieve plate are smaller than the minimum particle diameters of the first catalyst and the second catalyst;
the heat exchange device comprises a gas channel and a liquid channel, wherein the inlet of the liquid channel is used for receiving methanol aqueous solution, and the outlet of the liquid channel is connected with the material inlet; the inlet of the gas channel is connected with the gas outlet, and the outlet of the gas channel is used for discharging the cooled mixed gas;
the hydrogen source subsystem further comprises:
the gas cooling device is used for receiving the hydrogen-rich mixed gas discharged by the reforming hydrogen production reaction device, cooling the entering hydrogen-rich mixed gas and liquefying water vapor in the hydrogen-rich mixed gas;
the water removing device is used for collecting or removing water generated by the gas cooling device; the outlet of the water removing device is connected with the warehouse body;
the material storage device is used for storing methanol aqueous solution and is connected with the inlet of the liquid channel through the feeding pump.
2. The modified atmosphere fresh-keeping system according to claim 1, wherein the first screen plate and the second screen plate are located between a bottom plate and a top plate of the reforming hydrogen production reaction device, a distance between the first screen plate and the bottom plate is smaller than a distance between the second screen plate and the bottom plate, a distance between the second screen plate and the top plate is smaller than a distance between the first screen plate and the top plate, the distance between the first screen plate and the bottom plate is between 10 and 200 units, and a distance between the second screen plate and the top plate is between 10 and 200 units; the distance between the first sieve plate and the second sieve plate is 10-200 units long.
3. The controlled atmosphere fresh-keeping system according to claim 1, wherein the inner diameter of the reforming hydrogen production reaction device is within a range of 20-150 units of length and the height is within a range of 400-1500 units of length.
4. The modified atmosphere preservation system of claim 1, further comprising:
a mildew induction subsystem comprising: a detection device; the detection device is used for being placed in the interior of the warehouse body so as to detect CO in the warehouse body 2 Content parameters and/or temperature parameters.
5. The modified atmosphere preservation system of claim 4, further comprising:
a positioning subsystem, comprising: the positioning device is in communication connection with the positioning electronic equipment and is used for acquiring position information of the position and providing the position information for the positioning electronic equipment.
6. The modified atmosphere preservation system of claim 5, further comprising:
a control subsystem, comprising: a control device; the control device is electrically connected with the hydrogen source subsystem;
a gas detection subsystem, comprising: and the gas detection device is used for detecting the gas component parameter in the warehouse body to supply to the control device, and the control device is used for controlling the opening or closing of the hydrogen source subsystem according to the gas component parameter.
7. The modified atmosphere preservation system of claim 6, wherein the control device is further communicatively coupled to the mildew sensing subsystem; in the mildew induction subsystem, the detection device is used for being placed in the warehouse body to detect CO in the warehouse body 2 Content parameters and/or temperature parameters are provided to the control device, which is used for controlling the temperature according to the CO 2 The content parameter and/or the temperature parameter controls the on or off of the hydrogen source subsystem.
8. The modified atmosphere preservation system of claim 7, further comprising:
the emergency subsystem is connected with the control subsystem and is used for sending out a prompt in an opening state; the control device is used for controlling the CO 2 Content parameters and/or temperature parameters, or gas composition parameters to control the opening or closing of the emergency subsystem.
9. Use of the modified atmosphere preservation system of any one of claims 1-8 for storing seeds.
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| CN111616216A (en) * | 2020-06-08 | 2020-09-04 | 南京农业大学 | Application of hydrogen in modified atmosphere storage of plant seeds |
| CN114041497A (en) * | 2021-12-27 | 2022-02-15 | 广东蓝玖新能源科技有限公司 | Fresh-keeping method |
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