CN101870895B - Production method of solid methane - Google Patents
Production method of solid methane Download PDFInfo
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- CN101870895B CN101870895B CN2010101913470A CN201010191347A CN101870895B CN 101870895 B CN101870895 B CN 101870895B CN 2010101913470 A CN2010101913470 A CN 2010101913470A CN 201010191347 A CN201010191347 A CN 201010191347A CN 101870895 B CN101870895 B CN 101870895B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention relates to a method for producing solid methane by using gas methane produced in the process of garbage landfill, organic waste anaerobic digestion, high concentration organic waste water anaerobic treatment or the like. The invention can transport methane safely and conveniently and realize low carbon economic cycle. The method comprises the steps of pretreating, pressurizing and flow control, and solid methane generation. In the pretreating process, hydrogen sulfide and carbon dioxide can be removed in one step; in the pressurizing and flow control process, methane sent out by a gas storage bag is pressurized by a compressor, transported into a methane buffer tank, and transported to a high pressure reaction kettle through a relief valve; and in the solid methane generation process, the high pressure reaction kettle is used as the equipment, the methane is stirred by a stirring apparatus of the reaction kettle to finally generate solid methane. The invention has the characteristics of simpleness, practicality, and safe and reliable transportation, realizes low carbon economic cycle and prevents environmental pollution.
Description
Technical field
The gas biogas production that the present invention relates to produce in the processes such as garbage loading embeading, organic waste anaerobic digestion (processing) or high concentrated organic wastewater anaerobic treatment becomes the method for solid methane, can make the biogas convenience, transport safely, realizes the low-carbon economy circulation.
Background technology
Produce a large amount of biogas in garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment process, biogas is gas, and main component is methane.Methane gas is a kind of greenhouse gases, and the Greenhouse effect of generation are more than 20 times of carbonic acid gas, is again a kind of clear energy sources simultaneously.Yet, because biogas is inflammable and explosive, be difficult for the characteristic of conveying and transportation, make in garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment process, the biogas with producing that has directly discharges, have with after collecting methane, utilize torch form burning and exhausting, what have collects, cook for oneself heating up water, a small amount of generates electricity, but generated energy is unstable, generally will not network.Also have the rural area away from the city, people are but utilizing crop material, firewood, coal etc. as rudimentary, the necessary burning energy; Also have the big city, as Beijing, the Sweet natural gas of use is the high-carbon energy of the defeated underground mining in eastern gas west.
Summary of the invention
Be fully used in order to make the energy, the biogas that garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment are produced easily, being transported to the rural area and using nearby of safety, the present invention utilizes natural pond G﹠W effect, the production method of having invented a kind of solid methane that can burn.
Solid methane is a kind of hydrate, is the crystalloid cage compound that main component-methane in biogas and water form, and wherein water molecules forms body junction crystal mesh lattice by hydrogen bond, is full of the methane gas molecule in the hole in lattice.Solid methane is a kind of highdensity energy source mineral, and every cubic metre of solid methane can discharge the biogas of 180 cubic metres of left and right.The heat that the solid methane burning of unit volume discharges is approximately 10 times of coal, is 2 ~ 5 times of conventional gas.The thermal conductivity of solid methane is 18.7W/ (m. ℃), [approximately 22.7W/ (m. ℃)] is also low than general lagging material, so the storage vessel of solid methane does not need special adiabatic measure, can be in normal pressure, stably stored, transportation at temperature more than-15 ℃.With the solid methane heating, then the gas compression tinning that discharges or pipeline are transported to the user get final product behind the point of destination or before using.
Solid methane production method of the present invention, it comprises the following steps:
(1), pre-treatment: the present invention adopts the pre-treatment tank, can one-stoply remove hydrogen sulfide and carbonic acid gas.The sodium hydroxide solution of pH value 11-13 is housed in the pre-treatment tank, and when the biogas that garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment are produced, during by sodium hydroxide solution, carbonic acid gas and sodium hydroxide generate sodium carbonate; Hydrogen sulfide and and sodium hydroxide generation sodium sulphite.Be stored in gas-storing bag standby through the pretreated biogas of removing carbonic acid gas and hydrogen sulfide.
(2), supercharging and flow control: the biogas utilization compressor that gas-storing bag is sent compresses, be transported in the biogas surge tank after improving pressure, reducing valve is equipped with in the outlet of surge tank, the required pressure of step autoclave after entering in order to control, adjusting.Through the biogas of reducing valve, then be transported to autoclave by one after the flow control tube road direction with mass flowmeter.
(3), solid methane generates: the equipment that solid methane generates is autoclave.Be added with reaction solution in reactor, load responsive fluid accounts for the 1/4-2/5 of reactor useful volume, and reaction solution is the distilled water that contains tensio-active agent, and biogas passes in reactor after flowing out from surge tank.Kettle cover centre at autoclave is provided with whipping appts, by stirring, increases the speed of reaction of biogas in reaction solution.Mixing speed per minute 300-500 turns, churning time 30-50min.The kettle of reactor is jacketed type, and refrigeration agent is housed in chuck, by the heat exchange action of reactor inwall, the temperature in reactor is controlled to 4-20 ℃, and pressure-controlling is 2-6MPa.Gas, liquid temp, cooling and warming in the rotating speed of stirrer and churning time, reactor are all set, control and indicate by the reactor controller.When the mass flowmeter in the flow control pipeline no longer showed gas flow, the solid methane reaction was completed; Close all gas circuit valves, slowly open the exhaust pressure relief valve and carry out pressure release, after reacting kettle inner pressure is reduced to 0MPa, open the baiting valve of reactor bottom, solid methane is entered in storage vessel.
The present invention adopts the pre-treatment tank, one-stop hydrogen sulfide and the carbonic acid gas of removing, and with low cost, efficient is high.Characteristic feature of an invention is simple, practical, stores, transportation safety is reliable.Both realize the low-carbon economy circulation, prevented again environmental pollution.
Description of drawings
Fig. 1 is production method block diagram of the present invention
Fig. 2 is the schematic diagram of solid methane reactor
In figure: 1. pre-treatment canister incoming gas mouth, 2. pre-treatment tank, 3. gas-storing bag, 4. compressor, 5. surge tank intake valve, 6. tensimeter, 7. surge tank, 8. reducing valve, 9. mass flowmeter intake valve, 10. mass flowmeter by-pass valve, 11. mass flowmeters, 12. mass flowmeter air outlet valves, 13. mass flowmeter controllers, 14. reactor tensimeters, 15. rupture disk, 16. reactors, 17. intake valves, 18. reactor controllers.
16-1. apparatus capable of fluctuating, 16-2. belt, 16-3. servomotor, 16-4. screw, 16-5 exhaust pressure relief valve, 16-6. liquid phase platinum resistor temperature measuring instrument, 16-7. liquid adding bottle, 16-8. refrigeration agent, 16-9. gas phase platinum resistor temperature measuring instrument, 16-10. agitator, 16-11. gas distributor, 16-12. baiting valve, 16-13. kettle, 16-14. kettle cover, 16-15, handwheel, 16-16 compressor.
18-1. churning time controller, 18-2. frequency transformer, 18-3. gas phase temperature display instrument, 18-4. liquid phase temperature controller, 18-5. heating/refrigerating switch, 18-6. rotating speed display instrument.
Embodiment
Referring to Fig. 1, Fig. 2, production method of the present invention is carried out as follows:
Step 1: pre-treatment: in garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment process, methanobacteria has produced a large amount of biogas with organic substance decomposing.Main component in biogas is methane, and different owing to processing object, condition is different, so methane content is different, is generally 50-76%, other be carbonic acid gas, hydrogen sulfide and the minor amount of water impurity that grades, wherein carbonic acid gas accounts for the 20%-45% left and right, and hydrogen sulfide accounts for 3% left and right.Utilization rate of heat value is higher, transportation cost is lower in order to produce, and without the solid methane of corrosive nature, should remove carbonic acid gas and hydrogen sulfide before producing, and general dry type ferric oxide or the additive method of adopting only removes hydrogen sulfide in biogas utilization.The present invention adopts pre-treatment tank 2, one-stop hydrogen sulfide and the carbonic acid gas of removing, method is: with the biogas that produces in garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment process, send in pre-treatment tank 2 through pre-treatment canister incoming gas mouth 1 by pipeline, the pH value is housed in pre-treatment tank 2 is the sodium hydroxide solution of 12-13, biogas passes into sodium hydroxide solution, carbonic acid gas in biogas and sodium hydroxide generate sodium carbonate, hydrogen sulfide and sodium hydroxide generate sodium sulphite, and carbonic acid gas and hydrogen sulfide in biogas are removed.The biogas of having removed carbonic acid gas and hydrogen sulfide is sent to gas-storing bag 3 by pipeline from the outlet of pre-treatment tank 2 and stores for future use.When the pH of sodium hydroxide solution drops to lower than 11 the time, close pre-treatment canister incoming gas mouth 1, the sodium hydroxide solution that contains sodium carbonate and sodium sulphite from pre-treatment tank 2 bottoms discharge 1/4-3/4 volumes, replenish again new sodium hydroxide solution, until the pH value in pre-treatment tank 2 reaches 12-13, then open pre-treatment canister incoming gas mouth 1, pass into again biogas to pre-treatment tank 2.Above-mentioned treating processes so repeatedly.
Biogas is with after reaction solution contacts, due to the effect of hydrogen bond, the water molecules monomer connects to the water molecules network mutually, and the methane molecule in biogas enters the stability that has strengthened network after network, form metastable small size hydrate nucleus group, be expressed as with reaction equation:
M+H2O+(H2O)
r-1→M…(H2O)
R
(in formula: M represents methane molecule; The lower footnote of bracket represents the size of nucleus, and three points represent interaction weak between methane molecule and water molecules)
Then near water molecules and the methane molecule group grown as core take it, makes solid methane nucleus group size increase to critical size, forms stable solid methane nucleus, both:
M+H2O+M…(H2O)r→M.(H2O)c
After stable solid methane nucleus reaches enough concentration, be exactly and then the growth phase of solid methane:
M+H2O+M.(H2O)r→M.(H2O)n
Solid methane is a kind of non-stoichiometric compound.Temperature when forming of gas molecule in solid methane and the ratio of water molecules, pressure, contact area, churning time, mixing speed etc. are relevant.
Churning time is made as 30-50 minute, and better 40 minutes, 18-1 set and shows by the churning time controller; Gas phase temperature in reactor 16 is measured by the gas phase platinum resistor temperature measuring instrument 16-9 by kettle cover, is shown by gas phase temperature display instrument 18-3.Because the temperature of reaction of solid methane is 4 ℃, so liquidus temperature is made as 4 ℃, provide cold by the refrigeration agent 16-8 in reacting kettle jacketing, the liquid phase platinum resistor temperature measuring instrument 16-6 by kettle cover measures, and is set and shown by liquid phase temperature controller 18-4.Refrigeration agent 16-8 is ethanol or ethylene glycol, carries out compression refrigeration by compressor 16-16, and 18-5 controls by the heating/refrigerating switch; Reaction heat carries out heat exchange by inwall and the refrigeration agent 16-8 of reactor kettle 16-13.Between reactor tensimeter 14 and intake valve 17, rupture disk 15 is housed, in case pressure surpasses the insurance of reactor 16 when bearing pressure, rupture disk 15 pressure release of breaking, the safety of protective reaction still 16.When mass flowmeter 11 no longer shows gas flow, illustrate that solid methane reaction completes.Close all gas circuit valves this moment, slowly opens exhaust pressure relief valve 16-5 and carry out pressure release and emit biogas, and the biogas of emitting is reclaimed.
After the pressure of reactor tensimeter 14 is reduced to 0MPa, open the baiting valve 16-12 of reactor 16 bottoms, solid methane is entered in storage vessel.
After solid methane enters in storage vessel, then carry out again the preparation production of solid methane by described step 3.
Under normal pressure, solid methane is in-5 to-15 ℃ of preservations, transportation.
When needs are checked or are safeguarded reactor inside, can unclamp the connecting screw 16-4 of kettle cover 16-14 and kettle 16-13, rotate the turning handle 16-15 on lifting device 16-1, kettle cover 16-14 is risen operate.
Above embodiment is explanation of the invention, is not the restriction to invention, in the situation that without prejudice to spirit of the present invention, the present invention can do any type of modification
Claims (10)
1. the production method of a solid methane comprises following three steps:
(1) pre-treatment: the pre-treatment tank is adopted in pre-treatment, can one-stoply remove hydrogen sulfide and carbonic acid gas; The sodium hydroxide solution of pH value 11-13 is housed in the pre-treatment tank, and when the biogas that garbage loading embeading, organic waste anaerobic digestion or high concentrated organic wastewater anaerobic treatment are produced, during by sodium hydroxide solution, carbonic acid gas and sodium hydroxide generate sodium carbonate; Hydrogen sulfide and sodium hydroxide generate sodium sulphite; Be stored in gas-storing bag standby through the pretreated biogas of removing carbonic acid gas and hydrogen sulfide;
(2) supercharging and flow control: the biogas utilization compressor that gas-storing bag is sent compresses, be transported in the biogas surge tank after improving pressure, reducing valve is equipped with in the outlet of surge tank, in order to control, to regulate the pressure of the outlet of surge tank, through the biogas of reducing valve, then be transported to autoclave by one after the flow control tube road direction with mass flowmeter;
(3) solid methane generates: the equipment that solid methane generates is autoclave, be added with reaction solution in reactor, load responsive fluid accounts for the 1/4-2/5 of reactor useful volume, reaction solution is the distilled water that contains tensio-active agent, biogas flows out from surge tank, after reducing valve and flow control pipeline, pass in reactor; Stirred by the whipping appts that is provided with in reactor, mixing speed per minute 300-500 turns, churning time 30-50 minute; The kettle of reactor is jacketed type, and refrigeration agent is housed in chuck, by the heat exchange action of reactor inwall, the temperature in reactor is controlled to 4-20 ℃; Reacting kettle inner pressure is controlled to be 2-6MPa, and when the mass flowmeter in the flow control pipeline no longer showed gas flow, the solid methane reaction was completed; Close all gas circuit valves, slowly open the exhaust pressure relief valve and carry out pressure release, after reacting kettle inner pressure is reduced to 0MPa, open the baiting valve of reactor bottom, solid methane is entered in storage vessel.
2. production method according to claim 1 is characterized in that:
In described step (1) pre-treatment, when the pH of sodium hydroxide solution drops to lower than 11 the time, close pre-treatment canister incoming gas mouth, the sodium hydroxide solution that contains sodium carbonate and sodium sulphite from pre-treatment tank bottom discharge 1/4-3/4 volume, replenish again new sodium hydroxide solution, until the pH value in the pre-treatment tank reaches 12-13, then open pre-treatment canister incoming gas mouth, pass into again biogas to the pre-treatment tank;
Above-mentioned treating processes so repeatedly.
3. production method according to claim 1 is characterized in that:
In (2) supercharging of described step and flow control, by the compression of compressor, the pressure in surge tank is maintained between 6MPa-8MPa; During higher than 8MPa, compressor quits work when pressure, when pressure during lower than 6MPa, and compressor starts work.
4. according to claim 1 or 3 described production methods is characterized in that:
In (2) supercharging of described step and flow control, through the biogas of reducing valve decompression, control, pressure is adjusted to 5MPa.
5. production method according to claim 1 is characterized in that:
In (2) supercharging of described step and flow control, described flow control pipeline also comprises mass flowmeter intake valve, mass flowmeter air outlet valve and mass flowmeter by-pass valve except comprising mass flowmeter; In parallel with mass flowmeter by-pass valve pipeline after mass flowmeter intake valve, mass flowmeter and the series connection of mass flowmeter air outlet valve; The flow of biogas is measured by mass flowmeter; The open and close of flow, large and small, to be regulated by the mass flowmeter controller, instantaneous delivery and integrated flow show on its control panel.
6. production method according to claim 1 is characterized in that:
During described step (3) solid methane generated, it was 1/3rd that load responsive fluid accounts for the reactor useful volume.
7. production method according to claim 1 is characterized in that:
During described step (3) solid methane generated, tensio-active agent adopted sodium lauryl sulphate.
8. production method according to claim 7 is characterized in that:
In reaction solution, the volumetric molar concentration of Sodium Dodecyl Sulfate is 0.001mol/L.
9. production method according to claim 1 is characterized in that:
described step (3) solid methane after adding reaction solution, before passing into biogas, is first opened the exhaust pressure relief valve in generating, and with vacuum pump, the air in reactor is extracted out, then open the mass flowmeter by-pass valve, make the biogas that flows out from surge tank, through reducing valve and mass flowmeter by-pass valve, enter in reactor by the inlet pipe on kettle cover and the gas distributor in kettle, when the pressure of biogas in reactor reaches 5MPa, close the mass flowmeter by-pass valve, open mass flowmeter intake valve and mass flowmeter air outlet valve, biogas is passed through from mass flowmeter, then the agitator of opening in reactor stirs, mixing speed per minute 400 turns, churning time 40 minutes, temperature in reactor controls to 4 ℃, generate solid methane.
10. production method according to claim 1 is characterized in that:
During described step (3) solid methane generated, in reacting kettle jacketing, refrigeration agent was ethanol or ethylene glycol.
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| CN2010101913470A CN101870895B (en) | 2010-06-04 | 2010-06-04 | Production method of solid methane |
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| CN2010101913470A CN101870895B (en) | 2010-06-04 | 2010-06-04 | Production method of solid methane |
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| CN101870895B true CN101870895B (en) | 2013-05-22 |
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| CN1095496C (en) * | 1999-10-15 | 2002-12-04 | 余庆发 | Process for preparing liquefied natural gas |
| JP5117209B2 (en) * | 2007-01-30 | 2013-01-16 | 株式会社東芝 | Biogas biodesulfurization equipment |
| CN101659889B (en) * | 2008-08-25 | 2012-09-26 | 来铁路 | Methane purifying comprehensive utilization technology |
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