CN108584871A - The technique and system of carbon nanomaterial and hydrogen are recycled from the organic waste of city - Google Patents
The technique and system of carbon nanomaterial and hydrogen are recycled from the organic waste of city Download PDFInfo
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- CN108584871A CN108584871A CN201810440084.9A CN201810440084A CN108584871A CN 108584871 A CN108584871 A CN 108584871A CN 201810440084 A CN201810440084 A CN 201810440084A CN 108584871 A CN108584871 A CN 108584871A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Abstract
The invention discloses the technique for recycling carbon nanomaterial and hydrogen in a kind of organic waste from city, the technique of recycling carbon nanomaterial and hydrogen includes anaerobic fermentation and catalytic pyrolysis in the organic waste of the present invention from city.The invention also discloses the systems that carbon nanomaterial and hydrogen are recycled in a kind of organic waste from city.Carbon nanomaterial is recycled in the organic waste of the present invention from city and anaerobic fermentation technology and methane catalytic decomposition technology are effectively combined by the technique of hydrogen for the first time, the biological methane generated using city dirt waste anaerobic fermentation, since city dirt waste processing itself is non-gratuitous, the addition product (biological methane) handled using dirty waste can substantially reduce the cost of catalytic pyrolysis, and low price raw material is provided for methane catalytic decomposition.
Description
Technical field
The present invention relates to a kind of techniques and system preparing carbon nanomaterial and hydrogen, and in particular to a kind of organic from city
The technique and system of carbon nanomaterial and hydrogen are recycled in waste.
Background technology
Existing frequently-used methane process for making hydrogen is：Methane steam reforming, Hydrogen manufacture by partial oxidation.
The raw material of Methane Steam Reforming is natural gas.What methyl hydride catalyzed reformation hydrogen production gas was economically feasible, it is beautiful
State-owned 90% hydrogen of being more than is made from the steam reformation through methane.The approach of Methane Steam Reforming is：Steam methane weight
Whole, aqueous vapor displacement reaction and hydrogen purification.The reaction of methane steam reforming is：
CH4+H2O→3H2+CO
Optimum reaction condition is 700-850 DEG C of high temperature, pressure 0.3-2.5MPa.The reaction is the endothermic reaction, is needed
External input heat is wanted, institute's calorific requirement part is by unstripped gas (being less than 25%) or exhaust gas (purified gas in hydrogen purification system)
It provides.Synthesis gas after methane steam reforming is transported in one or more aqueous vapor metathesis reactors of next stage, by aqueous vapor
Displacement, the yield of hydrogen increase considerably：
CO+H2O→H2+CO2
The group of gas becomes hydrogen (70-80%), carbon dioxide, methane and a small amount of vapor and one in metathesis reactor
Carbonoxide.Finishing operation is hydrogen purification, and the purity of hydrogen is depending on purposes.
Hydrogen manufacture by partial oxidation is the method that another utilizes hydrocarbon hydrogen manufacturing, and methane or other hydrocarbons are former
Material (such as waste oil), which is partially oxidized, generates carbon monoxide and hydrogen.
2CH4+O2→4H2+CO
As previously mentioned, methane catalytic decomposition production hydrogen is advantageous in that：While obtaining regenerative resource, it can keep away
Exempt from CO2Generation, have prodigious benefit to natural environment.However, this technique is still in development phase at present, failing to be formed can
The methane catalytic decomposition hydrogen manufacturing production line of industrialization.
The research of methane catalytic decomposition focuses mostly in Ni-based, ferrum-based catalyst.As shown in table 1, with ferrum-based catalyst phase
Than nickel-base catalyst can generally generate a greater amount of hydrogen, while the catalytic temperature needed for it is also lower than ferrum-based catalyst.
The relationship of table 1 catalyst type and reaction condition, hydrogen yield
| Catalyst type | Reaction temperature (DEG C) | Hydrogen yield (mol/gcat.) |
| Fe/Al2O3 | 675 | 4.4 |
| Fe/SiO2 | 800 | 2.3 |
| Fe/Al2O3 | 700 | 0.6 |
| Ni | 500 | 66 |
| Ni/SiO2 | 500 | 32 |
| Ni-Fe-Al | 650 | 92 |
Although nickel-base catalyst cracks out more hydrogen than ferrum-based catalyst, the latter can greatly improve technique
Economic feasibility and environment friendly.The unit price of nickel is 10000 dollar per tonnes, therefore nickel-base catalyst can make entire methane
Catalytic pyrolysis enterprise of high cost, it is difficult to formed large-scale production.During methane catalytic decomposition hydrogen manufacturing, along with hydrogen
It generates, the carbon nanomaterial of high value can also be formed in the process, and be attached to catalyst surface.Therefore, it is produced in catalytic pyrolysis
Raw solid is typically carbon nanomaterial and the mixture of solid metal catalyst.As previously mentioned, nickel-base catalyst is at high price,
Therefore it usually requires carbon nanomaterial to be separated from nickel-base catalyst, realizes the recycling of nickel-base catalyst.It is this
Carbon nanomaterial isolation technics is related to burning process, on the one hand further increases the operation cost of system, on the other hand fires
Burn the CO generated2Also against reduction CO2The original intention of discharge.
Existing process for making hydrogen is all to be used as raw material by buying natural gas, therefore the expense for buying natural gas can be produced into
This most.The biological methane that anaerobic fermentation generates fails to enter the visual field of catalytic pyrolysis researcher, specific former
Because as follows：
(1), methane catalytic decomposition itself is a new technology, specializes in the chemical engineering personnel couple of catalytic pyrolysis research
The research of field of environment engineering anaerobic ferment process production methane is not well understood by, it is unclear that the available of biological methane；
(2), anaerobic ferment process needs are run under 35~40 degrees celsius, therefore have greater energy consumption demand in itself,
The biological methane combustion (of oil) insitu that general anaerobic fermentation generates is not used as catalysis and splits to meet the energy demand of anaerobic ferment process
Solution.
(3), the methane content that different anaerobic fermentation devices generate is widely different, after optimizing for methanogen growing environment
Anaerobic fermentation device can generate methane content up to 90% biogas, and not optimized fermentor, methane content only have
30%.Therefore, the application that realize anaerobic fermentation and catalytic pyrolysis combination process needs to cultivate stabilization in anaerobic fermentation device
Methanogen group, and the researcher for being engaged in catalytic pyrolysis may to the stock of knowledge of anaerobic fermentation, flora cultivation etc.
It is insufficient.
(4), the biogas that anaerobic fermentation generates includes not only methane, can also contain CO2Gas, if without carrying
It is pure to be sent directly into cat cracker, although not influencing the production of carbon nanomaterial, can not simultaneously output high-purity hydrogen, it is difficult to
Realize the purpose of hydrogen manufacturing.
Anaerobic fermentation refers to that waste is stabilized by the metabolic activity of microorganism under anaerobic, while with
Methane and CO2The variation of generation.Anaerobic fermentation includes three phases：Liquefaction, production acid, methane phase.Liquefaction stage mainly ferments
Bacterium is worked, including cellulose-decomposing bacterium and protein hydrolytic bacteria, and being mainly responsible for has the macromolecular in pending waste
Machine object is degraded into small-molecule substance.It is mainly that acetic acid bacteria works to produce acid phase, and the methane phase stage is mainly methane bacteria, they
The product degradation of acid phase generation will be produced into methane and CO2Utilize the hydrogen that production acid phase generates by CO simultaneously2It is reduced into methane.Detest
The influence factor of aerobe fermentation has：The carbon-nitrogen ratio of raw material proportioning, anaerobic fermentation is advisable with 20~30, the gas production when carbon-nitrogen ratio is 35
It is decreased obviously；Temperature is advisable at 35~40 DEG C；PH value for methane-producing bacteria, maintain mild alkaline conditions be it is indispensable,
Its optimum PH range is 6.8~7.5, and pH value is low, it makes CO2It increases, a large amount of water soluble organic substances and H2S is generated, and sulfide contains
The increase of amount inhibits the growth of methane backeria, lime can be added to adjust pH, but the best method for adjusting pH is adjustment raw material
Carbon-nitrogen ratio, because to antacid basicity being mainly ammonia nitrogen in substrate, substrate nitrogen content is higher, and basicity is bigger, when VFA (is waved
Hair property aliphatic acid)>When 3000, reaction can stop.
Although methane and hydrogen are all regenerative resource, the burning of methane will produce CO2, the greenhouse of the earth will be aggravated
Effect, and the moisture that the burning of hydrogen generates does not influence natural environment.Methane catalytic decomposition technology is by using metal
Catalyst promotes methane to be cracked into pure hydrogen and high value carbon nanomaterial under the high temperature conditions.In recent years, by methyl hydride catalyzed
Cracking technique hydrogen making is worldwide widely paid close attention to and is studied, but this technique is still in research and development rank at present
Section, fail to be formed can industrialization methane catalytic decomposition synchronize hydrogen manufacturing, carbon nanomaterial production line.
Invention content
It is provided a kind of from city organic waste it is an object of the invention to overcome the shortcomings of the prior art place
The technique and system of middle recycling carbon nanomaterial and hydrogen.
To achieve the above object, the technical solution that the present invention takes is：One kind recycling carbon from the organic waste of city and receives
The technique of rice material and hydrogen, includes the following steps：
(1), anaerobic fermentation：Municipal sludge, organic solid rubbish, sewage and organic liquid waste are subjected to anaerobic fermentation, obtained
Sludge after biological methane and fermentation；
(2), catalytic pyrolysis：Catalytic cracking reaction is carried out to the biological methane obtained by step (1), obtains hydrogen and carbon nanometer
Material.
The sewage and organic wastewater are preferably the high concentrated organic wastewater after concentration.
The present invention by the way of anaerobic fermentation to municipal sludge, organic solid rubbish, sewage and organic liquid waste at
Reason, under conditions of anaerobism, biology can be realized using floras such as hydrolytic bacteria, acetic acid bacteria, the methanogens cultivated in fermentation tank
The production of methane.Biological methane passes through catalytic pyrolysis, output pure hydrogen and carbon nanomaterial under certain conditions.Catalytic pyrolysis
The Hydrogen collection that system generates gets up the use of hydrogen supply energy enterprise, and carbon nanomaterial can be used as advanced water treatment material, also may be used
The carbon raw material made as lithium battery, ultracapacitor.
The present invention turns municipal sewage, sludge, organic solid waste rubbish anaerobic fermentation and methane catalytic decomposition combination process
It is melted into the bioenergy hydrogen and carbon nanomaterial of high-purity, the organic dirty waste in city is converted into cheap price high attached
Value added new energy, new material.The present invention substitutes natural gas using the biological methane of anaerobic fermentation system, is split as methyl hydride catalyzed
The raw material of solution reduces the cost of methane cracking.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, step (1) further include before step (1a)：The concentration of sewage and organic liquid waste：Using sewage and organic liquid waste as less salt
Solution carries out positive osmosis concentration processing with high level salt solution.
The sewage of the present invention and the condensing mode of organic wastewater preferably use positive osmosis concentration processing mode.Forward osmosis membrane
(FO) be using film one end low salt concn sewage in principle from hydrone to the high salt concentration solution natural diffuseness of the film other end,
Carry out the concentration of sewage of low concentration.Forward osmosis membrane unit separates high salinity solution and Low-salinity municipal sewage using forward osmosis membrane.
Since forward osmosis membrane is dense film, only hydrone is allowed to pass through, and molecules of salt cannot walk, therefore the moisture in Low-salinity sewage
Son can diffuse in high salinity solution, and dilute high salinity solution, and after high level salt solution is diluted to a certain degree, film both sides are molten
The salt error of liquid reaches balance, and then water diffusion stops.In the present invention, high level salt solution is used as using inorganic fertilizer, to less salt city
City's sewage carries out concentration.After the processing of forward osmosis membrane system, the relatively low municipal sewage of organic pollution content, organic waste
Liquid is concentrated, and is reduced the sewage volume into anaerobic fermentation system and is promoted organic concentration, improves anaerobic fermentation system
Biological methane production capacity.Municipal sludge, organic solid rubbish can then be directly entered anaerobic fermentation system and carry out biological methane production.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, in step (1a), the high level salt solution is inorganic fertilizer, and the concentration of the inorganic fertilizer is more than or equal to 1 mol/L.
Since sewage of low concentration hydrone enters in high level salt solution in positive process of osmosis, the change of forward osmosis membrane system high concentration
Fertile solution is then diluted, and greenhouse soilless culture irrigation is can be used for.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, in step (1a), volume when the volume of sewage of low concentration is into forward osmosis membrane unit 25% when, stopping just being oozed
The operating of permeable membrane unit, high-concentration sewage are delivered to anaerobic fermentation system progress biological methane and produce.
After above-mentioned positive infiltration repeats three times, high level salt solution (inorganic fertilizer), can be with due to being diluted accordingly
As crop irrigation.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, step (1) also include later and before step (2) step (2a)：Biological methane purifies：The biology that step (1) is generated
Methane is purified.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, in step (2a), the method for the methane purification is：The methane gas that step (2) is generated by sodium hydroxide solution,
Up to the methane after purification.Methane after purification is conducive to the quality of the efficiency and carbon material of subsequent catalyst cracking.Sodium hydroxide
The carbon dioxide of solution being mainly used in organism-absorbing methane.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, a concentration of 0.5~2mol/L of the sodium hydroxide solution.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, the sludge after the fermentation are used for soil improvement.
After anaerobic fermentation while city debirs are converted into biological methane, also have a small amount of excess sludge
It generates.These excess sludges are stabilized after Anaerobic Treatment, without harmful substances such as pathogens, but containing comparable
The elements such as nitrogen phosphorus, therefore these excess sludges can be used as soil improvement after the contracting dehydration of plate filtering pressure, realize the recycling profit of waste
With.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, in step (2), the catalyst of the catalytic pyrolysis is ferrum-based catalyst, and the grain size of the ferrum-based catalyst is less than or equal to
50 microns.
Ferrum-based catalyst of the present invention be porous material loading iron oxide, wherein porous material can be aluminium oxide,
The inorganic porous materials such as silica, molecular sieve and activated carbon.The present invention substitutes day using the biological methane of anaerobic fermentation system
Right gas, the raw material as methane catalytic decomposition；Meanwhile (ferrum-based catalyst price is about using cheap ferrum-based catalyst by the present invention
It is 80 beautiful yuan/ton, nickel-base catalyst price is up to 10000 beautiful yuan/ton), reduce the cost of methane catalytic decomposition with working along both lines.
Since ferrum-based catalyst is cheap, the mixture of carbon nanomaterial and catalyst after cracking reaction can integrally take out, and be not necessarily to
Separating treatment is done, directly recycling uses.The nickel-base catalyst used in research makes methane catalytic decomposition not yet due to expensive
The industrialization stage can be entered, the ferrum-based catalyst that the present invention uses is cheap, is not required to consider catalyst recycling problem, makes methane
Catalytic pyrolysis cost substantially reduces.The grain size of ferrum-based catalyst is conducive to catalyst less than or equal to 50 microns and is contacted with methane, urges
Change efficient, carbon nanotube can be prepared, and the ferrum-based catalyst of greater particle size is difficult to prepare carbon nanotube.As the present invention
The preferred embodiment of the technique of carbon nanomaterial and hydrogen is recycled in the organic waste from city, the iron oxide is in institute
It is 10~80% to state the weight percentage in ferrum-based catalyst.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, in step (2), the condition of the catalytic cracking reaction is：1~10 atmospheric pressure, temperature are 500~1000 DEG C, the time 8
~12h.
More preferable reality as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode is applied, the temperature of the catalytic cracking reaction is 700~800 DEG C.At such a temperature, in conjunction with 1~10 atmospheric pressure, carry out 8~
12 hours catalytic cracking reactions can selectivity prepare multi-walled carbon nanotube, the inner wall caliber of the multi-walled carbon nanotube
Ranging from 20~100nm.
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
The temperature of mode, the catalytic cracking reaction is 750 DEG C.
As the preferred embodiment for the technique for recycling carbon nanomaterial and hydrogen in the organic waste from city, step
Suddenly in (2), the flow velocity of the biological methane is 1.8~1.9L/h/gCat.L/h/gCat is l/h/gram ferrum-based catalyst
(the gas compartment speed per hour that namely for methane passes through catalyst layer：GHSV).
Preferred implementation as the technique for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, the waste heat in step (2) during catalytic cracking reaction make the anaerobic fermentation conditions in step (1) maintain 35 by water
~40 DEG C.
Common anaerobic fermentation system, takes combustion (of oil) insitu methane to heat fermentation reactor, and consuming has huge potential value
Methane, and cause a large amount of CO2Discharge, and the present invention is by way of water-bath Heat transmission, in cat-cracker in advance
The additional heat that hot device and reacting furnace generate is transferred to the continuous-stirring reactor of anaerobic fermentation, and catalytic pyrolysis is made full use of to produce
Raw waste heat reduces the energy demand of anaerobic fermentation.
Another object of the present invention is to provide carbon nanomaterial and hydrogen are recycled in a kind of organic waste from city
System, in the organic waste of the present invention from city the system of recycling carbon nanomaterial and hydrogen include anaerobic fermentation system and
Cat-cracker；The gas outlet of the anaerobic fermentation system is connected with the air inlet of the cat-cracker.As this hair
The preferred embodiment of the bright system that carbon nanomaterial and hydrogen are recycled from the organic waste of city, the system are also wrapped
Include positive permeation unit；The liquid outlet of the positive permeation unit is connected with anaerobic fermentation system.
Preferred implementation as the system for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, the system also includes biological methane purifying plants；The gas vent of the anaerobic fermentation system is purified with biological methane
The air inlet of device is connected, and the gas outlet of the biological methane purifying plant is connected with the air inlet of the cat-cracker.
Preferred implementation as the system for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode is equipped with methane air accumulator and pressure between the gas outlet and the air inlet of the cat-cracker of the methane purifying plant
Force lifting apparatus.
304 stainless steel of material of the methane air accumulator, sealing are using DN219 metal chuck sealeds, operating pressure
0.2Mpa.The methane air accumulator is equipped with pressure gauge, relief valve, blow valve and air compressor machine, can realize the liter to methane gas
Press operation.
Preferred implementation as the system for recycling carbon nanomaterial and hydrogen in the organic waste of the present invention from city
Mode, the cat-cracker include preheater, reactor, Hydrogen collection device and reacting furnace；The cat-cracker
Air inlet be connected with preheater, the preheater is connected with reactor, and the reacting furnace is used to maintain temperature in reactor,
The reactor is connected with Hydrogen collection device, and catalyst is equipped in the reactor.
The beneficial effects of the present invention are：The present invention provides one kind recycling carbon nanomaterial from the organic waste of city
With the technique of hydrogen, anaerobic fermentation technology and methane catalytic decomposition technology are effectively combined by the present invention for the first time, using city
The biological methane that dirt waste anaerobic fermentation in city's generates, since city dirt waste processing itself is non-gratuitous, at dirty waste
The addition product (biological methane) of reason can substantially reduce the cost of catalytic pyrolysis, and low price raw material is provided for methane catalytic decomposition.
The present invention also provides the systems that carbon nanomaterial and hydrogen are recycled in a kind of organic waste from city.
Description of the drawings
Fig. 1 is the technological process signal for recycling carbon nanomaterial and hydrogen described in embodiment 1 from the organic waste of city
Figure；
Fig. 2 a are in 0.8 l/h/gram ferrum-based catalyst of gas compartment speed per hour (GHSV), 100 ml/min methane gas
Under body supply, 5 atmospheric pressure, influence of the temperature to methane conversion efficiency；
Fig. 2 b are under 5 atmospheric pressure, and 100 ml/min methane gas are supplied, at 750 DEG C, gas compartment speed per hour (GHSV)
In influence of the initial period (first 30 minutes) that methane converts to methane conversion efficiency.
Fig. 3 is the carbon for the technique generation for recycling carbon nanomaterial and hydrogen described in embodiment 1 from the organic waste of city
The TEM of nano material schemes, wherein：The enlargement ratio of Fig. 3 a is 30,000 times；The enlargement ratio of Fig. 3 b is 800,000 times；The amplification of Fig. 3 c
Multiplying power is 30,000 times；The enlargement ratio of Fig. 3 d is 30,000 times；The enlargement ratio of Fig. 3 e is 30,000 times.
Fig. 4 is the carbon for the technique generation for recycling carbon nanomaterial and hydrogen described in embodiment 1 from the organic waste of city
The effect of nano material, high-quality Powdered Activated Carbon and treatment sewage in terms of (a) total organic carbon, the humic acid removal of (b) coloring
Fruit compares；
Fig. 5 is the carbon for the technique preparation for recycling carbon nanomaterial and hydrogen described in embodiment 1 from the organic waste of city
Nano material (CNOs) is with high-quality Powdered Activated Carbon (PACs) to caffeine, atenolol (drug residue), Primidone, atrazine
The comparison of (herbicide) removal rate；
Fig. 6 is the principle schematic of forward osmosis membrane unit described in embodiment 2；
Fig. 7 is the structural schematic diagram that anaerobic fermentation system, biological methane carry device and methane air accumulator described in embodiment 2；
Fig. 8 is methane air accumulator pressure charging system schematic diagram；
Fig. 9 is the structural schematic diagram of cat-cracker described in embodiment 2；
Figure 10 is heat reclamation device；
Wherein, 1, anaerobic fermentation system；2, biological methane purifying plant；3, methane air accumulator；4, excess methyl hydride combustion system
System；5, cat-cracker；501, preheater；502, reactor；503, reacting furnace；504, ferrum-based catalyst.
Specific implementation mode
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the technique of carbon nanomaterial and hydrogen is recycled in the organic waste of the present invention from city, this
Carbon nanomaterial is recycled from the organic waste of city and the technique of hydrogen includes the following steps described in embodiment：
(1), the concentration of sewage and organic liquid waste：Using sewage and organic liquid waste as low salt solutions, chemical fertilizer is as with high salt molten
Liquid carries out positive osmosis concentration processing, obtains high concentrated organic waste liquid；
(2), anaerobic fermentation：The high concentrated organic waste liquid that sludge, organic solid rubbish and step (1) are obtained carries out anaerobism
Fermentation obtains the sludge after biological methane and fermentation；
(3), biological methane purifies：The biological methane generated to step (2) purifies, the biological methane after must purifying；
(4), catalytic pyrolysis：Biological methane after purification in step (3) is carried out under the catalytic action of ferrum-based catalyst
Catalytic cracking reaction obtains hydrogen and carbon nanomaterial.
In step (1), the fertilizer solution after being diluted is used for agricultural fertilizer.In step (2), the sludge after fermentation is by detesting
Stabilized after oxygen processing, without harmful substances such as pathogens, but containing elements such as comparable nitrogen phosphorus, these sludge pass through
It is used as soil improvement after the contracting dehydration of plate filtering pressure.In step (3), the method for biological methane purification is：The biology that step (2) is generated
Methane gas is by the sodium hydroxide solution of 0.5-2mol/L to get the biological methane after purification.In step (4), carbon nanometer material
Material is for the efficient advanced treating of drinking water, membrane filtration prevention and cure of pollution (as shown in Figure 4,5).In step (4), catalytic cracking reaction mistake
Waste heat in journey makes the anaerobic fermentation conditions in step (2) maintain 35~40 DEG C by water-borne progress heat exchange.
In step (1), due to not external pressure demand, in terms of 1 square metre of forward osmosis membrane area, the place of sewage per ton
It is about 0.8 yuan/ton to manage energy consumption；In step (2), every square metre of forward osmosis membrane of the technique can handle 0.72 ton of sewage/day, with 6 days
Residence time counts, and 1 cube of anaerobic fermentation tank can handle 0.17 ton of sludge/day, and (or 0.034 ton of organic waste/day+0.136 is vertical
Side's concentration sewage), the methane production of anaerobic fermentation device reaches 11.56 cubes/day.In step (4), the technique is in 100 ml/mins
The supply of clock methane gas, 5 atmospheric pressure, often crack under conditions of 850 DEG C 1 cube of biological methane gas can output hydrogen 1.6 it is vertical
Side, 0.5 kilogram of carbon nanomaterial.
Fig. 2 a are in 0.8 l/h/gram ferrum-based catalyst of gas compartment speed per hour (GHSV), 100 ml/min methane gas
Under body supply, 5 atmospheric pressure, influence of the temperature to methane conversion efficiency.The determination of preferable temperature must methane gas with urge
Change is evaluated under conditions of coming into full contact with, and is otherwise reacted due to not left in advance with the catalytic methane of catalyst fully largely
Stove can cause influence of the different temperatures to methane conversion that can not embody, temperature is caused to be underestimated on what methane conversion influenced.It adopts
It is according to previous experiment experience with 0.8 l/h/gram ferrum-based catalyst, is that can ensure to realize that methane fully connects with catalyst
Tactile gas compartment speed per hour (GHSV), therefore used in the exploration of the preferable reaction temperature of the present embodiment.Further, since cracking
The production that single batch methane is converted into carbon nanomaterial and hydrogen can be improved to the compression of reaction gas in air pressure in journey
Amount, so the air pressure list in cracking process considers that with 10 atmospheric pressure be preferred (1-10 air of reaction requirement from yield angle
Pressure), however excessively high pressure demand can increase the energy consumption of reaction, therefore consider reaction yield and energy consumption, 5 air
The operating pressure of pressure is pressure selection when probing into preferable temperature.It can be seen that the raising with temperature, methane exist from Fig. 2 a
Theoretical conversion efficiency under reaction equilibrium state also increases；In addition, when temperature reaches 750 DEG C or more, methane can be with
Reach the conversion under reaction desirable balance state under the action of ferrum-based catalyst.Therefore it is 0.8 l/h/gram iron in GHSV
Under base catalyst, the supply of 100 ml/min methane gas, 5 atmospheric pressure, ideal response temperature is 750 DEG C.
Fig. 2 b are 5 atmospheric pressure, 100 ml/min methane gas are supplied, at 750 DEG C, and gas compartment speed per hour (GHSV) exists
Influence of the initial period (first 30 minutes) of methane conversion to methane conversion efficiency.As can be seen that working as the gas compartment from Fig. 2 b
Speed per hour is more than 2 l/h/gram ferrum-based catalysts, and the transformation efficiency of methane will decline.Therefore methane conversion effect is considered at the same time
In the case of rate and conversion rate, 1.8~1.9 l/h/gram ferrum-based catalysts are preferred GHSV.
All carbon materials are that (5 atmospheric pressure, the confession of 100 ml/min methane gas are made under same preparation condition in Fig. 3
Answer, 850 DEG C, 9 hours reaction time), wherein Fig. 3 a and the different amplification figure that Fig. 3 b are same batch carbon material, Fig. 3 c,
3d, 3e are respectively carbon material made from other different batches.The carbon material for reacting generation as can be seen from Figure 3 is Nano grade,
Size is between 20~100nm, and part is in a tubular form.
The carbon for recycling the technique generation of carbon nanomaterial and hydrogen described in Fig. 4 embodiments 1 from the organic waste of city is received
The effect of rice material, high-quality Powdered Activated Carbon and treatment sewage in terms of (a) total organic carbon, the humic acid removal of (b) coloring
Comparison.The carbon nanomaterial that technique described in embodiment 1 generates is can be seen that from Fig. 4 a to remove than high-quality Powdered Activated Carbon more
25% total organic carbon；It is seen from fig. 4b that the carbon nanomaterial that technique described in embodiment 1 generates is in removal coloring humic
Sour aspect (being discharged close to transparent after processing), than high-quality Powdered Activated Carbon, more preferably (coloration being discharged after processing is changed than raw water
It is kind, but still be in brown color).
Fig. 5 is the carbon for the technique preparation for recycling carbon nanomaterial and hydrogen described in the present embodiment from the organic waste of city
Nano material (CNOs) is with high-quality Powdered Activated Carbon (PACs) in caffeine, atenolol (drug residue), Primidone, atrazine
The comparison of the removal rate effect of micropollutants such as (herbicides).Carbon nanometer made from the present embodiment is can be seen that from the result of Fig. 5
Material is not much different compared with the micropollutants removal rate of high-quality Powdered Activated Carbon, even more excellent.
From Fig. 3~5 as can be seen that recycling carbon nanomaterial and hydrogen described in the present embodiment from the organic waste of city
The carbon nanomaterial obtained in technique is the carbon nanomaterial of high quality.
From the point of view of the technique for recycling carbon nanomaterial and hydrogen in the entire city organic waste in embodiment 1, the work
Forward osmosis membrane sewage concentration technique, anaerobic fermentation are generated methane by skill flow, ferrum-based catalyst catalytic cracking methane obtains carbon materials
Material and hydrogen, have also recycled the carbon nanomaterial and hydrogen of high quality while realizing the low-cost processes of city organic waste
Gas provides new direction for the organic waste treatment in future city.
Embodiment 2
A kind of embodiment of the system of carbon nanomaterial and hydrogen, institute are recycled in the organic waste of the present invention from city
State the system that carbon nanomaterial and hydrogen are recycled from the organic waste of city include forward osmosis membrane unit, anaerobic fermentation system,
Biological methane purifying plant and cat-cracker；The liquid outlet of the forward osmosis membrane unit is connected with anaerobic fermentation system,
The gas vent of the anaerobic fermentation system is connected with the air inlet of biological methane purifying plant, the biological methane purifying plant
Gas outlet be connected with the air inlet of the cat-cracker.
The structural schematic diagram of forward osmosis membrane unit described in the present embodiment is as shown in fig. 6, forward osmosis membrane unit is permeated using positive
Film separates the sewage of low concentration of fertilizer solution with high salt and less salt.The driving force of forward osmosis membrane is the salinity of film both sides solution
Difference, there are salinity difference, solution meeting free diffusing in both sides reaches mutual concentration balance.Forward osmosis membrane is to cause
Close film only allows hydrone to pass through, and molecules of salt cannot walk, therefore using forward osmosis membrane processing, in Low-salinity sewage
Hydrone can diffuse in high level salt solution, and dilute high level salt solution, after high level salt solution is diluted to a certain degree, film both sides
The salt error of solution reaches balance, and then water diffusion stops.Forward osmosis membrane unit takes batch-type processing mode：Fixed volume
The sewage of low concentration of less salt and fertilizer solution with high salt work as less salt respectively on forward osmosis membrane both sides with the speed loop of 8.5cm/S
After hydrone enters high level salt solution by forward osmosis membrane in sewage, stop when sewage of low concentration volume drops to the 25% of original volume
Only forward osmosis membrane unit operates, and the high-concentration sewage after concentration goes to anaerobic fermentation system and carries out anaerobic fermentation；Then it is just oozing
The sewage of low concentration of the less salt of identical initial volume is injected in permeable membrane unit, restarts new round concentration.In concentration 3
After the less salt sewage of batch, high level salt solution goes to soilless culture greenhouse due to being diluted, and carries out crop irrigation.
As shown in fig. 7, sludge, organic solid rubbish and high-concentration sewage are sent into anaerobic fermentation system 1, the present embodiment institute
It is continuous-stirring reactor (CSTR) to state anaerobic fermentation system 1, and it is online that device is equipped with dissolved oxygen, acid-base value, oxidation-reduction degree etc.
Monitoring device, the Whole Process Control of realization device maintain best anaerobic fermentation environment under conditions of Automatic Control.Even
The biogas that continuous stirred reactor generates is collected from the top of reactor, and is transferred to the hydroxide equipped with a concentration of 1mol/L
Sodium solution biological methane purifying plant 2 removes the carbon dioxide generated in anaerobic fermentation process, to purify biological methane.Through
The biological methane crossed after sodium hydroxide solution purification can be stored in methane air accumulator 3.When the storage first in methane air accumulator 3
When alkane is excessive, extra methane can open-top tank body top air pressure valve, into excess methyl hydride combustion system 4, it is ensured that will not occur
The case where methane gas excess stores.
As shown in figure 8, the biological methane stored in methane air accumulator is sent into cat-cracker after pulsometer pressurizes
Middle carry out catalytic pyrolysis, as shown in figure 9, cat-cracker 5 described in the present embodiment includes preheater 501, reactor 502, hydrogen
Gas collection device (not shown) and reacting furnace 503；The air inlet of the cat-cracker is connected with preheater 501, institute
It states preheater 501 with reactor 502 to be connected, the reacting furnace 503 is used to maintain the temperature in reactor 502, the reactor
502 be connected in Hydrogen collection device, is equipped with ferrum-based catalyst 504 in the reactor 502.Biological methane catalytic pyrolysis process
In, the biological methane after purification enters the reactor 502 for being filled with ferrum-based catalyst 504 with constant flow rate by preheater 501,
In 1~10 atmospheric pressure, under the conditions of temperature is 500~1000 DEG C, it is cracked into 8~12 hours.The hydrogen generated in reaction is reacting
It collects and is delivered in storage device in the Hydrogen collection device 503 at the top of device 502, the hydrogen being collected into can be sampled progress
Gas chromatographic detection；And it cracks carbon nanomaterial out and is then taken out from the bottom of reactor 502.
Hydrogen content by detecting 502 output gas of reactor understands the progress of catalytic cracking reaction, if hydrogen components
Decline, show that ferrum-based catalyst gradually loses activity in reactor, then the replacement for carrying out catalyst is needed, at this point, by reactor
In ferrum-based catalyst and carbon nanomaterial mixture take out, can be used as carbon nanomaterial for the efficient advanced treating of drinking water,
Membrane filtration prevention and cure of pollution etc..
The present embodiment carries out heat transmission by heat reclamation device as shown in Figure 10, specially：In cat-cracker
The additional heat that preheater 502 and reacting furnace 503 generate is transferred in fermentation tank, makes full use of catalytic pyrolysis to generate remaining
Heat reduces the energy demand of anaerobic fermentation.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. recycling the technique of carbon nanomaterial and hydrogen in a kind of organic waste from city, which is characterized in that including following step
Suddenly：
(1), anaerobic fermentation：Municipal sludge, organic solid rubbish, sewage and organic liquid waste are subjected to anaerobic fermentation, obtain biology
Sludge after methane and fermentation；
(2), catalytic pyrolysis：Catalytic cracking reaction is carried out to the biological methane obtained by step (1), obtains hydrogen and carbon nanometer material
Material.
2. the technique of carbon nanomaterial and hydrogen is recycled from the organic waste of city as described in claim 1, which is characterized in that
Further include step (1a) before step (1)：The concentration of sewage and organic liquid waste：Using sewage and organic liquid waste as low salt solutions,
Positive osmosis concentration processing is carried out with high level salt solution.
3. the technique of carbon nanomaterial and hydrogen is recycled from the organic waste of city as described in claim 1, which is characterized in that
Also include step (2a) after step (1) and before step (2)：Biological methane purifies：To step (1) generate biological methane into
Row purification.
4. the technique of carbon nanomaterial and hydrogen is recycled from the organic waste of city as claimed in claim 2, which is characterized in that
In the step (1a), the high level salt solution is inorganic fertilizer, and the concentration of the inorganic fertilizer is more than or equal to 1 mol/L.
5. the technique of carbon nanomaterial and hydrogen is recycled from the organic waste of city as described in claim 1, which is characterized in that
In step (2), the catalyst of the catalytic pyrolysis is ferrum-based catalyst, and the grain size of the ferrum-based catalyst is micro- less than or equal to 50
Rice.
6. the technique of carbon nanomaterial and hydrogen is recycled from the organic waste of city as described in claim 1, which is characterized in that
In step (2), the condition of the catalytic cracking reaction is：1~10 atmospheric pressure, temperature be 500~1000 DEG C, the time be 8~
12h；Preferably, the temperature of the catalytic cracking reaction is 700~800 DEG C；It is highly preferred that the temperature of the catalytic cracking reaction
It is 750 DEG C.
7. the system for recycling carbon nanomaterial and hydrogen in a kind of organic waste from city, which is characterized in that sent out including anaerobism
Ferment system and cat-cracker；The gas outlet of the anaerobic fermentation system is connected with the air inlet of the cat-cracker.
8. the system for recycling carbon nanomaterial and hydrogen from the organic waste of city as claimed in claim 7, which is characterized in that
The system also includes positive permeation units；The liquid outlet of the positive permeation unit is connected with anaerobic fermentation system.
9. the system for recycling carbon nanomaterial and hydrogen from the organic waste of city as claimed in claim 7, which is characterized in that
The system also includes biological methane purifying plants；The gas vent of the anaerobic fermentation system and biological methane purifying plant
Air inlet is connected, and the gas outlet of the biological methane purifying plant is connected with the air inlet of the cat-cracker.
10. the system for recycling carbon nanomaterial and hydrogen from the organic waste of city as claimed in claim 7, feature exist
In the cat-cracker includes preheater, reactor, Hydrogen collection device and reacting furnace；The cat-cracker
Air inlet is connected with preheater, and the preheater is connected with reactor, and the reacting furnace is used to maintain the temperature in reactor, institute
It states reactor with Hydrogen collection device to be connected, catalyst is equipped in the reactor.
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| CN111689466A (en) * | 2020-05-27 | 2020-09-22 | 深圳市中科纳米科技有限公司 | Comprehensive treatment method and treatment system for organic waste |
| CN111689467A (en) * | 2020-06-16 | 2020-09-22 | 中国矿业大学 | Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst |
| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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| CN103569993A (en) * | 2012-07-20 | 2014-02-12 | 上海永鸿实业集团化学科技有限公司 | Catalyst and method for producing nanometer carbon and hydrogen |
| CN106277667A (en) * | 2016-08-29 | 2017-01-04 | 西南化工研究设计院有限公司 | A kind of reclaiming city domestic sludge utilizes technique |
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| CN1600685A (en) * | 1998-03-13 | 2005-03-30 | 财团法人地球环境产业技术研究机构 | Carbon producing apparatus utilizing biomass |
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| CN111689466A (en) * | 2020-05-27 | 2020-09-22 | 深圳市中科纳米科技有限公司 | Comprehensive treatment method and treatment system for organic waste |
| CN111689467A (en) * | 2020-06-16 | 2020-09-22 | 中国矿业大学 | Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst |
| CN111689467B (en) * | 2020-06-16 | 2022-02-15 | 中国矿业大学 | Method for preparing hydrogen by catalyzing methane cracking with activated carbon as catalyst |
| CN112877084A (en) * | 2021-01-20 | 2021-06-01 | 西北大学 | Method for preparing oil-electricity-gas-heat from self-circulation oil-electricity balance domestic garbage |
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