CN106520170B - A method of it converts garbage into carbonize functional material - Google Patents
A method of it converts garbage into carbonize functional material Download PDFInfo
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- CN106520170B CN106520170B CN201610925698.7A CN201610925698A CN106520170B CN 106520170 B CN106520170 B CN 106520170B CN 201610925698 A CN201610925698 A CN 201610925698A CN 106520170 B CN106520170 B CN 106520170B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
- B09B3/45—Steam treatment, e.g. supercritical water gasification or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of method converted garbage into carbonize functional material, this method includes：Rubbish is pre-processed, rubbish is then packed into rubbish feeding device, wherein the pretreatment includes dregs, glass, stone, ceramics and the metal removed in rubbish, functionalization material is then added；Rubbish feeding device is set to pass through high temperature distillation carbonizing apparatus；Gas stream is taken out from high temperature distillation carbonizing apparatus top；The gas stream is set to pass through catalyst bed in a gaseous form；The effluent of self-catalysis agent in future bed is condensed and is detached, and liquid combustible object and water are obtained；Charing functional material is obtained from the rubbish feeding device across high temperature distillation carbonizing apparatus.Changing charing functional material realizes the good compound of charcoal and zeolite, can be efficiently used for being catalyzed everywhere, adsorption reaction.
Description
Technical field
The invention belongs to garbage as resource to utilize technical field, and in particular to one kind converts garbage into carbonize functional material
Method, relate more specifically to it is a kind of by municipal refuse carbonize prepare charing functional material method.
Background technology
Domestic waste typically refers to municipal solid wastes, is city dweller in daily life or is the daily life in city
Generated solid waste in the living activity that service is provided, main component include kitchen waste material, waste paper, waste plastics, useless fabric,
Old metal, cullet potsherd, brick and tile dregs, excrement, the assorted tool of useless household, waste electrical equipment and yard waste etc..With economy
Fast development, urbanization process are persistently accelerated so that the quantity in city and the scale in city are also constantly occurring variation, occur swollen
It is swollen, due in city resident population and urban size increased dramatically, domestic waste total amount increases considerably therewith.
Currently, the annual output of China's domestic waste is up to 1.8 hundred million tons, rubbish annual output is about 440 public affairs per capita in city
Jin, and rapidly increased with the speed more than 10% every year, it is predicted that the year two thousand thirty, Municipal Solid Waste in China annual output are up to
4.09 hundred million tons.The refuse production per capita of big and medium-sized cities, especially megalopolis is relatively high, and it is left that rate of rise reaches 20%
It is right.
If processing and disposition that cannot be appropriate to these rubbish, (heavy metal, cause of disease be micro- for that poisonous and harmful substance therein
Biology etc.) it will be entered in the ecosystem by certain surrounding medium such as soil, air, earth's surface or underground water and form dirt
Dye.This can not only destroy ecological environment, lead to irreversible Ecological Changes, but also can be good for animals and plants safety and the mankind
Health causes damages.
Garbage disposal at present can only reduce waste volumes by burning disposal.Burning disposal method will produce bioxin etc.
Various environmentally hazardous polluters, safe garbage incineration equipment price is high, scale of investment is big, and burning disposal can only lead to
It crosses handling to be used for maintaining to run, resin, Plastic account for 10% or so in conventional rubbish, and remaining is exactly kitchen, paper, wood chip
Deng.
CN104263388A disclose a kind of rubbish carbonization reaction system include reaction kettle, reaction chamber, steam generator and
Control device, wherein steam generator connects reaction kettle, and the steam generator is used to provide steam to the reaction kettle；Institute
Reaction chamber is stated for placing rubbish, when reacted, the reaction chamber is pushed into the reaction kettle reaction and generates carbonized mixture；When
After the completion of reaction, the reaction chamber is pulled out from the reaction kettle.
CN102304372A discloses a kind of superheated steam retort of processing organic waste, it includes superheated steam
The components composition such as stove, organic waste retort, steam turbine generator and gas-liquid separator, gas-liquid separator.
CN102606236A discloses a kind of garbage disposal waste heat power generation system with internal steam pipe, includes refuse gasification
Stove and steamer steam electric power generator, wherein steamer steam electric power generator include steam generator, vapour-discharge tube, steamdrum,
Steam turbine and generator, steamdrum, steam turbine and generator are sequentially connected, it is characterised in that：The steam generator is located at rubbish
In rubbish gasification furnace；Steam generator is the cylinder cage structure being made of upper ring pipe, multiple straight tubes and lower ring pipe, Mei Gezhi
The both ends of pipe are connected with upper ring pipe with lower ring pipe respectively；The upper ring pipe is connected to one end of vapour-discharge tube, is steamed
The other end of vapour discharge pipe is connected with steamdrum, and water inlet pipe is communicated on the lower ring pipe.
CN104976621A discloses a kind of domestic garbage pyrolysis gasification oven, furnace body ecto-entad include burn stove outer covering,
Fire brick layer burns furnace internal-lining；Bottom of furnace body is equipped with deslagging component, water-stop component；It is characterized in that, upper of furnace body is equipped with sky
Gas air inlet, combustible gas outlet；Bottom of furnace body is equipped with vapor import；Steam outlet is equipped at the top of furnace body；In fire brick layer
It is equipped with a hollow sandwich between burning furnace internal-lining；The interlayer bottom is connected to bottom in furnace body, the interlayer top and combustible gas
Outlet；Air inlet channel, the air inlet upper part of channel and the air inlet set by upper of furnace body are equipped in the interlayer
Mouth connection, the lower part in air inlet channel is connected to bottom in furnace body.
CN204325273U discloses a kind of using water vapour as the rubbish plasma gasification stove of gasifying medium including upper
Room occurs for the refuse gasification room in portion and the high-temperature water vapor of lower part, and refuse gasification room and high-temperature water vapor occur to be provided between room
Refuse gasification room room with high-temperature water vapor and separates by spaced water cooling chimney arch, water cooling chimney arch occur；The high-temperature water vapor
Inner wall circumferentially two plasma torch of room, the working gas using low temperature water vapour as plasma torch occurs.
CN102746903A discloses that a kind of to be divided into multiple standard destructive distillation to handle house refuse destructive distillation-gasification furnace single
Member is combined into large-scale house refuse destructive distillation-gasification furnace according to the needs of different disposal ability, and standard destructive distillation processing unit is
The retort section and dryer section of rubbish is arranged in cube furnace body, top, is under anaerobic state first rubbish destructive distillation, is divided using rubbish
Dry distillation gas and carbide residue are solved, carbide burns in lower section burning zone generates high temperature, gasifies with water vapour and air work
Agent, the CO that the carbide under the reduction zone condition of high temperature generates burning2And aqueous vapour reducing, gasification gas is generated, is not just generated
Bioxin；The gasification gas of high temperature, the heating of the rubbish of rubbish retort section, destructive distillation, continues to rise dry during rising
The rubbish of section adds drying, and the organic matter in rubbish is changed into clean gas, collects dry distillation gas and gasification gas is utilized,
It realizes Wu bioxin, non-exhaust emission.
WO2011/000513A1 discloses a kind of comprehensive waste treatment system and method comprising combustiblerefuse source makes
With the separator for detaching the combustiblerefuse from recyclable material, for drying the combustiblerefuse to produce
The vacuum desiccator of raw pyrolysis feed and for by the pyrolysis feed pyrolytic to generate the heat of coke and pyrolysis gas
Solve device.
GB2006/002409A discloses a kind of method for handling rubbish, the method includes：(i) (a) gasification step
Suddenly, the gasification step is included in the presence of oxygen and steam handles the rubbish in gasification unit, to generate exhaust gas and charcoal, or
Person (b) pyrolysis step, the pyrolysis step, which is included in pyrolysis unit, handles the rubbish, to generate exhaust gas and charcoal；(ii)
Plasma treatment step, the plasma treatment step include in the presence of oxygen and optionally in the presence of steam wait from
Corona treatment is carried out to the exhaust gas and charcoal in daughter processing unit.
In the recycling treatment mode of domestic waste " simple analysis ", Zhang Bei, Chinese municipal works, in June, 2013, the 3rd
Phase (total 166th phase) in 53-55, describes the processing of domestic waste from traditional landfill, burning and biochemical treatment side
Formula is gradually transition to circular economy and recycling treatment, and describes the closed low-temperature carbonization processing of house refuse and organic matter
The project construction of fixed-end forces factory, it is indicated that house refuse closed circulation low-temperature carbonization technology is a kind of solid biomass
Heat chemistry processing method, the technique generate high heating value fuel gas, and the technical resource degree is higher, part landfill leachate,
Shower water also can qualified discharge after biochemical treatment.
Above-mentioned document and it is other the inferior quality of the Carbon Materials of production has a single function, cheap in the prior art,
Therefore the benefit for making garbage as resource utilize is badly damaged.Therefore need a kind of high added value switchs to rubbish charing function material
The recycling processing method of material.
Invention content
To solve the above problems, the present inventor's process gos deep into and system research, the composition of domestic waste is fully combined,
Comprehensive research has been carried out in the full-flow process link of entire garbage disposal, following technology has been provided, with very economical cost
The charing functional material of high added value has been made by rubbish.
In one aspect of the invention, a kind of method converted garbage into carbonize functional material is provided, this method includes
Following steps：(1) rubbish is pre-processed, rubbish is then packed into rubbish feeding device, wherein the pretreatment includes removing
Remove dregs, glass, stone, ceramics and the metal in rubbish；(2) rubbish feeding device is made to pass through high temperature distillation carbonizing apparatus；(3)
Gas stream is taken out from high temperature distillation carbonizing apparatus top；(4) gas stream is made to pass through catalyst bed in a gaseous form；(5)
The effluent of self-catalysis agent in future bed is condensed and is detached, and liquid combustible object and water are obtained；(6) it is carbonized from across high temperature distillation
The rubbish feeding device of device obtains charing functional material.
The rubbish is preferably domestic waste.
Preferably, the pretreatment further includes that the rubbish after removing dregs, glass, stone, ceramics and metal carries out powder
It is broken, it then mixes functional material and is uniformly mixed.Certainly, it will be appreciated by the appropriately skilled person that the substance to be removed is unlimited
In dregs, glass, stone, ceramics and metal, as long as the substances such as inorganic or metallics that can not be carbonized, all give as far as possible
Removal.
In an especially preferred embodiment, the functional material is zeolite, more preferable natural zeolite.Natural zeolite
Due to its being easily obtained property, price is usually relatively low.
The study found that it is compound more importantly can to form charcoal-zeolite for the progress that zeolite can be catalyzed high temperature distillation charing
Object, the compound are to carbonize functional material, can be widely applied for the fields such as catalysis, absorption.
The zeolite is preferably natural zeolite, and average grain diameter is preferably 10-80 μm, and chemical empirical formula is preferably
Ca4K8Na8Mg4(Si40Al8)O96·24H2O.The natural zeolite can be for example commercially available.Through research, there is the chemistry empirical formula
Zeolite due to higher silica alumina ratio, contain alkali and alkaline earth metal ions element simultaneously, be more suitble to the catalysis of rubbish high
Temperature distillation charing.
Preferably, the weight ratio of zeolite and processed rubbish is 1:20-1:1, preferably 1:10-1:1.
Meanwhile taking out gas stream preferably in a continuous manner from high temperature distillation carbonizing apparatus top.
High temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam.
The temperature of the high temperature anaerobic steam is preferably 250-600 DEG C, more preferable 270-400 DEG C.The high temperature anaerobic steams
The pressure of vapour is preferably 0.2-1.0MPa.
Preferably, wherein including nitrogen in the high temperature anaerobic steam.It is highly preferred that nitrogen content is 10-80v.%, more
It is preferred that 20-60v.%.
For the present invention, compared with simple destructive distillation in the prior art, the presence of nitrogen can avoid rubbish from being carbonized
It burns in the process, makes the charcoal of generation that there is higher calorific value.In addition, compared with steam gasification pure in the prior art,
The presence of nitrogen can also increase heat medium calorific value, improve the efficiency of heating surface to improve charing efficiency, while can also save
Steam consumption more importantly by the addition of nitrogen, can provide required catalysis item for the catalysis upgrading of follow-up distillate
Part, such as required vapor partial pressure is adjusted, because excessively high vapour pressure can cause catalysis upgrading to be difficult to effectively carry out, nitrogen adds
Enter the vapor partial pressure that can be reduced in gas stream i.e. distillate.
The inventors discovered that in existing waste steam treatment technology, the composition often having ignored for rubbish has choosing
Steaming conditions are selected to selecting property, the difference of rubbish composition is had ignored, causes garbage treatment efficiency relatively low.The present inventor passes through
Numerous studies select different steaming conditions according to different rubbish compositions, obtain good steam treatment effect.It is special
Not, following high temperature distillation charing process condition is selected：The temperature of high temperature anaerobic steam is 250-450 DEG C, preferably 280-320
℃；Nitrogen content in high temperature anaerobic steam is 10-30v.%, preferably 10-20v.%；Stop in high temperature distillation carbonizing apparatus
It is 5-12h, preferably 6-10h to stay the time.
It clearly can be seen that the charing function of wrapping charing functional material zeolite-containing and do not include zeolite by H NMR spectroscopy
Material there are dramatically different, such as both there are larger differences peak at 84ppm and 89ppm, show charing work(zeolite-containing
The content of cellulose is apparent much lower in energy material, and the hemicellulose peak at 172ppm disappears, it means that zeolite has
It is horizontal conducive to the decomposition and charing for promoting rubbish.
In the present invention, the BET specific surface area of charing functional material obtained can be 70-500m2/ g, preferably from about
400m2/g；Mesopore volume can be 0.08-0.15mL/g, and macropore volume can be 3.0-10.0 μ L/g.Such specific surface area
Make the reforming reaction of the charing composite functional material particularly suitable for hydrocarbon, such as the reformation of alkane with pore volume distribution.
The study found that the such high temperature distillation carbonization condition of selection, is since plastic, rubber substance is high temperature distillation charcoal
One of the source of bio oil during change, the ingredients such as the rubbish from cooking that compares and wood grass are non-to steam distillation carbonization condition
It is often sensitive, when its content is high, needs to make its decomposition using higher temperature and water vapour, but distill carbonization time and again cannot
It is long, it is otherwise easy to that the bio oil of generation is made to resolve into micro-molecular gas, biological oil yield is caused to reduce, and generate harmful pair
Product.
When organic species content is higher in rubbish, above-mentioned steaming conditions are particularly conducive to generate liquid combustible object
Generation；And organic species content it is relatively low when, be particularly conducive to charing functional material generation.
In a preferred embodiment, the catalyst in the catalyst bed is that inorganic oxide or silicate load
The mixture of ferrum-based catalyst ferrum-based catalyst or the two that either charcoal loads.
In the particularly preferred embodiment of the present invention, the present inventor passes through numerous studies, develops a kind of energy
Enough effectively to carrying out the catalyst for adding hydrogen upgrading from the bio oil in the gas stream that high temperature distillation carbonizing apparatus top is taken out,
The catalyst includes the active constituent of carrier and load on the carrier, and wherein carrier can be Al2O3、SiO2、TiO2, point
One or more mixtures in son sieve, activated carbon, catalytic active component can be Fe2O3With at least two transition metal with
And the mixture of at least one noble metal.The transition metal is selected from Ni, Cu, Fe, Ce etc., and the noble metal is selected from Pt, Pd, Ru
Deng.
In an especially preferred embodiment, catalyst can be catalyst shown in following formula：Ni-Cu-Pd-
Co2O3-Fe2O3/ HZSM-5, the wherein molar ratio of Ni, Cu, Pd, Co, Fe are (1- 2):(5-10):(0.1-0.5):(1-2):
(10-20) is based on overall catalyst weight gauge, Ni-Cu-Pd-Co2O3-Fe2O3The content of active constituent is 1-10%, preferably 2-
8%, more preferable 5%.HZSM-5 is carrier.Preferably, HZSM-5 be low silica-alumina ratio HZSM-5, such as silica alumina ratio be less than 15,
More preferably less than 10, most preferably less than 5, this is because finding that acid strong HZSM-5 is more advantageous to splitting for bio oil heavy component
Solution, bio oil bottoms are minimum.
The ingredient of bio oil is usually relatively complex, and mainly may include acids, aldehydes, ketone, alcohols, phenols, furans, ester
Class, ethers and a small amount of nitrogenous compound and other multi-functional compounds.Since bio oil thermal stability is poor, acid and corrosivity
By force, water content is high, calorific value is low and is not easy the characteristics such as to dissolve each other with petroleum-based products, therefore bio oil can only realize that primary is answered at present
With for example for heat power equipments such as Industrial Stoves and oil burning boilers, oil product cannot being substituted and directly apply to internal combustion engine or turbine
The burning of machine cannot be satisfied modern high-grade commercial Application.In order to improve bio oil application, need to be transformed into Gao Pin
The liquid fuel of position reaches the requirement of transport fuel, and to realize replacement or partial alternative oil product, this just must be to biology
Oil is modified upgrading, its chemical constituent is made to be converted into hydrocarbon by hydrocarbon oxygen compound.How effectively to bio oil
One of the key for carrying out upgrading is the exploitation of catalyst.
The study found that in the above-mentioned catalyst of the present invention, Niδ+Than conventional Moδ+With higher activity, Ni's makes
With that can obtain C6-C12 hydrocarbon (preferably alkane) with high selectivity, the use of Cu can obtain C16 hydrocarbon (preferably alkane with high selectivity
Hydrocarbon), Ni, Cu while, uses, it has surprisingly been found that it may also be ensured that obtaining a certain amount of C18 and C19 hydrocarbon, surface Ni, Cu's makes
Hydrogenolysis effectively occurs with the C-O keys in bio oil can be made.
It is different from general improving quality of biomass oil, in the gas stream of the present invention, the steam containing higher proportion, therefore
Very high request is proposed to the hydrothermal stability of catalyst.The conventional catalyst for improving quality of biomass oil cannot be used for this
The upgrading of the gas stream of invention.Iron catalyst is to remove a kind of common catalyst of oxygen in plant base material, however iron is catalyzed
Agent meet water when fail, although and palladium catalyst meet water when effectively, the effect of its deoxygenation is not fine, and costly, and
Minimal amount of palladium is added in iron, can get synergistic effect well.Inventor is the study found that the addition of a small amount of palladium contributes to hydrogen
It is covered in the surface of iron in catalyst, reaction is made to accelerate, and prevents water blocking from reacting, thus hydrogen consumption is small, in activity, stability
With selectivity aspect far better than individual iron catalyst, 2 times or more can be improved in catalytic life.
The present inventor also found that the addition of Co advantageously reduces the crystallite dimension of catalytic active component, can through research
Enough be effectively embedding in the duct of HZSM-5 molecular sieves, this for improve catalytic active component activity, selectivity and stabilization
Property has very positive meaning.However, if Co amounts are excessive, Co can cover hydrogenation sites Ni, Cu etc., be urged to reduce
The activity of agent.
Contain more non-aromatic hydro carbons in the bio oil of gas stream, the acid centre on HZSM-5 molecular sieves can
It is effectively aromatic compound by the non-aromatic hydrocarbon conversion.Carboxylic acid in bio oil largely derives from the acetyl of hemicellulose
Base, thermal decomposition product are mainly acetic acid, and HZSM-5 molecular sieves have preferable decarboxylation ability, and the carboxylic acid in bio oil is in molecular sieve
Decarboxylic reaction and deoxygenation occur under catalytic action so that carboxylic acid content is greatly decreased in the bio oil after upgrading.
There is not been reported in prior document for above-mentioned particularly a preferred catalyst, is that the present invention is directed to from garbage reclamation
What the concrete composition feature of gas stream and bio oil targetedly designed, achieve good upgrading effect.
It is prepared by the dipping calcination method that this field routine may be used in the catalyst.Specifically, it weighs according to the above ratio
A certain amount of precursor salt such as Ni (NO3)2、Cu(NO3)2、Pd(NO3)2、Co(NO3)2、Fe(NO3)3(or their hydrate form)
And citric acid, add deionized water dissolving, stir evenly, be made into the solution of a concentration of 0.5-1.5mol/L, weighs a certain amount of
HZSM-5 molecular sieves are put into reaction vessel, and the solution prepared is poured into reaction vessel, are placed in the constant temperature with blender and are added
Heating, stirs 1h-10h at a temperature of 60-120 DEG C, is then placed in 100 DEG C of -150 DEG C of dryings in drying box in deep fat bath apparatus
Obtained catalyst precursor is then placed in 500 DEG C of -800 DEG C of calcining 1h-6h in Muffle furnace, then in H by 12h2In the presence of in
Ni-Cu-Pd-Co is made in reduction activation at 200-300 DEG C2O3-Fe2O3/ HZSM-5 catalyst.
For the present invention, the gas stream is preferably substantially free of bioxin.Because of the distillation that heats up under anaerobic state, institute
It, can be with environment protection not will produce the harmful substances such as bioxin.This has prodigious excellent compared to common burning method
Gesture.
Preferably, the high temperature anaerobic steam wherein used in high temperature distillation carbonizing apparatus comes from high pressure through-flow steam oven.
In another aspect of this invention, the liquid combustible object obtained according to preceding method is provided.Preferably, the liquid
Oxygen content is less than 10 weight %, preferably shorter than 5 weight %, more preferably less than 2 weight % in combustible.Further, the liquid
The higher calorific value of combustible is more than 40MJ/kg.
In another aspect of this invention, the charing function of obtaining according to the method for any one of preceding claims is provided
Material.
Description of the drawings
Fig. 1 is the vertical view of high temperature distillation carbonizing apparatus according to the present invention；
Fig. 2 is the NMR comparison diagrams for adding zeolite and not adding zeolite charing functional material obtained；
Fig. 3 is the SEM figures of the according to embodiments of the present invention 1 charing functional material obtained.
Specific embodiment
With reference to following embodiment and comparative example, the present invention is described in further detail, but the embodiment party of the present invention
Formula is without being limited thereto.
Embodiment 1
Choose the domestic waste that garbage compression transfer station is occupied from five tunnel of Haidian District, Beijing City, the composition of the rubbish
It is as shown in table 1 below after testing：
Table 1：Domestic waste is at being grouped as
High temperature distillation charing is carried out to above-mentioned rubbish by following steps：Rubbish is pre-processed, then fills rubbish
Enter rubbish feeding device, wherein removing dregs, glass, stone, the pottery in rubbish by garbage sorting machine such as specific gravity separator
Then porcelain and metal mix natural zeolite (deriving from natural zeolite powder factory of Jinyun county), the weight of zeolite and processed rubbish
Than being 1:15, it is uniformly mixed；Rubbish feeding device is set to pass through high temperature distillation carbonizing apparatus；It is taken from high temperature distillation carbonizing apparatus top
Go out gas stream；The gas stream is set to pass through catalyst bed in a gaseous form；The effluent of self-catalysis agent in future bed is condensed
And separation, obtain liquid combustible object and water；Charing function material is obtained from the rubbish feeding device across high temperature distillation carbonizing apparatus
Material.The high temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam, and the temperature of high temperature anaerobic steam is 280 DEG C, high
Nitrogen content in warm anaerobic steam is 12v.%, and processing average time is 6.0 hours.Liquid combustible object uses hydrogenation deoxidation side
Method carries out upgrading, and upgrading catalyst used is Ni-Cu-Pd-Co2O3-Fe2O3/ HZSM-5, wherein Ni, Cu, Pd, Co, Fe rub
You are than being 2:8:0.15:1.5:15, it is based on overall catalyst weight gauge, Ni-Cu-Pd-Co2O3-Fe2O3Catalytic active component contains
Amount is 5%, and it is 250 DEG C to add hydrogen upgrading condition, 8.0MPa hydrogen pressures, 2h.Coke is obtained by this method and through the biology of upgrading
Oil.Oxygen content in the bio oil is 5.3wt.%, and catalyst life is about 720h.
Due to the catalytic action of zeolite, only need can complete carbonization reaction within about 6 hours.By the SEM figures of the carbon of Fig. 3
As can be seen that particularly well In-situ reaction has arrived in Carbon Materials zeolite, completely not with the physical mixed of Carbon Materials and zeolite
Together, it to have more excellent performance, such as is greatly improved in chemical stability.
The porosity and surface area that functional material is carbonized using QuadraSorb SIMP apparatus measures, wherein according to ISO
Standard 9277 measures the BET specific surface area for obtaining charing functional material.Fig. 2 is addition zeolite and is obtained when not adding zeolite
The NMR comparison diagrams of functional material must be carbonized.The BET specific surface area of the charing functional material obtained of embodiment 1 is 12.5m2/g；In
Pore volume is 0.12mL/g, and macropore volume is 6.0 μ L/g.
Comparative example 1
The comparative example does not mix zeolite with differing only in for embodiment 1 in raw material.Biological oily yield is only embodiment 1
About 40%.Show that a large amount of bio oils may have occurred decomposition.The BET specific surface area of charing functional material obtained is 3.5m2/g；
Mesopore volume is 0.15mL/g, and macropore volume is 1.1 μ L/g.
Comparative example 2
The temperature for differing only in high temperature anaerobic steam of the comparative example and embodiment 1 is 500 DEG C, in high temperature anaerobic steam
Nitrogen content be 50v.%.Biological oily yield is only about the 40% of embodiment 1.Show that a large amount of bio oils may have occurred point
Solution.
Comparative example 3
The NiMo/Al for differing only in the catalyst that bio oil upgrading uses and being conventional of the comparative example and embodiment 12O3
Catalyst.Oxygen content in the bio oil through upgrading obtained is 19.8wt.%, and catalyst life is about 120h.
By above-described embodiment and comparative example clearly it can be seen from the present invention method successfully by charcoal and zeolite functionalization
Ground organic composite obtains higher specific surface area and macropore volume together, higher specific surface area and macropore volume
Make it in catalysis, there is better catalytic performance especially in the catalytic reforming of hydrocarbon.
In addition, the method for the present invention can obtain higher biological oily yield, and the bio oil of the method for the present invention upgrading,
With lower oxygen content, to have higher calorific value and stability, the catalyst life of this back end hydrogenation upgrading to greatly improve.
This written description discloses the present invention, including optimal mode using example, and also enables those skilled in the art
It manufactures and using the present invention.The present invention can patentable scope be defined by the claims, and may include this field skill
Other examples that art personnel expect.If this other examples have not different from the structural elements of the literal language of claims
Element, or if this other examples include with equivalent structure element of the literal language of claims without substantial differences,
Then this other examples are intended within the scope of claims.In the case where inconsistent degree will not be caused, by reference to
It will be incorporated herein in place of all references referred to herein.
Claims (3)
1. a kind of method converted garbage into carbonize functional material, this approach includes the following steps：
(1) rubbish is pre-processed, rubbish is then packed into rubbish feeding device, wherein the pretreatment includes removing rubbish
In dregs, glass, stone, ceramics and metal；The pre-treatment step further includes that will remove dregs, glass, stone, ceramics and gold
Rubbish after category crushes, and then mixes and functional material and is uniformly mixed, and the functional material is zeolite, zeolite with through processing
Rubbish weight ratio be 1:20-1:1；
(2) make rubbish feeding device that high temperature distillation carbonizing apparatus, the high temperature distillation carbonizing apparatus be passed through to pass through high temperature anaerobic steam
It is heated, the temperature of the high temperature anaerobic steam is 250-600 DEG C, and the pressure of the high temperature anaerobic steam is 0.2-
1.0MPa；Include 10-80v.% nitrogen in the high temperature anaerobic steam；
(3) gas stream is taken out from high temperature distillation carbonizing apparatus top；
(4) gas stream is made to pass through catalyst bed in a gaseous form；
(5) effluent of self-catalysis in future agent bed is condensed and is detached, and obtains liquid combustible object and water；
(6) charing functional material is obtained from the rubbish feeding device across high temperature distillation carbonizing apparatus.
2. according to the method described in claim 1, the wherein described rubbish is domestic waste.
3. according to the method for preceding claims 1 or 2, wherein the gas stream is free of bioxin.
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