CN106362689B - The reuse method of Combustion Properties of Municipal Solid Waste carbide - Google Patents

The reuse method of Combustion Properties of Municipal Solid Waste carbide Download PDF

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Publication number
CN106362689B
CN106362689B CN201610925728.4A CN201610925728A CN106362689B CN 106362689 B CN106362689 B CN 106362689B CN 201610925728 A CN201610925728 A CN 201610925728A CN 106362689 B CN106362689 B CN 106362689B
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high temperature
rubbish
carbon materials
added
catalyst
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CN106362689A (en
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韩先福
王红军
贺伟力
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Beijing qihonglan Environmental Protection Technology Co.,Ltd.
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New Austrian Ecological Environment Management Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONAGEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

Abstract

The present invention provides the reuse methods of Combustion Properties of Municipal Solid Waste carbide, the Carbon Materials that Combustion Properties of Municipal Solid Waste charing obtains are modified, the absorption for heavy metal ion.Adsorbent cost made from the method for the present invention is low, and adsorption effect is good.

Description

The reuse method of Combustion Properties of Municipal Solid Waste carbide
Technical field
The invention belongs to waste resource recovery reutilization technology fields, and in particular to Combustion Properties of Municipal Solid Waste carbide is again Using method, relate more specifically to the carbide i.e. Carbon Materials being modified the method for preparing adsorbent.
Background technique
Active carbon is a kind of porous carbon containing matter, and there is highly developed hole to construct for it, compares table with very high Area is a kind of extremely excellent adsorbent.And its suction-operated is reached by physical adsorption capacity and chemically adsorption capacity.Its Component other than carbon element, still contain a small amount of hydrogen, nitrogen, oxygen and ash, structure be then charcoal formed six ring objects accumulation and At.Due to the irregular alignment of six ring charcoals, so that active carbon has the characteristic of more micro pore volumes and high surface area.
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 for being 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, atmosphere, 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.It is each that burning disposal method can generate dioxin etc. The environmentally hazardous polluter of kind, safe garbage incineration equipment price is high, scale of investment is big, and burning disposal can only pass through Handling is used to maintain to run, and resin, Plastic account for 10% or so in conventional rubbish, and remaining is exactly kitchen, paper, wood chip etc..
CN103949214A disclose it is a kind of using Chinese medicine slag as the heavy metal adsorption active carbon of raw material, be by Chinese medicine slag by Respectively through high temperature carbonization and steam activation after the classification of rhizome mass of residue percentage composition, after remixing and hydrogen peroxide carries out oxygen Then change reaction is modified through methacrylic acid and is solidified using crosslinking agent, finally dry, crushing is prepared.
CN104150480A disclose it is a kind of adsorb heavy metal activated carbon with high specific surface area preparation method, pass through by Biomass material drying is put into microwave reactor after being crushed to 60~100 mesh, is passed through N2, control microwave power, carburizing temperature Microwave carbonization is carried out, microwave is carbonized after 50~100min, cooling carbonized material.Take carbonized material and organic alkoxide activator by 1:1 After~10 quality is more uniform than ground and mixed, it is put into atmosphere furnace and is warming up to 800~1000 DEG C and keeps the temperature 100~300min, it is cold But it is taken out to room temperature, after salt pickling, then is washed to neutrality, it is dry to get active carbon.
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 using rubbish rubbish destructive distillation, is divided 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 Dioxin;The gasification gas of high temperature, rubbish heating, the destructive distillation of rubbish retort section, 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 without dioxin, non-exhaust emission.
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 reaction was completed, the reaction chamber is pulled out from the reaction kettle.
CN102606236A discloses a kind of garbage disposal waste heat power generation system with internal steam pipe, includes refuse gasification Furnace 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, is communicated with water inlet pipe 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 And it burns and is equipped with a hollow sandwich between furnace internal-lining;The interlayer bottom is connected to bottom in furnace body, the interlayer top and combustible gas Outlet;Air inlet channel, air inlet set by the air inlet upper part of channel and 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 furnace of gasifying medium, including top Refuse gasification room and the high-temperature water vapor of lower part room occurs, refuse gasification room and high-temperature water vapor occur between being provided between room Every the water cooling chimney arch of arrangement, refuse gasification room room with high-temperature water vapor and separates by water cooling chimney arch occurs;The high-temperature water vapor hair The inner wall of raw room circumferentially two plasma torch, the working gas using low temperature water vapour as plasma torch.
WO2011/000513A1 discloses a kind of comprehensive waste treatment system and method comprising combustiblerefuse source makes With for separating the separator of the combustiblerefuse from recyclable material, for the combustiblerefuse is dry to produce Give birth to the vacuum desiccator of pyrolysis feed and the heat for the pyrolysis feed pyrolytic to be generated to coke and pyrolysis gas Solve device.
GB2006/002409A discloses a kind of method for handling rubbish, which comprises (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 heat of solid biomass Chemical processes, the technique generate high heating value fuel gas, and the technical resource degree is higher, part landfill leachate, spray Water drenching can also qualified discharge after biochemical treatment.
Above-mentioned document and it is other in the prior art, it is not high to the comprehensive utilization degree of rubbish, and be made product quality It is lower.Therefore a kind of recycling processing method that rubbish can be made to be comprehensively utilized is needed.
Summary of the invention
To solve the above problems, the present inventor's process gos deep into and system research, the composition of domestic waste is sufficiently combined, Comprehensive research and optimization have been carried out in the full-flow process link of entire garbage disposal, has provided following rubbish comprehensive utilization processing Method.
In one aspect of the invention, the processing and resource utilization method of rubbish are provided, method includes the following steps: (1) sorting pretreatment will be carried out as the rubbish of waste, removes the non-combustible solids in rubbish, rubbish is then packed into rubbish Feeding device;(2) rubbish feeding device is made to pass through high temperature distillation carbonizing apparatus;(3) it is taken out from high temperature distillation carbonizing apparatus top Gas stream;(4) gas stream is made to pass through catalyst bed in a gaseous form;(5) effluent of self-catalysis in future agent bed carries out Condensation and separation, obtain liquid combustible object and water;(6) raw material of wood-charcoal is obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus Material is pyrolytic carbon compound.
The rubbish is preferably domestic waste.
The Carbon Materials are active carbon.
This field it is generally believed that Carbon Materials made from rubbish since the impurity such as organic matter contained is excessive, specific surface area Less than normal, pore structure is unreasonable, can not be used for the preparation of high standard adsorbent, is only used for the preparation of common adsorbents.So And the present inventor it has been investigated that, Carbon Materials produced by the present invention being capable of the very good preparation for adsorbent.Speculate it Reason can generate acid such as HCl, in forming process under high temperature steam environments during high temperature garbage is distilled and carbonized Charcoal and last obtained charcoal play good activation, simultaneously as the effect of high temperature and high pressure steam, organic matter is with steaming Vapour material is sufficiently removed, and keeps the content of organic matter in Carbon Materials extremely low.
Preferably, the pretreatment further includes that the rubbish after removing dregs, glass, stone, ceramics and metal carries out powder It is broken.Certainly, it will be appreciated by the appropriately skilled person that the substance to be removed is not limited to dregs, glass, stone, ceramics and metal, As long as the substances such as the inorganic or metal solid object that can not be carbonized, are all removed as far as possible.
Preferably, the modification includes surface grafting tannin.
Gas stream is taken out 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, most preferably 300-350 ℃.The pressure of the high temperature anaerobic steam 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 be avoided rubbish and be carbonized It burns in the process, makes the charcoal calorific value with higher generated.In addition, compared with steam gasification pure in the prior art, The presence of nitrogen can also increase heat medium calorific value, improve heating efficiency 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 subsequent distillate Part, such as required vapor partial pressure is adjusted, because excessively high vapour pressure will lead to catalysis upgrading and 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 the composition often having ignored for rubbish has choosing in existing waste steam processing technique Steaming conditions are selected to selecting property, the difference of rubbish composition is had ignored, causes garbage treatment efficiency lower.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, select following high temperature distillation charing process condition: 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 Staying the time is 5-12h, preferably 6-10h.
In the present invention, the BET specific surface area of Carbon Materials obtained can be 100-600m2/ g, preferably from about 200-500m2/ g;Macropore volume can be 5.0-10.0 μ L/g, and macropore volume accounts for the 60-90% of total pore volume, preferably 70-90%.Such ratio Surface area and pore volume distribution (especially big pore size distribution) make the adsorbent as made from the Carbon Materials that there is splendid absorption to hold Amount and heavy metal adsorption selectivity.
The Carbon Materials preferably as include below step method be modified: the Carbon Materials made from as carrier, with Tannin is immobilized on Carbon Materials in a manner of covalent cross-linking as crosslinking agent the crosslinking agent by glyoxaline compound, system Obtain adsorbent.
Preferably, the Carbon Materials are preferably as including that the method for below step is modified: the Carbon Materials made from are Carrier, carrying out surface modification to Carbon Materials with amination reagent makes surface have-NH2 group, is then made with glyoxaline compound For crosslinking agent, tannin is immobilized on Carbon Materials in a manner of covalent cross-linking the crosslinking agent, adsorbent is made.
Containing the ortho position phenolic hydroxyl group that can be largely complexed with metallic ion coordination on the B ring of tannin molecular structure, simultaneously Also contain galloyl base on its C ring, thus higher compatibility is shown to each metal ion species.But tannin is usually water solubility Compound, needs to be supported on and is prepared into the insoluble adsorbent of water on the insoluble carrier of water and could use.Many sites in tannin molecule All there is very high necleophilic reaction activity, can be grafted to by Mannich reaction and contain-NH2Carrier on prepare novel suction Attached dose.
The tannin is preferably persimmon tannin.
Before being crosslinked with glyoxaline compound to Carbon Materials, surface preferably is carried out to Carbon Materials with amination reagent Amination processing.
The amination reagent is preferably N- (β-aminoethyl) 2- aminopropyl triethoxysilane.
Adsorbent obtained is to Hg2+、Cu2+、Cd2+Etc. heavy metal ion have good suction-operated.
It is modified adsorbent obtained, adsorption capacity and regenerating stability with higher by the method for the invention.It grinds Study carefully discovery, the surface of Carbon Materials has biggish tannin grafting amount, for Cu2+、Hg2+、Cd2+Etc. the absorption of heavy metal ion go Except having the characteristics that adsorption capacity is big, the rate of adsorption is fast, adsorptive selectivity is high and be easy to desorb, it can be used for Heavy Metals in Waters Adsorption.
Preferably, the modification is carried out by method comprising the following steps: (1) alkane solvent, alcohol ethers surface is living Property agent and n-hexyl alcohol be added in a certain amount of deionized water by the volume ratio of (5-10): 1:l and be configured to mixed liquor, control temperature It is 25-60 DEG C, quantitative Carbon Materials and N- (β-aminoethyl) 2- aminopropyl-triethoxy silicon is added after magnetic agitation 10-60min The hydrolysis that appropriate ammonium hydroxide promotes N- (β-aminoethyl) 2- aminopropyl triethoxysilane is added, to water in alkane, and sustained response 1-5h Solution is completely rear to be added proper amount of acetone demulsification, and filtering obtains amidized Carbon Materials, after being washed and dried repeatedly with deionized water It is spare;(2) it takes a certain amount of amination Carbon Materials obtained above to be added in the solution containing persimmon tannin, adds after stirring 5-20h Enter 10.0-30.0mL 2-ethyl-4-methylimidazole, reacts 10-30h, filtration washing, 30-60 DEG C of vacuum again at 20-50 DEG C Dry 10-30h is to get the adsorbent for being grafted persimmon tannin to Carbon Materials.
It is further preferred that the modification is carried out by method comprising the following steps: (1) by thiacyclohexane, polyethylene glycol Single nonylplenyl ether and n-hexyl alcohol are added in a certain amount of deionized water by the volume ratio of 6:1:l is configured to mixed liquor, control Temperature is 30 DEG C, and quantitative Carbon Materials and N- (β-aminoethyl) 2- aminopropyl triethoxysilane are added after magnetic agitation 5min, And sustained response 2h, the hydrolysis that appropriate ammonium hydroxide promotes N- (β-aminoethyl) 2- aminopropyl triethoxysilane is added, wait hydrolyze Proper amount of acetone demulsification is added after complete, filtering obtains amidized Carbon Materials, spare after being washed and dried repeatedly with deionized water; (2) it takes 50g amination Carbon Materials to be added in the solution of 200.0mL 10.0g containing persimmon tannin, 20.0mL is added after stirring 12h 2-ethyl-4-methylimidazole, reacts 20h, filtration washing again at 40 DEG C, and 40 DEG C of vacuum drying are grafted for 24 hours to get to Carbon Materials The adsorbent of persimmon tannin.
In the present invention, inventor's research is it has furthermore been found that selection high temperature distillation carbonization condition of the invention, is due to modeling Material rubber-like material be bio oil in high temperature distillation carbonization process one of source, the ingredients such as the rubbish from cooking that compares and wood grass, It is very sensitive to steam distillation carbonization condition, when its content is high, needs to make its point using higher temperature and water vapour Solution, again cannot be too long but distill carbonization time, is otherwise easy to that the bio oil generated is made to resolve into micro-molecular gas, causes to give birth to Object oil yield reduces, and generates harmful side 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 lower when, be particularly conducive to the generation of Carbon Materials.
In a preferred embodiment, the catalyst in the catalyst bed is the ferrum-based catalyst of charcoal load.
In a particularly preferred embodiment of the invention, the present inventor passes through numerous studies, develops a kind of energy It is enough effectively to the catalyst for carrying out 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 is preferably aluminium oxide, catalytic activity group Dividing can be Fe2O3With the mixture of at least two transition metal and at least one noble metal.The transition metal be selected from Ni, Cu, Fe, Ce etc., the noble metal are selected from Pt, Pd, Ru etc..
In an especially preferred embodiment, the catalyst of charcoal load can be catalyst shown in following formula: Ni- Cu-Pd-Co2O3-Fe2O3/Al2O3, wherein the 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 meter, Ni-Cu-Pd-Co2O3-Fe2O3The content of active constituent is 1-10%, preferably 2-8%, more preferable 5%.
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, the characteristics such as water content is high, calorific value is low and is not easy 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 is unable to satisfy modern high-grade industrial 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, to realize substitution or part substitution 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 above-mentioned catalyst of the invention, Niδ+Than conventional Moδ+With higher activity, Ni's makes With that can obtain with high selectivity C6-C12 hydrocarbon (preferably alkane), the use of Cu can obtain C16 hydrocarbon (preferably alkane with high selectivity Hydrocarbon), Ni, Cu while, uses, it has surprisingly been found that surface Ni, Cu's makes it may also be ensured that obtaining a certain amount of C18 and C19 hydrocarbon With can make the C-O key in bio oil that hydrogenolysis effectively occur.
It is different from general improving quality of biomass oil, in gas stream of the 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 a kind of common catalyst for removing oxygen in plant base material, however iron is catalyzed Agent is failed when meeting water, although and palladium catalyst when meeting water effectively, the effect of its deoxygenation be not very well, 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 facilitates hydrogen Be covered in the surface of iron in catalyst, accelerate reaction, and prevent water blocking from reacting, thus hydrogen consumption is small, activity, stability and For selectivity aspect far better than individual iron catalyst, 2 times or more is 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, makes activity through research The dispersion degree of component in the carrier is high, and can reduce catalyst agglomeration, this is for improving the activity of catalytic active component, selecting Selecting property and stability have very positive meaning.However, Co can cover hydrogenation sites Ni, Cu etc. if Co amount is excessive, To reduce the activity of catalyst.
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.
The catalyst can be prepared using the dipping calcination method of this field routine.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, is made into the solution that concentration is 0.5-1.5mol/L, weighs a certain amount of Al2O3(preferably α-Al2O3With γ-Al2O3Mixture, the two weight ratio is preferably 1:3) be put into reaction vessel, will prepare Solution pour into reaction vessel, be placed in the heated at constant temperature oil bath device with blender and heat, at a temperature of 60-120 DEG C 1h-10h is stirred, 100 DEG C -120 DEG C dry 12h in drying box is then placed in, obtained catalyst precursor is then placed in horse Not in furnace under nitrogen atmosphere in 300 DEG C of -600 DEG C of calcining 1h-6h, then in H2In the presence of the reduction activation at 200-300 DEG C, Ni-Cu-Pd-Co is made2O3-Fe2O3/Al2O3Catalyst.
For the present invention, the gas stream is preferably substantially free of dioxin.Because of the distillation that heats up under anaerobic state, institute The harmful substances such as dioxin will not be generated, atmospheric environment can protect.This has very big excellent compared to common incineration method Gesture.
Preferably, wherein high temperature anaerobic steam 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 lower 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 greater than 40MJ/kg.
Detailed description of the invention
Fig. 1 is the top view of high temperature distillation carbonizing apparatus according to the present invention;
Fig. 2 is the SEM figure of according to embodiments of the present invention 1 Carbon Materials obtained.
Specific embodiment
Below with reference to following embodiment and comparative example, the present invention is described in further detail, but embodiment party of the 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 through detecting:
Table 1: domestic waste is at being grouped as
High temperature distillation charing is carried out to above-mentioned rubbish by following steps: being removed by garbage sorting machine such as specific gravity separator After removing the dregs in rubbish, glass, stone, ceramics and metal, rubbish is packed into rubbish feeding device, then crushes rubbish; 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;Make the gas Body logistics passes through catalyst bed in a gaseous form;The effluent of self-catalysis agent in future bed is condensed and is separated, and obtaining liquid can Combustion things and water;Carbon Materials are obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus.The high temperature distillation carbonizing apparatus It is heated by high temperature anaerobic steam, the temperature of high temperature anaerobic steam is 320 DEG C, and nitrogen content in high temperature anaerobic steam is 12v.%, processing average time are 8.0 hours.The Carbon Materials are modified by following method: by thiacyclohexane, polyethylene glycol Single nonylplenyl ether and n-hexyl alcohol are added in a certain amount of deionized water by the volume ratio of 6:1:l is configured to mixed liquor, control Temperature is 30 DEG C, and quantitative Carbon Materials and N- (β-aminoethyl) 2- aminopropyl triethoxysilane are added after magnetic agitation 5min, And sustained response 2h, the hydrolysis that appropriate ammonium hydroxide promotes N- (β-aminoethyl) 2- aminopropyl triethoxysilane is added, wait hydrolyze Proper amount of acetone demulsification is added after complete, filtering obtains amidized Carbon Materials, spare after being washed and dried repeatedly with deionized water; It takes 50g amination Carbon Materials to be added in the solution of 200.0mL 10.0g containing persimmon tannin, 20.0mL 2- is added after stirring 12h Ethyl -4-methylimidazole, reacts 20h, filtration washing again at 40 DEG C, and 40 DEG C of vacuum drying are grafted persimmon for 24 hours to get to Carbon Materials The adsorbent of Chinese tannin.
After tested, which is containing 0.05 weight %Hg2+Wastewater treatment in equilibrium adsorption capacity be 60mg/g, regeneration After 16 times, adsorption capacity is only dropped to initial 81%.
Comparative example 1
The operation of embodiment 1 is repeated, the difference is that (deriving from Guangdong using commercially available active carbon and wind environment technology being public Department) it is modified to prepare adsorbent.
After tested, which is containing 0.05 weight %Hg2+Wastewater treatment in equilibrium adsorption capacity be 68mg/g, regeneration After 16 times, adsorption capacity is only dropped to initial 85%.
Comparative example 2
Repeat embodiment 1 operation, the difference is that Carbon Materials be it is non-modified, be directly used as the suction of heavy metal ion Attached dose.
After tested, which is containing 0.05 weight %Hg2+Wastewater treatment in equilibrium adsorption capacity be 8mg/g, regeneration 8 After secondary, adsorption capacity is only dropped to initial 31%.
The Carbon Materials and the higher commercially available work of price that the method for the present invention obtains it can be seen from above-described embodiment and comparative example Property charcoal compare, adsorption capacity and power of regeneration do not have notable difference, therefore have very big cost advantage.In addition, using this After inventive method is modified, adsorption capacity is dramatically increased, and absorption validity is also greatly improved.
By above-described embodiment and comparative example clearly it can be seen from method of the invention charcoal successfully be made in charcoal be applied to In the preparation of catalyst, compared with expensive commercially available active carbon, in the case where catalyst life is roughly the same, catalytic hydrogenation is de- Oxygen effect slightly reduces, to greatly save cost.It especially needs to recycle metal component regeneration in catalyst and needs In the case where big carbon content active, the cost of active carbon plays a key effect to the economy of entire technique.
This written description discloses the present invention, including optimal mode using example, and also enables those skilled in the art The manufacture and use present invention.It is of the 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 the equivalent structure element with the literal language of claims without substantial differences, Then this other examples are intended within the scope of claims.In the case where not will cause inconsistent degree, by reference to It will be incorporated herein in place of all references referred to herein.

Claims (3)

1. the reuse method of Combustion Properties of Municipal Solid Waste carbide, this method includes the charcoal for obtaining Combustion Properties of Municipal Solid Waste Material is modified, and prepares adsorbent for heavy metal, wherein the modification includes surface grafting tannin, the modification is logical Cross method comprising the following steps progress: (1) by alkane solvent, alcohol ether surfactants and n-hexyl alcohol by (5-10): 1:l's Volume ratio is added in a certain amount of deionized water and is configured to mixed liquor, controlled at 25-60 DEG C, magnetic agitation 10-60min Quantitative Carbon Materials and N- (β-aminoethyl) 2- aminopropyl triethoxysilane, and sustained response 1-5h are added afterwards, is added appropriate Ammonium hydroxide promotes the hydrolysis of N- (β-aminoethyl) 2- aminopropyl triethoxysilane, and proper amount of acetone demulsification is added after hydrolyzing completely, Filtering obtains amidized Carbon Materials, spare after being washed and dried repeatedly with deionized water;(2) it takes a certain amount of obtained above Amination Carbon Materials are added in the solution containing persimmon tannin, and 10.0-30.0mL 2- ethyl -4- methyl is added after stirring 5-20h Imidazoles, reacts 10-30h, filtration washing again at 20-50 DEG C, and 30-60 DEG C of vacuum drying 10-30h is grafted to get to Carbon Materials The adsorbent of persimmon tannin;
The Combustion Properties of Municipal Solid Waste prepare carbide the following steps are included:
(1) sorting pretreatment will be carried out as the rubbish of waste, removes the non-combustible solids in rubbish, is then packed into rubbish Rubbish feeding device;
(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) effluent of self-catalysis in future agent bed is condensed and is separated, and liquid combustible object and water is obtained, under the catalyst is Catalyst shown in formula: Ni-Cu-Pd-Co2O3-Fe2O3/Al2O3, wherein the 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 meter, Ni-Cu-Pd-Co2O3-Fe2O3Active constituent Content is 2-8%;
(6) Carbon Materials i.e. pyrolytic carbon compound is obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus;
Wherein high temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam, and the temperature of the high temperature anaerobic steam is 250- 600 DEG C, the pressure of the high temperature anaerobic steam is 0.2-1.0MPa;It include 10-80v.% nitrogen in the high temperature anaerobic steam.
2. according to the method described in claim 1, wherein the non-combustible solids includes dregs, glass, stone, ceramics and gold Belong to.
3. according to the method described in claim 1, the temperature of the high temperature anaerobic steam is 270-600 DEG C.
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