CN106390939B - A kind of adsorbent for heavy metal - Google Patents
A kind of adsorbent for heavy metal Download PDFInfo
- Publication number
- CN106390939B CN106390939B CN201610925751.3A CN201610925751A CN106390939B CN 106390939 B CN106390939 B CN 106390939B CN 201610925751 A CN201610925751 A CN 201610925751A CN 106390939 B CN106390939 B CN 106390939B
- Authority
- CN
- China
- Prior art keywords
- high temperature
- carbon materials
- rubbish
- adsorbent
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of adsorbent for heavy metal, which is modified obtained, adsorption capacity and regenerating stability with higher by the Carbon Materials for obtaining Combustion Properties of Municipal Solid Waste charing.
Description
Technical field
The invention belongs to technical field of absorbent, and in particular to a kind of adsorbent for heavy metal.
Background technique
Heavy metal ion is that a kind of environmental pollution most serious and the mankind endanger maximum substance.Most metal ions and
Its compound is easy to be adsorbed by suspended particulate in water and be deposited in water-bed sedimentary, long-term pollution water body.Certain huge sum of moneys
Category and its compound can be enriched in fish and other aquatic organisms and in crops tissue, accumulate and participate in biosphere and follow
Ring, people drink rear toxicity amplification, the bigger organic matter of toxicity are generated in conjunction with other toxin in water.
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.Active carbon by
Adsorption for heavy metal ion.
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.
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, the high production cost of active carbon, and active carbon is to heavy metal ion
Adsorption capacity is lower, and reproducibility is bad.This field needs a kind of pair of heavy metal ion to have high absorption weight, reproducibility good
Good and low production cost adsorbent.
Summary of the invention
To solve the above problems, the present inventor with system research, abundant carbonize in conjunction with domestic waste by deeply producing
The composition of object has carried out comprehensive research and optimization in the full-flow process link of entire garbage disposal, to rubbish carbonizing production into
Row is modified, and provides a kind of new adsorbent, which, which can be provided simultaneously with, has high absorption weight, again to heavy metal ion
The feature that natural disposition is good and production cost is low, that is, above-mentioned technical problem can be solved simultaneously.
In one aspect of the invention, a kind of adsorbent for heavy metal is provided, the adsorbent is by by urban life rubbish
The Carbon Materials that rubbish pyrolysis charring obtains are modified obtained.
Preferably, it includes Hg that the adsorbent, which is heavy metal ion,2+、Cu2+、Cd2+、Cr6+One of or it is a variety of.
Preferably, the modification includes surface grafting tannin.
Crosslinking agent can be used in the grafting process.
The tannin is preferably persimmon tannin.
In another aspect of this invention, the method for preparing above-mentioned adsorbent is additionally provided comprising by domestic waste
Charcoal material surface, is then modified by the Carbon Materials that pyrolysis charring obtains.
The modification may include surface grafting tannin.
The tannin can be persimmon tannin
The Carbon Materials that Combustion Properties of Municipal Solid Waste charing is obtained the following steps are included: (1) by the rubbish as waste
Rubbish carries out sorting pretreatment, removes the non-combustible solids in rubbish, and rubbish is then packed into rubbish feeding device；(2) make rubbish
Rubbish feeding device passes through high temperature distillation carbonizing apparatus；(3) gas stream is taken out from high temperature distillation carbonizing apparatus top；(4) make this
Gas stream passes through catalyst bed in a gaseous form；(5) effluent of self-catalysis in future agent bed is condensed and is separated, and obtains liquid
Body combustible and water；(6) Carbon Materials i.e. pyrolytic carbon compound is obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus.
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 (such as the chlorine of generation the polyvinyl chloride in plastics during high temperature garbage is distilled and carbonized
Gas and vapor generate dilute hydrochloric acid after combining), to the charcoal and last charcoal obtained in forming process under high temperature steam environments
Good activation is played, simultaneously as the effect of high temperature and high pressure steam, organic matter is sufficiently removed with steam material,
Keep 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 300-500m2/
g；Macropore volume can be 5.0-10.0 μ L/g, and macropore volume accounts for the 60-95% of total pore volume, preferably 70-90%, preferably 80%
More than.Such specific surface area and pore volume distribution (especially big pore size distribution) have the adsorbent as made from the Carbon Materials
Splendid adsorption capacity 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-NH2Then group is 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+、Cr6+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+、Cr6+Etc. heavy metal ion suction
Attached removal has the characteristics that adsorption capacity is big, the rate of adsorption is fast, adsorptive selectivity is high and is easy to desorb, and can be used for a huge sum of money in water body
The Adsorption of category.
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 for repeating embodiment 1 the difference is that only and (be derived from Guangdong using commercially available active carbon and wind environment technology is 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 only Carbon Materials be it is non-modified, be directly used as heavy metal ion
Adsorbent.
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 (4)
1. a kind of method for preparing adsorbent for heavy metal, this method includes the charcoal for obtaining Combustion Properties of Municipal Solid Waste charing
Material is modified obtained adsorbent, and the modification is carried out by method comprising the following steps: (1) by alkane solvent, alcohol ether
Class surfactant and n-hexyl alcohol are added in a certain amount of deionized water by the volume ratio of (5-10): 1:l is configured to mixed liquor,
Controlled at 25-60 DEG C, quantitative Carbon Materials and N- (β-aminoethyl) 2- aminopropyl three are added after magnetic agitation 10-60min
Ethoxysilane, and sustained response 1-5h are added appropriate ammonium hydroxide and promote N- (β-aminoethyl) 2- aminopropyl triethoxysilane
Hydrolysis, is added proper amount of acetone demulsification after hydrolyzing completely, and filtering obtains amidized Carbon Materials, washed repeatedly with deionized water
And it is spare after drying；(2) it takes a certain amount of amination Carbon Materials obtained above to be added in the solution containing persimmon tannin, stirs 5-
10.0-30.0mL 2-ethyl-4-methylimidazole is added after 20h, reacts 10-30h, filtration washing, 30-60 again at 20-50 DEG C
DEG C vacuum drying 10-30h to get to Carbon Materials grafting persimmon tannin adsorbent；
Described carbonize Combustion Properties of Municipal Solid Waste obtains Carbon Materials the following steps are included: (1) carries out the rubbish as waste
Sorting pretreatment, removes the non-combustible solids in rubbish, and rubbish is then packed into rubbish feeding device；(2) transport rubbish
Device passes through high temperature distillation carbonizing apparatus；(3) gas stream is taken out from high temperature distillation carbonizing apparatus top；(4) make the gas object
Stream passes through catalyst bed in a gaseous form；(5) effluent of self-catalysis in future agent bed is condensed and is separated, and obtains liquid combustible
Object and water, the catalyst are catalyst shown in following formula: Ni-Cu-Pd-Co2O3-Fe2O3/Al2O3, wherein Ni, Cu, Pd, Co,
The molar ratio of Fe is (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%；(6) it is obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus
Carbon Materials, that is, pyrolytic carbon compound, the high temperature distillation charing process condition: the temperature of high temperature anaerobic steam is 250-450 DEG C；
The high temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam, nitrogen content in the high temperature anaerobic steam
For 10-30v.%, the residence time in high temperature distillation carbonizing apparatus is 5-12h；
The BET specific surface area of Carbon Materials obtained is 100-600m2/ g, macropore volume are 5.0-10.0 μ L/g, and macropore volume Zhan is total
The 60-95% of pore volume.
2. according to the method described in claim 1, it includes Hg that wherein the adsorbent, which is heavy metal ion,2+、Cu2+、Cd2+、Cr6+
One of or it is a variety of.
3. method according to claim 1 or 2, wherein the modification includes surface grafting tannin.
4. according to the method described in claim 3, wherein the tannin is persimmon tannin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610925751.3A CN106390939B (en) | 2016-10-31 | 2016-10-31 | A kind of adsorbent for heavy metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610925751.3A CN106390939B (en) | 2016-10-31 | 2016-10-31 | A kind of adsorbent for heavy metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106390939A CN106390939A (en) | 2017-02-15 |
| CN106390939B true CN106390939B (en) | 2019-05-28 |
Family
ID=58013237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610925751.3A Active CN106390939B (en) | 2016-10-31 | 2016-10-31 | A kind of adsorbent for heavy metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106390939B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538437B (en) * | 2022-02-17 | 2023-05-26 | 青海民族大学 | Carbon material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361058A (en) * | 2002-01-28 | 2002-07-31 | 韩璋鑫 | Active carbon producing method with city garbage and carbonizing furnace |
| CN101234331A (en) * | 2007-10-30 | 2008-08-06 | 浙江大学 | Preparation and using method for biological carbonaceous adsorption agent |
| CN102266754A (en) * | 2011-07-29 | 2011-12-07 | 湖北食为天药业科技有限公司 | Method for preparing activated carbon-persimmon tannin compound absorbent |
| CN104974770A (en) * | 2015-06-16 | 2015-10-14 | 李小林 | Harmless oxygen-free carbonization treatment system for domestic garbage |
-
2016
- 2016-10-31 CN CN201610925751.3A patent/CN106390939B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361058A (en) * | 2002-01-28 | 2002-07-31 | 韩璋鑫 | Active carbon producing method with city garbage and carbonizing furnace |
| CN101234331A (en) * | 2007-10-30 | 2008-08-06 | 浙江大学 | Preparation and using method for biological carbonaceous adsorption agent |
| CN102266754A (en) * | 2011-07-29 | 2011-12-07 | 湖北食为天药业科技有限公司 | Method for preparing activated carbon-persimmon tannin compound absorbent |
| CN104974770A (en) * | 2015-06-16 | 2015-10-14 | 李小林 | Harmless oxygen-free carbonization treatment system for domestic garbage |
Non-Patent Citations (3)
| Title |
|---|
| "Tannin-immobilized mesoporous silica bead(BT-SiO2) as an effective adsorbent of Cr(III) in aqueous solutions";Xin Huang et al.;《Journal of Hazardous Materials》;20090808;第173卷;第33-39页 |
| "二氧化硅接枝杨梅单宁用于水体中Cu2+的吸附去除";冯远春等;《皮革科学与工程》;20100428;第20卷(第2期);第10-15页 |
| "生物炭吸附重金属的研究进展";林雪原等;《环境污染与防治》;20140515;第36卷(第5期);第83-87页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106390939A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103979491B (en) | Method for producing hydrogen by blending and gasifying sludge and biomass | |
| CN108913175B (en) | Combined cycle system for treating organic wastewater based on waste biomass catalytic pyrolysis products and use method thereof | |
| CN109679672B (en) | Reaction system and method for preparing gas fuel by catalytic pyrolysis of organic solid waste | |
| CN106732502B (en) | A kind of hydrogenation catalyst | |
| CN110302756B (en) | Method for removing heavy metal ions by using industrial waste residue modified biochar | |
| CN106732704B (en) | A kind of antigravity system reducing biomass char oil content in bio oil | |
| CN106495153B (en) | The method for producing carbon material | |
| CN106390939B (en) | A kind of adsorbent for heavy metal | |
| CN102134072A (en) | Process for preparing activated carbon by using excess sludge from pesticide chemical industry sewage treatment | |
| CN106492873B (en) | A kind of catalyst for bio oil upgrading | |
| CN106732351B (en) | A kind of modified activated carbon and preparation method thereof | |
| CN106362689B (en) | The reuse method of Combustion Properties of Municipal Solid Waste carbide | |
| CN210419850U (en) | Reaction system for preparing gas fuel by catalytic pyrolysis of organic solid waste | |
| CN106378348B (en) | Treatment of wastes produced and resource utilization method | |
| CN106753461B (en) | By the method for municipal refuse hydro-thermal charing process under undercritical conditions | |
| CN106622349B (en) | Catalyst for the processing of high temperature garbage retort gas | |
| CN106398728A (en) | Multi-section garbage carbonization heating furnace | |
| CN106381165B (en) | A kind of combustible organic plus hydrogen method for upgrading | |
| CN214244305U (en) | Horizontal anaerobic pyrolysis and carbonization device for household garbage | |
| CN106635075B (en) | A kind of production method of bio-fuel | |
| CN106520170B (en) | A method of it converts garbage into carbonize functional material | |
| CN106398726B (en) | A kind of composting charing method | |
| CN106433770B (en) | It is a kind of for handle be derived from rubbish bio oil antigravity system | |
| CN219828838U (en) | Energy-saving double-fluidized-bed waste salt treatment device | |
| CN202610185U (en) | Equipment for refining fuel oil by using organic refuse |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200227 Address after: 2-6-3, No. 150, Changjiang Road, Zhongshan District, Dalian, Liaoning 116000 Patentee after: Liu Yan Address before: 100190, room 9, No. 1708 West Fourth Ring Road, Haidian District, Beijing Patentee before: New Austrian Ecological Environment Management Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201221 Address after: 201-257, 2 / F, building 2, yard 1, gaolizhang Road, Haidian District, Beijing 100089 Patentee after: Beijing qihonglan Environmental Protection Technology Co.,Ltd. Address before: 2-6-3, No. 150, Changjiang Road, Zhongshan District, Dalian City, Liaoning Province Patentee before: Liu Yan |
|
| TR01 | Transfer of patent right |