CN106362438B - Water-oil separationg film and its application - Google Patents
Water-oil separationg film and its application Download PDFInfo
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- CN106362438B CN106362438B CN201611032406.3A CN201611032406A CN106362438B CN 106362438 B CN106362438 B CN 106362438B CN 201611032406 A CN201611032406 A CN 201611032406A CN 106362438 B CN106362438 B CN 106362438B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
Abstract
The present invention provides a kind of water-oil separationg film and its application, the seperation film is the seperation film based on polyvinylidene fluoride.The bio oil that high temperature garbage distillation charing obtains can be effectively separated from water by the seperation film, to obtain high-quality biological oil.
Description
Technical field
The invention belongs to filtration and separation techniques fields, and in particular to a kind of water-oil separationg film and its application.
Background technique
Membrane separation technique is used widely, wherein many membrane separation techniques have application to water-oil separating.Bio oil crude oil
Quality is usually poor, needs just to be able to satisfy demanded fuel through successive modified upgrading.Bio oil upgrading mainly include hydrogenation deoxidation,
Catalytic cracking, catalytic reforming and catalytic esterification, catalysis upgrading can change the composition of bio oil, fundamentally change bio oil
Quality.How bio oil to be separated from water to obtain low water content or water-free bio oil is always the technological challenge of this field
One of.
With rapid economic development, urbanization process is persistently accelerated, so that the quantity in city and the scale in city are also continuous
Ground changes, and expands, due in city resident population and urban size increased dramatically, domestic waste total amount with
Increase considerably.The year two thousand thirty is predicted, Municipal Solid Waste in China annual output is up to 4.09 hundred million tons.Big and medium-sized cities, especially
Be megalopolis refuse production per capita it is relatively high, rate of rise reach 20% or so.
If processing and disposition that cannot be appropriate to these rubbish, poisonous and harmful substance therein will pass through certain ring
Border medium such as soil, atmosphere, earth's surface or underground water enter in the ecosystem and form pollution.This can not only destroy ecological environment,
Lead to irreversible Ecological Changes, but also can cause damages to the health of animals and plants safety and the mankind.
Garbage disposal at present is typically all to reduce waste volumes by burning disposal.Burning disposal method can generate dioxin
Etc. various environmentally hazardous polluters, safe garbage incineration equipment price is high, scale of investment is big, and burning disposal can only
It is used to maintain to run by handling, resin, Plastic account for 10% or so in conventional rubbish, and remaining is exactly kitchen, paper, wood chip
Deng.
CN105771673A discloses a kind of polymeric membrane for separation, which is pressurizeed by macromolecule meson material
It is thermally formed, the macromolecule meson material is by hydrophilic resin or oleophilic resin, silica, shell particles, iron oxide, plant grain
Son is obtained with curing agent mixture.
CN105396468A discloses a kind of PVDF seperation film, using Kynoar as the raw material of film, Kynoar system
Standby steps are as follows: 1) 1~2 parts by weight hydroxyethyl cellulose, 2.4 parts by weight hydrogen peroxide, 3.7 parts by weight of inorganic are put into reaction kettle
Aqueous slkali is uniformly mixed, then to put into 0.7 parts by weight nonylphenol ethylene oxide carboxylic, 9.7 parts by weight, ten trifluoroethane molten
Agent, 1.8 parts by weight isobutyryl chloride solution, are stirred to react 39 minutes at -7.5 DEG C；2) 2.8 parts by weight castor oil polyoxy second are put into again
Alkene ether, 5.7 parts by weight N-Methyl pyrrolidone solution, 83 parts by weight vinylidene fluoride monomers, 2.6 parts by weight chlorocyclopentanes,
21 DEG C are stirred to react, and pressure terminates reaction when dropping to 0.23MPa or less；3) it is filtered, washed, dries to get powdered poly- inclined
Vinyl fluoride.
CN103167904 discloses a kind of seperation film, containing hydrophilic molecule and has in its supply side and penetrates side
At least one surface on 80 microns to 2000 microns of difference in height being formed, wherein in over dry seperation film hydrophilic molecule weight
Amount is calculated as 0.1% to 40% on the basis of the weight of over dry seperation film for having deducted the weight of hydrophilic molecule.
CN105536556A discloses a kind of seperation film with oleophobic properties, by immersion or spraying method in porous base
Film surface modification improves the oleophobic properties of seperation film by curing process rich in all-fluoroalkyl compound coating, can apply air
Gases and the liquid handling fields such as filtering, membrane distillation desalination, water-oil separating, improve the anti-fouling performance of film.
CN103961905A discloses a kind of super-hydrophobic/oleophylic water-oil separating low in cost and high-efficient water-oil separating
The preparation method of nethike embrane.The present invention by using low-cost inorganic matter as part material, using relatively mild preparation work
Skill is formed nanoscale papillary structure on metal mesh with sol method, and is received with low-surface-energy organic modifier to what is constructed
Rice SiO2It is modified, has been prepared into super-hydrophobic/oleophylic oil-water separation mesh film.
CN102085459A discloses a kind of preparation method of anti-pollution high-efficiency water-oil separating ultrafiltration membrane, by casting solution quality
100 meters, solvent n,N-Dimethylformamide dissolve the cellulose acetate of 16.0% mass, and ethyl orthosilicate, mass fraction is added
It is 15.0~30.0%, scrapes the nascent state film of 240 μ m-thicks on a glass；25 are immersed again after placing 10~30 seconds in air
DEG C coagulation bath；Aqueous hydrochloric acid solution and sodium hydrate aqueous solution is respectively adopted in coagulation bath；By film from coagulation bath take out, be placed in from
In sub- water, every 5h changes a water, obtains CA (TEOS)-HCl and CA (TEOS)-NaOH modified ultrafiltration membrane
CN103861466A discloses a kind of preparation method of hydrophily seperation film.The seperation film includes basement membrane support
Hydroaropic substance is introduced into through hydroxylating treated basement membrane branch by layer and hydrophily separation membrane layer by film surface chemical reaction
Support layer surface forms hydrophilic separating layer.
CN101402874A discloses the combustion oil-forming method of a kind of biological sludge and organic waste, and this method is by biological sludge
It is pyrolyzed to obtain the method for oily substance as raw material with organic waste, biological sludge includes the dirt that Sewage Biological Treatment obtains
Mud and algae sludge, organic waste include domestic waste, agricultural crop straw and trees material.
CN101724679A discloses a kind of method using kitchen garbage production biodiesel, includes the following steps:
Except the solid sundries in kitchen garbage, mashing is added water, adjusts pH value to faintly acid, sterilizing；Kitchen garbage is homogenized inoculation ferment
Mother cell carries out liquid state fermentation, 25~30 DEG C of 70~75h of air agitations fermentation；Fermentation liquid collects yeast cells after filtering；Ferment
For mother cell through high-pressure homogeneous crusher machine, extractant is added in smudge cells, and extraction collects upper layer organic solvent and mutually obtains miscella,
Solvent in evaporation recycling miscella obtains microbial oil；Microbial oil obtains biodiesel after esterification reaction of organic acid.
KR20110084323A discloses food-trash treatment and biological oil extraction device, and composition is, by food refuse
Fermentation drying machine and the fermenting cellar for putting into existing microorganism investment are dry through fermentation in 24 hours and decompose and be reduced, by drying and
The organic matter of decomposition is ground into small particles using pulverizer, then low temperature adds under environment under low pressure in alembic by the particle of crushing
The gas of heat, vapor, oil of the separation discharge through thermal decomposition gasification, discharge is separated into moisture after the cooled liquefaction of destilling tower
(liquid carbon fertilizer) and oil, then the oil of separation is supplied to whizzer after vacuum canister seals collection to refine.
WO2012/148359A1 discloses a kind of polymer film for being separated from water oil, the hole of the polymer film
Diameter is 0.005 μm to 5 μm, and with a thickness of 50 μm to 1,000 μm, water contact angle is 0 ° to 60 °, and oily contact angle is 40 ° to 100 °, institute
Stating film includes hydrophobic matrix polymer and the functional polymer containing hydrophobic framework and side chain, each described side chain, which has, to be dredged
The end segment and hydrophilic inner section of oil.
US2014/056714A is disclosed to be gathered by crosslinking rubber polyurethane-ether polymer manufacture crosslinking rubber polyurethane-ether
Film is closed, there are four the tetrols of hydroxy functional group to synthesize by diisocyanate terminated polyethers and tool for the polymer, on the tetrol
Hydroxyl is reacted with the isocyanate groups on the diisocyanate terminated polyethers to form ammonia ester bond, the crosslinking rubber polyurethane-
Ether polymeric membrane selectively penetrating condensable vapours, simultaneously such as C3 to C35 hydrocarbon, aromatic compounds, vapor, carbon dioxide and hydrogen sulfide
Methane and ethane are retained, which has to the high osmosis of condensable vapours, to condensable steaming
Gas is more than highly selective and to liquid chemical the height endurability to methane and ethane.
" novel water-oil separating membrane material progress ", Luo Yongle etc., New Chemical Materials, 11 phases in 2015, to current
Water-oil separationg film investigation of materials status has carried out detail discussion, looks forward to its future research trends on this basis.
" structure of super impregnating porous film designs and emulsification water-oil separating application study ", Jin Jian, Chinese Chemical Society the 29th
Annual Conference abstract collection the-the 09 branch: applied chemistry, 2014, around efficient lotion separation perforated membrane structure design and
Research designs the structure and performance boost of regulation film with Bionic Idea, breaks through the structure and performance limit of conventional polymer seperation film
System realizes high-throughput, efficient lotion water-oil separating, and by regulating and controlling macromolecule inversion of phases process, building surface is multiple with micro-nano
The high-molecular porous filter membrane for closing structure makes film have the different special wellabilities for oil and water, while having both macromolecule filter
The nano pore structure of film realizes for the big flux of various Water-In-Oils and oil-in-water micron and nanoscale emulsion, efficiently divides
From.
Above-mentioned document and it is other in the prior art, although having some seperation films about grease or hydrocarbon fuel and water,
However, by the high temperature garbage distillation obtained bio oil of charing and common grease or hydrocarbons, there are larger differences, even if adding
After hydrogen upgrading processing, ingredient is still very complicated, and compared with grease or hydrocarbon fuel, composition quantity will have more several times, and also deposit
In various polarity component, lotion easily is formed with water, when being separated using common seperation film, separative efficiency is also very low,
Such as it is difficult to efficiently separate and to separate flux very low.This field needs one kind that can effectively obtain high temperature garbage distillation charing
Bio oil, particularly improving quality of bio oil be separated from water to obtain the seperation film of high-quality biological oil.
Summary of the invention
To solve the above problems, the present inventor with system research, abundant distill in conjunction with high temperature garbage by deeply carbonizing
The composition and property feature of the bio oil arrived, have made intensive studies seperation film, provide following seperation film, thus effectively
The bio oil that high temperature garbage distillation charing obtains is separated from water.
In one aspect of the invention, a kind of water-oil separationg film is provided, which is point based on polyvinylidene fluoride
From film.
Preferably, which is modified polyvinylidene fluoride-hexafluoropropene seperation film.
Preferably, which is modified using cellulose.The cellulose is preferably carboxymethyl cellulose.
Content of cellulose can be 10-20wt.%, preferably 15wt.% in seperation film.
For the present invention, film used in UF membrane (i.e. seperation film) is hydrophilic film.
Preferably, the average pore size of the film is about 0.5-0.7 μm, and maximum diameter of hole is no more than 0.90 μm.
It is highly preferred that the water contact angle of the film is essentially 0.
It is further preferred that the elasticity modulus of the film is 60.0-90.0MPa.
In an especially preferred embodiment, the film is the seperation film based on polyvinylidene fluoride.It is further excellent
Selection of land, the seperation film based on polyvinylidene fluoride are polyvinylidene fluoride-hexafluoropropene seperation film.
The present inventor separates polyvinylidene fluoride-hexafluoropropene by further further investigation, by using cellulose
Film is modified, and is obtained a kind of polyvinylidene fluoride-hexafluoropropene seperation film of new modification, is particularly suited for the present invention
The separation of bio oil and water that middle high temperature garbage distillation charing obtains.
Particularly, the method for modifying is preferably as follows:
(1) polyvinylidene fluoride-hexafluoropropene (PVDF-HFP) is dissolved in acetone and DMF mixed solution (acetone: DMF
Volume ratio is 1:5-5:1) in, it is 5-15wt.%, the preferably solution of 10wt.% that concentration, which is made,；
(2) Electrospun then is carried out using electric spinning device (for example, Nanon-01A is purchased from Japanese MECC), wherein
Electrospun chamber temp is room temperature to 40 DEG C, preferably room temperature, relative humidity 40-70%；The solution is placed in Electrospun note
In emitter, syringe needle diameter is 0.2-0.8mm, preferably 0.5mm；Apply 10-40kV between syringe needle and rotating disk, preferably
The voltage of 25kV, solution feed rate remain 0.5-2.0ml/h, preferably 1.0ml/h, collect the film that electricity spinning fibre is constituted
It (i.e. electricity spinning fibre film) and is dried at 45 DEG C for 24 hours, electricity spinning fibre film obtained is subjected to hot pressing；
(3) ionic liquid shown in cellulose (such as microcrystalline cellulose) and lower formula (I) or (II) is depressurized respectively
It is dry:
Wherein, drying temperature is 65-80 DEG C independently of one another, such as is 70 DEG C, and drying time is 10- independently of one another
30h, such as be 20h；
(4) cellulose after drying is added in the ionic liquid, 2-8wt.%, preferably 5wt.% is made
Cellulose solution, then the cellulose solution is coated in made from step (1) on electricity spinning fibre film, allows cellulose solution
Electricity spinning fibre film 1-5h, preferably 3h are penetrated through, then has the electricity spinning fibre film of the cellulose to be immersed in the water infiltration
To remove the ionic liquid, 1-3h, preferably 2h are then rotated in boiling water, and be washed with deionized, seperation film is made.
Certainly, it will be appreciated by those of skill in the art that can be separated to above-mentioned modified polyvinylidene fluoride-hexafluoropropene
Membrane preparation method makes scaling up.
With reference to Fig. 1, which shows the hole that cellulose is attached between the fiber surface and fiber of electricity spinning fibre film
In.The high surface area of this nanofiber of electricity spinning fibre film enables cellulose to be forcefully attached to electricity spinning fibre
In the whole thickness of film.Speculate its reason, compared with general organic solvent, the use of the ionic liquid can be by fiber
Effect is known as to carry into the hole of electricity spinning fibre film.
Electricity spinning fibre film after cellulose impregnates has 0.5-0.7 μm, preferably from about 0.65 μm of average pore size, wherein
The aperture of largest hole is no more than 0.90 μm, and since the dipping of cellulose is filled, porosity drops to 45% by original 90%.This
The diameter for the emulsion droplet that the improving quality of bio oil of invention and the mixture of water are formed is typically larger than 18 μm, therefore separation of the invention
Film can play good oil resistance effect.
For seperation film of the invention due to the introducing of cellulose, water contact angle is essentially 0, to have splendid hydrophily
Energy.
In addition, the inventors discovered that, the cellulose after the immersion of the ionic liquid shown in formula (I) or formula (II), before immersion
It compares, forms three-dimensional hydrogen bond network, the structure of cellulose is made to be effectively improved and be kept, and can effectively control hole
Rate, hydrophily and mechanical performance, and general solvent can not obtain this effect.In addition, shown in selection formula (I) or formula (II)
Ionic liquid, be because the ionic liquid in nitrogen-atoms can with cellulose formed hydrogen bond, and its spatial configuration of molecules with
The hole of electricity spinning fibre film matches, on the one hand can be by the effective band of cellulose to Electrospun fibre compared with other ionic liquids
In the hole for tieing up film, on the other hand, and it is unlikely to " to block " in the hole of electricity spinning fibre film and be difficult to remove.When the formula of using
(II) shown in when ionic liquid, due to the strong electron attraction of Cl atom and the polarity of hydroxyl, cellulose can be made more evenly
With the pore surface for being securely attached to electricity spinning fibre film.
Preferably, content of cellulose is 10-20wt.% in the seperation film.
Preferably, the elasticity modulus of the seperation film is 60.0-90.0MPa, tensile strength 10.0-12.0MPa, fracture
Elongation is 100-150%.
The cellulose is preferably carboxymethyl cellulose.
In an especially preferred embodiment, the cellulose is modified cellulose, preferably by the following method
It is modified:
2.0g cellulose and 4.0g polyglutamic acid (monomer mole ratio about 1:2.5-3) mixing are weighed, then under infrared lamp
It is fully ground 30min and obtains uniform fine-powder, make cosolvent with 20mL dimethyl sulfoxide (DMSO), 30min is stirred by ultrasonic, make it
In even dispersion DMSO dicyandiamide solution, system is warming up to 120 DEG C by oil bath, sulphur acid as catalyst is added under heating stirring, instead
6h is answered, reaction system is filtered, filter residue ethyl alcohol, deionized water are washed, then washed with saturated sodium bicarbonate, and deionization is then used
Water washing is finally successively washed with ethyl alcohol, acetone, 80 DEG C of drying obtain modified cellulose again to neutrality.
By using above-mentioned chemical modification method, modification can be carried out to the polyhydroxy of cellulose surface, led to simultaneously
Introducing carboxyl, amino groups are crossed, in modified cellulosic molecule, has been grafted carboxylic acid functional, to be effectively improved its parent
It is aqueous.In addition, the use of polyglutamic acid, hydrophilic simultaneously being effectively improved its compared with other modifying agent, and do not deteriorate fibre
It ties up the intensity of element and influences the performance of its cellulosic nature.
In another aspect of this invention, above-mentioned water-oil separationg film and its application are provided, can be applied to the life through upgrading
Bio oil and water separates in the mixture of object oil and water.
The mixture of the bio oil and water through upgrading can be obtained by following technique, which includes following step
It is rapid: (1) rubbish to be subjected to high temperature distillation charing and obtain the gas stream comprising coarse biometric oil and vapor；(2) by the gas
Logistics carries out hydrotreating, and coarse biometric oil therein is carried out upgrading；(3) gas stream through hydrogenated processing is carried out cold
It is solidifying, obtain the mixture of bio oil and water through upgrading.
More specifically, the step (1) are as follows: rubbish is packed into rubbish feeding device；Rubbish feeding device is set to pass through high temperature
Distill carbonizing apparatus.
In step (3), the mixture of improving quality of bio oil and water is obtained after condensation, it is raw to obtain upgrading by membrane separating method
Object oil.
Normally, in the mixture of improving quality of bio oil and water, water content 20-60wt.%, preferably 30-50wt.%, more
It is preferred that 40wt.%.
Preferably, in step (2), the gas stream is made to pass through catalyst bed in a gaseous form.The catalyst bed is preferred
For hydrogenation catalyst bed.
Preferably, the rubbish is domestic waste.
In a preferred embodiment, high temperature distillation carbonizing apparatus is heated by high temperature anaerobic steam.
The temperature of the high temperature anaerobic steam is preferably 320-560 DEG C, and more preferable 360 DEG C.
It preferably, include nitrogen in the high temperature anaerobic steam.
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.%.
In the present invention, it is preferred to rubbish without any pretreatment.
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
, do not select following high temperature distillation charing process condition: (1) when rubbish composition in the total weight of rubbish, organic species
When content >=80 weight %, the temperature of high temperature anaerobic steam is 300-450 DEG C, preferably 300-400 DEG C；In high temperature anaerobic steam
Nitrogen content is 10-30v.%, preferably 10-20v.%；Residence time in high temperature distillation carbonizing apparatus is 8-12h；(2)
When in rubbish composition with the total weight of rubbish, when organic species content 80 weight % of < and preferably plastic, rubber substance
When 10 weight % of content <, the temperature of high temperature anaerobic steam is 450 DEG C -600 DEG C, preferably 500 DEG C -550 DEG C；High temperature anaerobic steam
In nitrogen content be 40-80v.%, preferably 60-80v.%；Residence time in high temperature distillation carbonizing apparatus is 5-8h.
In a preferred embodiment, the catalyst in the catalyst bed is that inorganic oxide or silicate load
Ferrum-based catalyst perhaps charcoal load ferrum-based catalyst or the two mixture.
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 can be zeolite or molecular sieve, catalysis
Active component can be Fe2O3With the mixture of at least two transition metal and at least one noble metal.The transition metal choosing
From Ni, Cu, Fe, Ce etc., the noble metal is selected from Pt, Pd, Ru etc..
In an especially preferred embodiment, catalyst can be catalyst shown in following formula: Ni-Cu-Pd-
Co2O3-Fe2O3/ HZSM-5, 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%.HZSM-5 is carrier.Preferably, HZSM-5 is the HZSM-5 of low silica-alumina ratio, such as silica alumina ratio is lower than 15,
More preferably less than 10, this is because the acid strong HZSM-5 of discovery is more advantageous to the cracking of bio oil heavy component, bio oil is steamed
It is minimum to evaporate residue.
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, can through research
Enough be effectively embedding in the duct of HZSM-5 molecular sieve, this for improve catalytic active component activity, selectivity and stabilization
Property has very positive meaning.However, Co can cover hydrogenation sites Ni, Cu etc. if Co amount is excessive, 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 sieve 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 sieve has 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.
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
HZSM-5 molecular sieve is put into reaction vessel, and the solution prepared is poured into reaction vessel, is placed in the constant temperature with blender and is 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 hot oil 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.
When using the catalyst, the oxygen content in the bio oil through upgrading is 5.2wt.%, and catalyst life is about
720h.In contrast, using conventional NiMo/Al2O3Oxygen when catalyst, in the bio oil through upgrading of acquisition
Content is 19.7wt.%, and catalyst life is about 120h.
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 bio oil through upgrading obtained according to preceding method is provided.Preferably, described
Oxygen content is lower than 10 weight %, preferably shorter than 5 weight %, more preferably less than 2 weight % in bio oil through upgrading.Further
The higher calorific value on ground, the bio oil through upgrading is greater than 40MJ/kg.
In another aspect of this invention, the charcoal class object of method according to any of the preceding claims acquisition is provided
Matter.
Preferably, the charcoal substance is active carbon.It may be used as catalyst carrier, such as above-mentioned for replacing
HZSM-5 molecular sieve is as catalyst carrier.
Detailed description of the invention
Fig. 1 is the according to embodiments of the present invention 1 modified polyvinylidene fluoride-hexafluoropropene seperation film surface obtained
SEM figure.
Fig. 2 is the according to embodiments of the present invention 1 modified polyvinylidene fluoride-hexafluoropropene seperation film cross section obtained
SEM figure.
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
Polyvinylidene fluoride-hexafluoropropene seperation film is modified with cellulose by following method, to prepare modification
Polyvinylidene fluoride-hexafluoropropene seperation film: (1) polyvinylidene fluoride-hexafluoropropene (PVDF-HFP) is dissolved in acetone
In DMF mixed solution (acetone: DMF volume ratio is 3:1), the solution that concentration is 10wt.% is made；(2) electrospinning is then used
Silk device (Nanon-01A is purchased from MECC Japan) carries out Electrospun, and wherein Electrospun chamber temp is room temperature, relative humidity
It is 45%；The solution is placed in Electrospun syringe, syringe needle diameter is 0.3mm；Between syringe needle and rotating disk
Apply the voltage of 25kV, solution feed rate remains 1.0ml/h, collects film (the i.e. electricity spinning fibre that electricity spinning fibre is constituted
Film) and dried for 24 hours at 45 DEG C, electricity spinning fibre film obtained is subjected to hot pressing；(3) by cellulose (such as microcrystalline cellulose)
It is dried under reduced pressure respectively with ionic liquid shown in lower formula (I):
Wherein, drying temperature is 70 DEG C, and drying time is 20h；(4) cellulose is added to the ionic liquid
In, the cellulose solution of 5wt.% is made, the cellulose solution is then coated in electricity spinning fibre film made from step (1)
On, it allows cellulose solution slowly to penetrate through electricity spinning fibre film 3h, then infiltration is had to the electricity spinning fibre of the cellulose
Film is immersed in the water to remove the ionic liquid, 2h is then rotated in boiling water, and be washed with deionized, and modified polyvinilidene is made
Difluoroethylene-hexafluoropropene seperation film.
Embodiment 2
Choose the house refuse from Haidian District, Beijing City garbage compression transfer station, by following steps to above-mentioned rubbish into
Row high temperature distillation charing: (1) rubbish is packed into rubbish feeding device；(2) disguise rubbish feeding device across high temperature distillation charcoal
It sets；(3) gas stream of coarse biometric oil and vapor is taken out from high temperature distillation carbonizing apparatus top；(4) make the gas stream with
Gaseous form passes through catalyst bed；(5) effluent of self-catalysis in future agent bed is condensed, and obtains bio oil and water through upgrading
Mixture；(6) charcoal substance is obtained from the rubbish feeding device for passing through high temperature distillation carbonizing apparatus.The high temperature distillation charing
Device is heated by high temperature anaerobic steam, and the temperature of high temperature anaerobic steam is 350 DEG C, and the nitrogen in high temperature anaerobic steam contains
Amount is 12v.%, and processing average time is 9.0 hours.Combustible organic is mentioned using hydrodeoxygenation process in gas stream
Matter, the catalyst of the catalyst bed are Ni-Cu-Pd-Co2O3-Fe2O3/ HZSM-5, wherein mole of Ni, Cu, Pd, Co, Fe
Than being based on overall catalyst weight meter, Ni-Cu-Pd-Co for 2:8:0.15:1.5:152O3-Fe2O3The content of catalytic active component
It is 5%, adding hydrogen upgrading condition is 250 DEG C, 8.0MPa hydrogen pressure, 2h.Coke is obtained by this method and through the bio oil of upgrading.
Oxygen content in the bio oil is 5.2wt.%, and catalyst life is about 720h.
The seperation film prepared using embodiment 1 separates the mixture of bio oil and water through upgrading, oil separation effect
Oil × 100% existing for rate=(oil carried in the water that oil-existing for oil hydrosol Central Plains filters out)/oil hydrosol Central Plains.Point
From test condition are as follows: oil hydrosol amount is 5.0L, and the vacuum that seperation film applies is 65kPa, disengaging time 15min, seperation film
Area 20cm2.After tested, the separation of water is realized in 15min, in addition, separation membrane separation efficiency (i.e. oily separative efficiency) is
92%.
Comparative example 1
The difference of the comparative example and embodiment 2 is only that seperation film is polyvinylidene fluoride-hexafluoropropene film, i.e., without this
Modified polyvinylidene fluoride-hexafluoropropene the seperation film of inventive method.After tested, the separation of water is just realized through 1h, in addition, point
It is 51% from membrane separation efficiency (i.e. oily separative efficiency).
By above-described embodiment and comparative example clearly it can be seen from technique of the invention charing distilled to high temperature garbage obtain
Bio oil and water mixture (lotion) have extraordinary water-oil separating efficiency.In addition, seperation film of the invention have compared with
Good separation flux, that is, separating the required time is obviously shortened, to mean that separating capacity is stronger.
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 (8)
1. a kind of water-oil separationg film, which is modified polyvinylidene fluoride-hexafluoropropene seperation film, which uses
Cellulose is modified, and the method for modifying is as follows:
(1) polyvinylidene fluoride-hexafluoropropene (PVDF-HFP) is dissolved in acetone and DMF mixed solution, wherein acetone:
DMF volume ratio is 1:5-5:1, and the solution that concentration is 5-15wt.% is made；
(2) Electrospun then is carried out using electric spinning device, wherein Electrospun chamber temp is room temperature to 40 DEG C, and relative humidity is
40-70%；The solution is placed in Electrospun syringe, syringe needle diameter is 0.2-0.8mm；In syringe needle and rotating disk
Between apply the voltage of 10-40kV, solution feed rate remains 0.5-2.0ml/h, and collecting the film that electricity spinning fibre is constituted is
Electricity spinning fibre film is simultaneously dried for 24 hours at 45 DEG C, and electricity spinning fibre film obtained is carried out hot pressing；
(3) ionic liquid shown in cellulose and lower formula (I) or (II) is dried under reduced pressure respectively:
Wherein, drying temperature is 65-80 DEG C independently of one another, and drying time is 10-30h independently of one another；
(4) cellulose after drying is added in the ionic liquid, the cellulose solution of 2-8wt.% is made, so
The cellulose solution is coated on electricity spinning fibre film made from step (2) afterwards, cellulose solution is allowed to penetrate through Electrospun
Then infiltration is had the electricity spinning fibre film of the cellulose to be immersed in the water to remove the ionic liquid, so by tunica fibrosa 1-5h
1-3h is rotated in boiling water afterwards, and is washed with deionized, seperation film is made.
2. seperation film according to claim 1, the cellulose is carboxymethyl cellulose.
3. seperation film according to claim 1 or 2, wherein content of cellulose is 10-20wt.% in seperation film.
4. application of the seperation film according to any one of the preceding claims in the mixture of separating bio-oil and water.
5. application according to claim 4, wherein the mixture of the bio oil and water is from high temperature garbage retort carbon
Change processing.
6. application according to claim 5, wherein the bio oil is the bio oil of hydrogenated upgrading.
7. application according to claim 5 or 6, wherein the rubbish is domestic waste.
8. application according to claim 5 or 6, wherein high temperature distillation carbonizing apparatus is added by high temperature anaerobic steam
Heat.
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| CN112108016A (en) * | 2020-10-13 | 2020-12-22 | 天津工业大学 | Preparation method of spider-web-structure-imitated oil-water separation membrane |
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| CN101720257A (en) * | 2007-05-26 | 2010-06-02 | 斯托尼布鲁克水净化公司 | High flux fluid separation membranes comprising a cellulose or cellulose derivative layer |
| CN102085459A (en) * | 2009-12-03 | 2011-06-08 | 中国石油天然气股份有限公司 | Method for preparing anti-polluting oil-water separation ultra-filtration membrane |
| CN103521095A (en) * | 2013-10-31 | 2014-01-22 | 上海赛奥分离技术工程有限公司 | Method for preparing tubular ceramic membrane for oil-water separation |
| CN105833741A (en) * | 2016-04-25 | 2016-08-10 | 中国科学院兰州化学物理研究所 | Preparation method for polyvinylidene fluoride (PVDF) porous film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101720257A (en) * | 2007-05-26 | 2010-06-02 | 斯托尼布鲁克水净化公司 | High flux fluid separation membranes comprising a cellulose or cellulose derivative layer |
| CN102085459A (en) * | 2009-12-03 | 2011-06-08 | 中国石油天然气股份有限公司 | Method for preparing anti-polluting oil-water separation ultra-filtration membrane |
| CN103521095A (en) * | 2013-10-31 | 2014-01-22 | 上海赛奥分离技术工程有限公司 | Method for preparing tubular ceramic membrane for oil-water separation |
| CN105833741A (en) * | 2016-04-25 | 2016-08-10 | 中国科学院兰州化学物理研究所 | Preparation method for polyvinylidene fluoride (PVDF) porous film |
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