CN103980531B - Cellulose aerogels-amino formate compound oil spilling administers the preparation method of material - Google Patents
Cellulose aerogels-amino formate compound oil spilling administers the preparation method of material Download PDFInfo
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- CN103980531B CN103980531B CN201410244025.6A CN201410244025A CN103980531B CN 103980531 B CN103980531 B CN 103980531B CN 201410244025 A CN201410244025 A CN 201410244025A CN 103980531 B CN103980531 B CN 103980531B
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Abstract
Cellulose aerogels-amino formate compound oil spilling administers a preparation method for material, relates to the preparation method of the porous network shape structured material that a kind of hydrophobic-lipophilic-solidifying oiliness can have concurrently.Described method steps is as follows: the preparation of (1) cellulose aerogels; (2) preparation of superhydrophobic fibers element aerogel; (3) alkyl carbamate class fuel thickener is prepared; (4) preparation of cellulose aerogels-alkyl carbamate class fuel thickener matrix material.The present invention adopts the Mierocrystalline cellulose of natural reproducible to carry out hydrophobically modified to prepare oil absorption material as raw material, oil spilling prepared by oil absorption material and the effective compound of fuel thickener is administered material and have the solidifying oiliness energy of fuel thickener and the oil absorptiveness of oil absorber concurrently, have that cost is low, environmental friendliness, oil suction fast, solidifying oil is effective, protect many advantages such as oily rate is high, economic, biodegradable.
Description
Technical field
The present invention relates to the preparation method of the porous network shape structured material that a kind of hydrophobic-lipophilic-solidifying oiliness can have concurrently, be specifically related to the preparation method that a kind of cellulose aerogels-alkyl carbamate class fuel thickener compound oil spilling administers material.
Background technology
Growing along with global economy, more and more higher to the demand of oil and products thereof, in the exploitation and transportation of oil, there is many serious oil spill accidents.According to statistics, the annual oil spilling flowed into the sea because of various accident is up to 3000 ~ 5000kt in the world, also serious harm natural ecological environment while causing resource huge waste.As: 2010, the oil spill disaster occurring in the Gulfian caused wound that is huge, that be difficult to recovery to local environment; 2013, occur in " 11.22 " yellow Weihe River pipe laying explosion hazard in Qingdao, cause crude oil leakage, part crude oil overflowed into Qingdao sea area, brought safely huge injury also to the people's lives and property.In addition, etesian Oil spills accident also has a lot, so how effectively administering oil spilling is one of difficult point of facing of every country always, because the material requiring to administer oil spilling will not only effectively but also do not cause secondary pollution.Current main oil spilling control measures comprises the Physicals such as the oil fence, asphalt felt, oil skimmer vessel, and the biological methods such as oily microorganism are bitten in the chemical method such as oil spill dispersant, fuel thickener and input.Wherein, oil absorber is the class material developing the earliest, study most species, and it can active adsorption oil spilling, is convenient to salvage, reclaim, but also exist efficiency low, protect the shortcomings such as oily rate variance.Oil spilling rapid coagulation can be become solid or semi-solid mass by fuel thickener, and float on the water surface and be convenient to machinery salvaging, effectively can suppress the diffusion of oil, toxicity is low, and condensation of oil is convenient to reclaim.
Therefore, how to prepare efficient, cheap oil spilling and administer one of the focus and difficult point that material is current research, in order to avoid causing secondary pollution in oil spilling governance process, when last large study hotspot is exactly prepare oil spilling with natural, good biocompatibility, readily biodegradable material to administer material.Wherein, oil absorption material extensively adopts the cotton fibre of some modifications, the renewable sponge etc. of modification, and what fuel thickener current research was more is with the oil phase in organic gelling agent selectivity gelling oil-water mixture.Oil absorber can active adsorption oil spilling, but sometimes also there is shortcomings such as protecting oily rate variance, and fuel thickener can effectively by effective for oil phase gelling, and Oil keeping can be much higher than general oil absorption material.Therefore, consider fuel thickener and oil absorption material to carry out compound, prepare the compound oil spilling of a kind of oil absorber-fuel thickener and administer material, this will be the good direction that oil spilling administers Materials.
Summary of the invention
The object of this invention is to provide the preparation method that a kind of cellulose aerogels-amino formate compound oil spilling administers material, the fuel thickener that current research is compared focus by the method organically combines with the oil absorber prepared by natural product, prepares a kind of composite shape matl administered for oil spilling.
The object of the invention is to be achieved through the following technical solutions:
Cellulose aerogels-amino formate compound oil spilling administers a preparation method for material, and concrete operation step is as follows:
(1) freeze-drying is adopted to prepare cellulose aerogels: with wood pulp or other Mierocrystalline cellulose for raw material, by its in a certain amount of water with high pressure homogenizer by fiber homogeneity, cellulose aqueous solution concentration is 0.5 ~ 10wt%, then within the scope of 15 ~ 50 DEG C, carry out gel, prepare nanofiber hydrogel.This hydrogel to be spent the night in-5 ~-10 DEG C of cryogenic refrigerators pre-freeze, to be then placed at freeze drier-30 ~-50 DEG C fully lyophilize 12 ~ 48h, the cellulose aerogels of low density, high porosity can be obtained.
(2) preparation of superhydrophobic fibers element aerogel: adopt atomic layer deposition method between 100 ~ 200 DEG C in cellulose aerogels surface deposition one deck TiO prepared by step one
2or SiO
2deng inorganic coating, deposit thickness 10nm ~ 10 μm, make aerogel have super-hydrophobic, oleophylic performance.The aerogel of preparation is divided into the size of suitable dimension, this determines according to practical situations simultaneously.
(3) alkyl carbamate class fuel thickener is prepared: by the Toluene-2,4-diisocyanate of 1mol, the C of 4-vulcabond (TDI) and 2 ~ 2.2mol
4~ C
22fatty alcohol be raw material, both are joined in the suitable solvent of 100 ~ 200mL (as chloroform, acetone etc.), are uniformly mixed, be placed in water-bath or the oil bath stirring reaction of 40 ~ 60 DEG C.After reaction terminates, with atmospheric distillation distillation except desolventizing, pour in glass dish while hot, vacuum-drying at 120 ~ 140 DEG C by concentrated solution, cooling, pulverizing can obtain the alkyl carbamate class fuel thickener prepared.
In this step, described fatty alcohol is the mixture of one or more in propyl carbinol, n-hexyl alcohol, hexalin, n-Octanol, nonanol-, nonylcarbinol, undecyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, behenyl alcohol etc.
(4) preparation of cellulose aerogels-alkyl carbamate class fuel thickener matrix material: the fuel thickener prepared in step 3 is dissolved in abundant stirring in suitable organic solvent (as chloroform, acetone etc.) and obtains the homogeneous phase solution that concentration is 10 ~ 30wt%.A certain size super-hydrophobic, the plain aerogel of lipophilic fiber prepared in step 2 are joined in this solution, add-on is 10 ~ 50wt% of steeping fluid, flood, apply a certain amount of coating, coating time 0.5 ~ 3d, then organic solvent drying is removed.
Tool of the present invention has the following advantages:
1, in the present invention, oil absorber is selected, with natural product-Mierocrystalline cellulose, to prepare the cellulose aerogels of low density, high porosity, then at its surface deposition part inorganic coating, as TiO through methods such as simple lyophilize, supercritical dryings
2, SiO
2deng, obtain cellulose aerogels that is super-hydrophobic, oleophylic performance, be directly used in the preparation that compound oil spilling administers material.Mierocrystalline cellulose is natural polymer ancient, the abundantest on the earth, is inexhaustible, the natural reproducible resource that the mankind are the most valuable, and the hydroxyl isoreactivity group containing more easy reaction in its molecular structure, can so that further modify.
2, fuel thickener selects the supramolecule fuel thickener that current research is warmmer, it mainly utilizes micromolecular self-assembly performance, three-dimensional network structure can be self-assembled into by non-covalent interactions such as hydrogen bond, Van der Waals force, electrostatic attractions between small molecules, utilize surface tension, capillary force etc. by oil spilling equal solvent molecular retention on this basis or be fixed in network and form gel.In the present invention, fuel thickener selects Toluene-2,4-diisocyanate, 4-vulcabond (TDI) and C
4~ C
22fatty alcohol is raw material, and prepare alkyl carbamate class phase selectivity fuel thickener through simple single stage method, it has fibrous three-dimensional net structure, can form gel by effectively catching oil spilling molecule.
3, the present invention adopts the Mierocrystalline cellulose of natural reproducible and inorganic coating to prepare oil absorption material as raw material, the oil spilling both effective compounds prepared is administered material and is had the solidifying oiliness energy of fuel thickener and the oil absorptiveness of oil absorber concurrently, have that cost is low, environmental friendliness, oil suction fast, solidifying oil is effective, protect many advantages such as oily rate is high, economic, biodegradable.The fuel thickener selected also is the focus of current research.Mierocrystalline cellulose is again a kind of natural product, has good biocompatibility and biodegradability, and the inorganic coating of deposition is also nontoxic, so cause secondary pollution few.Therefore, the cellulose aerogels prepared-preparation of fuel thickener compound oil spilling improvement material is simple, cost is low, novel environment friendly, with good oleophylic and solidifying oiliness energy, solidifying oil-composite material for oil absortion prepared by the method is the new direction that oil spilling administers Materials.
4, prepared by the present invention hydrophobic, the using method that oleophylic cellulose aerogels-compound oil spilling of alkyl carbamate class fuel thickener administers material is simple, direct oil spillage 5 ~ 30wt% by this oil-spill chemical uniform broadcasting oil spilling surface or oil-water mixture in, namely can effective phase selectivity ground absorption-gelling oil phase and not absorbing water after 5 ~ 30min, wherein during 10wt% consumption, Russia's oil (~ 30min), diesel oil (~ 20min), treatment time of the oil products such as gasoline (~ 20min) higher than pure organic solvent as hexanaphthene (~ 5min), the treatment time of benzene (~ 8min) etc.Add in rear 12h, namely oil spilling can be adsorbed, gelling becomes block, salvaging can be carried out reclaim by direct fishing tool.
Embodiment
Below technical scheme of the present invention is further described, but does not limit to so, everyly technical solution of the present invention is modified or equivalently to replace, and do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: present embodiment is prepared the compound oil spilling of hydrophobic, oil loving cellulose aerogels-12CTDI alkyl carbamate class fuel thickener in accordance with the following steps and administered material:
Step one: the preparation of cellulose aerogels
Take paper pulp as raw material, by its with high pressure homogenizer by fiber homogeneity, make the size of cellulosic fibre at micron or Nano grade.Be dispersed in water and regulate the concentration of cellulose aqueous solution at about 0.5wt%, leave standstill within the scope of 35 DEG C and carry out gel, prepare nanofiber hydrogel.This hydrogel to be spent the night in the cryogenic refrigerator of-10 DEG C pre-freeze, obtain freezing cellulose aquagel.To be placed in freeze drier abundant vacuum lyophilization 48h at-30 DEG C, the cellulose aerogels of low density, high porosity can be obtained.
Step 2: the preparation of superhydrophobic fibers element aerogel
Adopt the cellulose aerogels surface deposition TiO that atomic layer deposition method is prepared in step one
2inorganic coating, depositing temperature 110 DEG C, depositing time 15min, make aerogel have super-hydrophobic, oleophylic performance, the aerogel of preparation be divided into the suitable size of 0.5mm × 0.5mm.
Step 3: prepare alkyl carbamate class fuel thickener
By the Toluene-2,4-diisocyanate of 1mol, the lauryl alcohol of 4-vulcabond (TDI) and 2mol is raw material, both is joined in 150mL chloroform, is uniformly mixed, and is placed in the stirred in water bath reaction of 60 DEG C.After reaction terminates, remove desolventizing with atmospheric distillation distillation at 90 DEG C, pour in glass dish while hot, vacuum-drying 8h at 140 DEG C by concentrated solution, cooling, pulverizing can obtain the 12CTDI alkyl carbamate class fuel thickener prepared.
Step 4: cellulose aerogels-alkyl carbamate class fuel thickener matrix material preparation
The fuel thickener 10g prepared in step 3 is dissolved in suitable 100mL chloroform fully stirring and obtains homogeneous phase solution.A certain size super-hydrophobic, the plain aerogel 20g of lipophilic fiber that prepare in step 2 are joined in this solution, dipping 3d, make the abundant self-assembly of hydroxyl isoreactivity group on alkyl carbamate base active group in fuel thickener and cellulose aerogels surface, fuel thickener is self-assembled in the hole of cellulose aerogels.Finally, impregnated cellulose aerogels is pulled out standing, when dripping to there is no organic solvent, being transferred in air dry oven fully dry at 80 DEG C, organic solvent finish-drying is removed.
Embodiment two: present embodiment is prepared the compound oil spilling of hydrophobic, oil loving cellulose aerogels-14CTDI alkyl carbamate class fuel thickener in accordance with the following steps and administered material:
Step one: the preparation of cellulose aerogels
Take paper pulp as raw material, by its with high pressure homogenizer by fiber homogeneity, make the size of cellulosic fibre at micron or Nano grade, be dispersed in water, regulate cellulosic concentration at 1wt%, leave standstill within the scope of 35 DEG C and carry out gel, prepare nanofiber hydrogel.This hydrogel to be spent the night in-10 DEG C of cryogenic refrigerators pre-freeze, obtain freezing cellulose aquagel.To be placed in freeze drier abundant vacuum lyophilization 48h at-30 DEG C, the cellulose aerogels of low density, high porosity can be obtained.
Step 2: the preparation of superhydrophobic fibers element aerogel
Adopt the cellulose aerogels surface deposition TiO that atomic layer deposition method is prepared in step one
2inorganic coating, depositing temperature 110 DEG C, depositing time 15min, make aerogel have super-hydrophobic, oleophylic performance, the aerogel of preparation be divided into the suitable size of 0.5mm × 0.5mm.
Step 3: prepare alkyl carbamate class fuel thickener
With the Toluene-2,4-diisocyanate of 1mol, the tetradecyl alcohol of 4-vulcabond (TDI) and 2mol is raw material, both is joined in 150mL acetone, is uniformly mixed, and is placed in the stirred in water bath reaction of 50 DEG C.After reaction terminates, remove desolventizing with atmospheric distillation distillation at 90 DEG C, pour in glass dish while hot, vacuum-drying 8h at 140 DEG C by concentrated solution, cooling, pulverizing can obtain the 14CTDI alkyl carbamate class fuel thickener prepared.
Step 4: cellulose aerogels-alkyl carbamate class fuel thickener matrix material preparation
The fuel thickener 10g prepared in step 3 is dissolved in suitable 100mL acetone fully stirring and obtains homogeneous phase solution.A certain size super-hydrophobic, the plain aerogel 10g of lipophilic fiber that prepare in step 2 are joined in this solution, dipping 3d, make the abundant self-assembly of hydroxyl isoreactivity group on alkyl carbamate base active group in fuel thickener and cellulose aerogels surface, fuel thickener is self-assembled in the hole of cellulose aerogels.Finally, impregnated cellulose aerogels is pulled out standing, when dripping to there is no organic solvent, being transferred in air dry oven fully dry at 80 DEG C, organic solvent finish-drying is removed.
Embodiment three: present embodiment is prepared the compound oil spilling of hydrophobic, oil loving cellulose aerogels-alkyl carbamate class fuel thickener in accordance with the following steps and administered material:
Step one: the preparation of cellulose aerogels
Take paper pulp as raw material, by its with high pressure homogenizer by fiber homogeneity, make the size of cellulosic fibre at micron or Nano grade.Be dispersed in water and regulate the concentration of cellulose aqueous solution at about 0.5wt%, leave standstill within the scope of 35 DEG C and carry out gel, prepare nanofiber hydrogel.This hydrogel to be spent the night in the cryogenic refrigerator of-10 DEG C pre-freeze, obtain freezing cellulose aquagel.To be placed in freeze drier abundant vacuum lyophilization 48h at-30 DEG C, the cellulose aerogels of low density, high porosity can be obtained.
Step 2: the preparation of superhydrophobic fibers element aerogel
Adopt the cellulose aerogels surface deposition SiO that atomic layer deposition method is prepared in step one
2inorganic coating, depositing temperature 150 DEG C, depositing time 20min, make aerogel have super-hydrophobic, oleophylic performance, the aerogel of preparation be divided into the suitable size of 0.5mm × 0.5mm.
Step 3: prepare alkyl carbamate class fuel thickener
With the Toluene-2,4-diisocyanate of 1mol, the lauryl alcohol of 4-vulcabond (TDI) and 2mol is raw material, both is joined in 150mL chloroform, is uniformly mixed, and is placed in the stirred in water bath reaction of 60 DEG C.After reaction terminates, remove desolventizing with atmospheric distillation distillation at 90 DEG C, pour in glass dish while hot, vacuum-drying 8h at 140 DEG C by concentrated solution, cooling, pulverizing can obtain the 12CTDI alkyl carbamate class fuel thickener prepared.
Step 4: cellulose aerogels-alkyl carbamate class fuel thickener matrix material preparation
The fuel thickener 10g prepared in step 3 is dissolved in suitable 100mL chloroform fully stirring and obtains homogeneous phase solution.A certain size super-hydrophobic, the plain aerogel 20g of lipophilic fiber that prepare in step 2 are joined in this solution, dipping 3d, make the abundant self-assembly of hydroxyl isoreactivity group on alkyl carbamate base active group in fuel thickener and cellulose aerogels surface, fuel thickener is self-assembled in the hole of cellulose aerogels.Finally, impregnated cellulose aerogels is pulled out standing, when dripping to there is no organic solvent, being transferred in air dry oven fully dry at 80 DEG C, organic solvent finish-drying is removed.
Claims (6)
1. cellulose aerogels-alkyl carbamate class fuel thickener compound oil spilling administers a preparation method for material, it is characterized in that described method concrete operation step is as follows:
(1) preparation of cellulose aerogels: take Mierocrystalline cellulose as raw material, by its in water with high pressure homogenizer by fiber homogeneity, then carry out gel at 15 ~ 50 DEG C, prepare nanofiber hydrogel; Then this hydrogel to be spent the night in-5 ~-10 DEG C of cryogenic refrigerators pre-freeze, to be placed at freeze drier-30 ~-50 DEG C fully lyophilize 12 ~ 48h, can cellulose aerogels to be obtained;
(2) preparation of superhydrophobic fibers element aerogel: adopt atomic layer deposition method at cellulose aerogels surface deposition one deck inorganic coating between 100 ~ 200 DEG C, deposit thickness 10nm ~ 10 μm, make aerogel have super-hydrophobic, oleophylic performance;
(3) alkyl carbamate class fuel thickener is prepared: with the Toluene-2,4-diisocyanate of 1mol, the C of 4-vulcabond and 2 ~ 2.2mol
4~ C
22fatty alcohol be raw material, both are joined in 100 ~ 200mL organic solvent and are uniformly mixed, stirring reaction under the condition of 40 ~ 60 DEG C; After reaction terminates, except desolventizing, pour in glass dish while hot by concentrated solution, vacuum-drying at 120 ~ 140 DEG C, cooling, pulverizing can obtain alkyl carbamate class fuel thickener;
(4) preparation of cellulose aerogels-alkyl carbamate class fuel thickener matrix material: the fuel thickener prepared in step 3 is dissolved in abundant stirring in organic solvent and obtains homogeneous phase solution; The cellulose aerogels prepared in step 2 is joined in this solution and flood 0.5 ~ 3d, then organic solvent drying is removed.
2. cellulose aerogels according to claim 1-alkyl carbamate class fuel thickener compound oil spilling administers the preparation method of material, it is characterized in that described inorganic coating is TiO
2or SiO
2.
3. cellulose aerogels according to claim 1-alkyl carbamate class fuel thickener compound oil spilling administers the preparation method of material, it is characterized in that described fatty alcohol is the mixture of one or more in propyl carbinol, n-hexyl alcohol, hexalin, n-Octanol, nonanol-, nonylcarbinol, undecyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, behenyl alcohol.
4. cellulose aerogels according to claim 1-alkyl carbamate class fuel thickener compound oil spilling administers the preparation method of material, it is characterized in that described organic solvent is chloroform and/or acetone.
5. cellulose aerogels according to claim 1-alkyl carbamate class fuel thickener compound oil spilling administers the preparation method of material, and it is characterized in that in described homogeneous phase solution, the concentration of fuel thickener is 10 ~ 30wt%.
6. cellulose aerogels according to claim 1-alkyl carbamate class fuel thickener compound oil spilling administers the preparation method of material, it is characterized in that the add-on of described cellulose aerogels is 10 ~ 50wt% of steeping fluid.
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| CN106367947A (en) * | 2016-10-12 | 2017-02-01 | 武汉纺织大学 | Method for improving tensile mechanical property of fibers |
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