CN107043462B - A method of nano lignin is prepared using reversed-phase emulsion - Google Patents

A method of nano lignin is prepared using reversed-phase emulsion Download PDF

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CN107043462B
CN107043462B CN201710376235.4A CN201710376235A CN107043462B CN 107043462 B CN107043462 B CN 107043462B CN 201710376235 A CN201710376235 A CN 201710376235A CN 107043462 B CN107043462 B CN 107043462B
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reversed
lignin
emulsion
phase emulsion
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CN107043462A (en
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苏胜培
汪绍军
李军桦
汪巧蕾
刘志刚
邹海平
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Hunan Normal University Chemical New Materials Research Institute Co ltd
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Hunan Normal University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00Macromolecular compounds derived from lignin, e.g. tannins, humic acids

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Abstract

A method of nano lignin is prepared using reversed-phase emulsion, lipophilic emulsifier is dissolved in oil-based solvent and prepares oily phase, hydrophilic emulsifier and alkali lignin are dissolved in water preparation water phase, then water phase is added drop-wise in oily phase, and alkali lignin reversed-phase emulsion is prepared under being vigorously stirred;Dilute acid soln is added drop-wise in oily phase with vigorous stirring and prepares diluted acid reversed-phase emulsion, diluted acid reversed-phase emulsion is mixed with alkali lignin reversed-phase emulsion again, it is slowly stirred certain time after mixing, obtains nano lignin after being finally demulsified, filtered, washed and being freeze-dried.Prepared by the method nano lignin size uniformity, partial size is in 100-150 nm, and present invention process process is simple, and solution used is recyclable, to environment without negative effect, has a good application prospect.

Description

A method of nano lignin is prepared using reversed-phase emulsion
Technical field
The present invention relates to a kind of methods for preparing nano lignin, prepare nanometer using reversed-phase emulsion more particularly, to a kind of The method of lignin.
Background technique
Lignin is the most abundant renewable and biodegradable natural organic high-molecular in the world in addition to cellulose, It is one of the important substrate of new bio sill.It is main containing a large amount of phenyl ring, hydroxyl, methoxyl group etc. in lignin molecule structure Structural unit and group are wanted, makes lignin that there are special physicochemical properties.Pair of the alkali lignin as pulp and paper industry Product, annual global yield have 70,000,000 tons, and 95% is used as fuel or is discharged with black liquor, and only 5% is used for High value added product is produced, mainly includes additive, dispersing agent, adhesive and surfactant.In recent years, with human society Attention to resource and environment sustainable development, the development and utilization of the renewable biomass resources such as lignin gradually cause extensively Concern.
The continuous development of nanotechnology provides a new way for lignin-base product high value added utilization, and nanometer is wooden Crude granule possess bigger serface, antibacterial, with the features such as polymer substrate compatibility is good and no cytotoxicity, nano wood can be promoted Application of the quality in fields such as inorganic filler, organizational project, photocatalysis carrier and regenerative medicines.Chinese invention patent CN105829406A、CN104497322A、CN102002165A、CN103145999A、CN105153720A、 CN105854936A, CN103275331A and CN103254452A have been utilized respectively the precipitation method, supercritical fluid technique, Static Spinning The technologies such as silk technology, high pressure homogenizer method are prepared for nano lignin.But the precipitation method, supercritical fluid method and electrostatic spinning The nano lignin partial size of method preparation is uncontrollable, and the equipment cost of high pressure homogenizer method is high, limits it to a certain extent It is widely applied.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome the deficiencies of the prior art and provide it is a kind of operation it is simpler, cost compared with The low method using reversed-phase emulsion preparation nano lignin, obtained nano lignin size tunable.
The technical solution used to solve the technical problems of the present invention is that a kind of prepare nano lignin using reversed-phase emulsion Method, comprising the following steps:
(1) lipophilic emulsifier is dissolved in oil-based solvent and prepares oily phase, the quality for controlling lipophilic emulsifier in oily phase contains Amount is 6%-10%;
(2) alkali lignin and hydrophilic emulsifier are dissolved in water preparation water phase, the quality for controlling alkali lignin in water phase contains Amount is 1%-15%, and the mass content for controlling hydrophilic emulsifier in water phase is 5%-10%;The alkali lignin is in terms of effective ingredient;
(3) under being vigorously stirred that low whipping speed is 1000-1500r/min, water phase prepared by step (2) is added drop-wise to portion In the oily phase prepared in (1) step by step, the mass ratio of control water phase and oily phase is 1:1-5, is continued with mixing speed 1000- 1500r/min is vigorously stirred 28min or more, obtains alkali lignin reversed-phase emulsion;
(4) under being vigorously stirred that low whipping speed is 1000-1500r/min, dilute acid soln is added drop-wise to system in step (1) In standby another part oil phase, the mass ratio of control dilute acid soln and oily phase is 1:1-3, is continued with mixing speed 1000- 1500r/min is vigorously stirred 28min or more, obtains diluted acid reversed-phase emulsion;
(5) the alkali lignin reversed-phase emulsion prepared in the diluted acid reversed-phase emulsion and step (3) that prepare in step (4) is mixed (PH of back control system just defines the additional amount of diluted acid reversed-phase emulsion), is acutely stirred with mixing speed 1000-1500r/min 9min or more is mixed, then 0.9h or more is slowly stirred with mixing speed 100-300r/min, the PH for controlling whole system is 5-6, is obtained Mixed emulsion;
(6) mixed emulsion obtained by step (5) is slowly stirred at 50-60 DEG C with mixing speed 100-300r/min 28min or more carries out demulsification processing, and de-laminating solvent is added after demulsification makes creaming of emulsion, control hierarchy solvent and step (5) gained The mass ratio of mixed emulsion is 1:1-3, separates fuel-displaced phase, receives remaining aqueous mixture;
(7) it will repeatedly be washed after the filtering of residue aqueous mixture obtained in step (6), until the PH of cleaning solution is in Property, after being freeze-dried 12-24h, obtain nano lignin.
Further, in step (1), the lipophilic emulsifier is one of SP80, SP60, SP65 or a variety of.
Further, in step (1), the oil-based solvent includes one of white oil, hexamethylene, hexane, toluene, vegetable oil Or it is a variety of.
Further, in step (2), the alkali lignin is that wood pulp alkali lignin, Straw Pulp alkali lignin, bamboo pulp alkali are wooden One of element is a variety of.
Further, in step (2), the hydrophilic emulsifier is OP10, tween80, in Myrj 45 It is one or more.
Further, in step (4), the dilute acid soln is sulfuric acid solution, in hydrochloric acid solution, nitric acid solution, phosphoric acid solution It is one or more.Preferred mass concentration is the dilute acid soln of 5-15%.
Further, in step (6), the de-laminating solvent be one of ether, carbon tetrachloride, chloroform, dichloroethanes or It is a variety of.
The method using reversed-phase emulsion preparation nano lignin of the present invention, the nano lignin size uniformity of preparation, grain Diameter is in 100-150nm, and present invention process process is simple, and solution used is recyclable, to environment without negative effect, has good Good application prospect.Gained nano lignin size tunable, be beneficial to push its catalyst carrier, ion adsorbing material, The application in the fields such as biomedicine.
Detailed description of the invention
Fig. 1 is the SEM figure of the nano lignin prepared in comparative example 1;
Fig. 2 is the SEM figure of the nano lignin prepared in embodiment 1;
Fig. 3 is the SEM figure of the nano lignin prepared in embodiment 2.
Specific embodiment
Below in conjunction with specific embodiment the present invention is explained in more detail.
In each embodiment, unless otherwise stated, the mass concentration of diluted acid is 10%.The alkali lignin refers to effectively Composition.
Comparative example 1:
(1) 10 grams of lipophilic emulsifier SP80 are dissolved in 90 grams of white oils and prepare oily phase;
(2) 10 grams of wood pulp alkali lignins and 10 grams of hydrophilic emulsifier OP10 are dissolved in 80 grams of water preparation water phases;(3) in play Under strong stirring (mixing speed 1000r/min), 40 grams of water phases prepared by step (2) are added drop-wise to preparation in 80 grams of steps (1) In oily phase, continue to obtain alkali lignin reversed-phase emulsion after being vigorously stirred (mixing speed 1000r/min) 30min;
(4) in the case where being vigorously stirred (mixing speed 1000r/min), 10 grams of dilute hydrochloric acid solutions are added drop-wise to 120 grams of steps (3) In the alkali lignin reversed-phase emulsion of preparation, continue to be slowly stirred (stirring after being vigorously stirred (mixing speed 1000r/min) 30min Speed 100r/min) 1h, then lotion is slowly stirred to (mixing speed 100r/min) 30min at 60 DEG C and carried out at demulsification Reason, 130 grams of ether are added after demulsification makes creaming of emulsion, separates fuel-displaced phase, receives filtering and multiple water after remaining aqueous mixture It washes, until the PH of cleaning solution obtains nano lignin after being freeze-dried 14h at neutrality.The size of gained nano lignin is distributed Uniform, partial size is in 200-800nm, as shown in Figure 1.
Embodiment 1:
(1) 10 grams of lipophilic emulsifier SP80 are dissolved in 90 grams of white oils and prepare oily phase;
(2) 10 grams of wood pulp alkali lignins and 10 grams of hydrophilic emulsifier OP10 are dissolved in 80 grams of water and prepare water phase;
(3) in the case where being vigorously stirred (mixing speed 1000r/min), water phase prepared by 40 grams of steps (2) is added drop-wise to 80 grams In the oily phase prepared in step (1), continues after being vigorously stirred (mixing speed 1000r/min) 30min, obtain alkali lignin reverse phase Lotion;
(4) in the case where being vigorously stirred (mixing speed 1000r/min), 10 grams of dilute hydrochloric acid solutions are added drop-wise to 10 grams of steps (1) In the oily phase of middle preparation, continue to obtain dilute hydrochloric acid reversed-phase emulsion after being vigorously stirred (mixing speed 1000r/min) 30min;
(5) again that the dilute hydrochloric acid reversed-phase emulsion prepared in 20 grams of steps (4) and the alkali prepared in 120 grams of steps (3) is wooden Plain reversed-phase emulsion mixing, is slowly stirred (mixing speed 100r/min) after being vigorously stirred (mixing speed 1000r/min) 10min 1h, the PH for controlling whole system is 6, obtains mixed emulsion;
(6) 140 grams of mixed emulsions obtained by step (5) are then slowly stirred (mixing speed 100r/min) at 50 DEG C 30min carries out demulsification processing, and 140 grams of ether are added after demulsification makes creaming of emulsion, mixed emulsion obtained by de-laminating solvent and step (5) Mass ratio be 1:1, separate fuel-displaced phase, receive remaining aqueous mixture;
(7) it will repeatedly be washed after the filtering of residue aqueous mixture obtained in step (6), until the PH of cleaning solution is in Property, nano lignin is obtained after being freeze-dried 14h.The size uniformity of gained nano lignin, partial size is in 100-150nm, such as Fig. 2 It is shown.
Embodiment 2:
(1) 10 grams of lipophilic emulsifier SP60 are dissolved in 90 grams of hexamethylenes and prepare oily phase;
(2) 10 grams of Straw Pulp alkali lignins and 10 grams of hydrophilic emulsifier tween80 are dissolved in 80 grams of water and prepare water phase;
(3) in the case where being vigorously stirred (mixing speed 1000r/min), water phase prepared by 40 grams of steps (2) is added drop-wise to 80 grams In the oily phase prepared in step (1), continues after being vigorously stirred (mixing speed 1000r/min) 30min, obtain alkali lignin reverse phase Lotion;
(4) in the case where being vigorously stirred (mixing speed 1000r/min), 10 grams of dilution heat of sulfuric acid are added drop-wise to 10 grams of steps (1) In the oily phase of middle preparation, continue to obtain dilute sulfuric acid reversed-phase emulsion after being vigorously stirred (mixing speed 1000r/min) 30min;
(5) again that the 20 grams of dilute sulfuric acid reversed-phase emulsions prepared in step (4) and the alkali prepared in 120 grams of steps (3) are wooden Plain reversed-phase emulsion mixing, is slowly stirred (mixing speed 100r/min) after being vigorously stirred (mixing speed 1000r/min) 10min 1h, the PH for controlling whole system is 6, obtains mixed emulsion;
(6) 140 grams of mixed emulsions obtained by step (5) are slowly stirred (mixing speed 100r/min) 30min at 60 DEG C Demulsification processing is carried out, 140 grams of carbon tetrachloride are added after demulsification makes creaming of emulsion, separates fuel-displaced phase, receives remaining aqueous mixture;
(7) it will repeatedly be washed after the filtering of residue aqueous mixture obtained in step (6), until the PH of cleaning solution is in Property, nano lignin is obtained after being freeze-dried 14h.The size uniformity of gained nano lignin, partial size is in 100-150nm, such as Fig. 3 It is shown.

Claims (8)

1. a kind of method using reversed-phase emulsion preparation nano lignin, which comprises the following steps:
(1) lipophilic emulsifier is dissolved in oil-based solvent and prepares oily phase, the mass content for controlling lipophilic emulsifier in oily phase is 6%-10%;
(2) alkali lignin and hydrophilic emulsifier are dissolved in water preparation water phase, the mass content for controlling alkali lignin in water phase is 1%-15%, the mass content for controlling hydrophilic emulsifier in water phase is 5%-10%;The alkali lignin is in terms of effective ingredient;
(3) under being vigorously stirred that low whipping speed is 1000-1500r/min, water phase prepared by step (2) is added drop-wise to part step Suddenly in the oily phase prepared in (1), the mass ratio of control water phase and oily phase is 1:1-5, is continued with mixing speed 1000-1500r/ Min is vigorously stirred 28min or more, obtains alkali lignin reversed-phase emulsion;
(4) under being vigorously stirred of low whipping speed 1000-1500r/min, dilute acid soln is added drop-wise to the another of the middle preparation of step (1) In a part of oil phase, the mass ratio of control dilute acid soln and oily phase is 1:1-3, is continued acute with mixing speed 1000-1500r/min Strong stirring 28min or more, obtains diluted acid reversed-phase emulsion;
(5) the alkali lignin reversed-phase emulsion prepared in the diluted acid reversed-phase emulsion and step (3) that prepare in step (4) is mixed, with Mixing speed 1000-1500r/min is vigorously stirred 9min or more, then with mixing speed 100-300r/min be slowly stirred 0.9h with On, the PH for controlling whole system is 5-6, obtains mixed emulsion;
(6) by mixed emulsion obtained by step (5) at 50-60 DEG C with mixing speed 100-300r/min be slowly stirred 28min with On carry out demulsification processing, de-laminating solvent is added after demulsification makes creaming of emulsion, mixed emulsion obtained by control hierarchy solvent and step (5) Mass ratio be 1:1-3, separate fuel-displaced phase, receive remaining aqueous mixture;
(7) it will repeatedly be washed after the filtering of residue aqueous mixture obtained in step (6), until the PH of cleaning solution is at neutrality, it is cold After dry 12-24h is lyophilized, nano lignin is obtained.
2. the method according to claim 1 using reversed-phase emulsion preparation nano lignin, which is characterized in that step (1) In, the lipophilic emulsifier is one of SP80, SP60, SP65 or a variety of.
3. the method according to claim 1 or 2 using reversed-phase emulsion preparation nano lignin, which is characterized in that step (1) in, the oil-based solvent includes one of white oil, hexamethylene, hexane, toluene, vegetable oil or a variety of.
4. the method according to claim 1 or 2 using reversed-phase emulsion preparation nano lignin, which is characterized in that step (2) in, the alkali lignin is one of wood pulp alkali lignin, Straw Pulp alkali lignin, bamboo pulp alkali lignin or a variety of.
5. the method according to claim 1 or 2 using reversed-phase emulsion preparation nano lignin, which is characterized in that described Hydrophilic emulsifier is one of OP10, tween80, Myrj 45 or a variety of.
6. the method according to claim 1 or 2 using reversed-phase emulsion preparation nano lignin, which is characterized in that step (4) in, the dilute acid soln is one of sulfuric acid solution, hydrochloric acid solution, nitric acid solution, phosphoric acid solution or a variety of.
7. the method according to claim 6 using reversed-phase emulsion preparation nano lignin, which is characterized in that the diluted acid Solution is the dilute acid soln that mass concentration is 5-15%.
8. the method according to claim 1 or 2 using reversed-phase emulsion preparation nano lignin, which is characterized in that step (6) in, the de-laminating solvent is one of ether, carbon tetrachloride, chloroform, dichloroethanes or a variety of.
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