CN109054045A - A kind of preparation method of sub-micron lignin - Google Patents
A kind of preparation method of sub-micron lignin Download PDFInfo
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- CN109054045A CN109054045A CN201810919662.7A CN201810919662A CN109054045A CN 109054045 A CN109054045 A CN 109054045A CN 201810919662 A CN201810919662 A CN 201810919662A CN 109054045 A CN109054045 A CN 109054045A
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- lignin
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- black liquor
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- 229920005610 lignin Polymers 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 4
- 229920001587 Wood-plastic composite Polymers 0.000 abstract 1
- 230000008092 positive effect Effects 0.000 abstract 1
- 239000011155 wood-plastic composite Substances 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 36
- 239000005060 rubber Substances 0.000 description 36
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 17
- 229910052901 montmorillonite Inorganic materials 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000012043 crude product Substances 0.000 description 7
- -1 methoxyl groups Chemical group 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000011897 real-time detection Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a kind of preparation methods of sub-micron lignin, comprising the following steps: (1) is filtered to lignin suspension, obtains lignin black liquor；(2) organic acid and dispersing agent are added into the lignin black liquor, obtains solid-liquid mixing system；(3) solid-liquid mixing system is separated by solid-liquid separation, by obtained solid washing, dry, crushing to get sub-micron lignin.The sub-micron lignin particles that the present invention is prepared are uniformly dispersed, of light color, have positive effect in terms of the mechanical property, thermal stability and the barrier property that improve wood plastic composite.
Description
Technical field
The invention belongs to high-qualityization of biomass process fields, and in particular to a kind of preparation method of sub-micron lignin.
Background technique
Lignin be it is a kind of the amorphous polymer formed is keyed by ester bond and carbon-to-carbon by phenylpropane units,
There are methoxyl groups on phenyl ring, and C content about 60%~66%, hydrogen content is lower.It is connected between structural unit with ehter bond or carbon-carbon bond,
The former is main connection type.It is now recognized that there are three types of basic structures: guaiacyl structure, purple fourth obtain based structures and p-hydroxyphenyl
Structure.Lignin on earth next in number only to cellulose, can produce 150,000,000,000 tons every year, be a kind of renewable carbon abundant
Resource, and it is nontoxic, but do not utilized well so far.
The exploitation of sub-micron lignin provides a new way for the high value added utilization of lignin-base product.Lignin
Granular size its application performance is had a significant impact, it is wooden compared to micron and the lignin powder of larger particle, sub-micron
Crude granule possesses bigger specific surface area.When with different mixed with polymers, submicron particles can be with the close phase of polymer substrate
Interaction is uniformly distributed in the polymer matrix.These lignin submicron particles can improve the mechanical property of composite material, heat
Stability and barrier property.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of sub-micron lignin.
To achieve the above object, the present invention adopts the following technical solutions:
A kind of preparation method of sub-micron lignin, comprising the following steps:
(1) lignin suspension is filtered, obtains lignin black liquor；
(2) organic acid and dispersing agent are added into the lignin black liquor, obtains solid-liquid mixing system；
(3) solid-liquid mixing system is separated by solid-liquid separation, by obtained solid washing, dry, crushing to get sub-micron
Lignin.
In step (1), the lignin suspension be paper industry generate lignin suspension (pH about 11.5~
13.0), main component has lignin, cellulose and hemicellulose, and wherein content of lignin is 18~25g/L.
In step (1), described be filtered into is filtered lignin suspension using 300 mesh and the above nylon-type filter cloth.
Contain more fiber fines in lignin suspension, size is small, structural form, and chemical property is inhomogenous, filters using nylon-type
Cloth can retain the fiber fines in lignin suspension, obtain lignin black liquor.The nylon-type filter cloth is preferably
Polypropylene fibre filter cloth.
In step (2), the organic acid is acetic acid aqueous solution or aqueous oxalic acid.The excessively high concentration of organic acid is easy
Cause local supersaturation, be unfavorable for mass transfer, too low concentration is easily reduced the yield of lignin.Solute in organic acid (acetic acid or
Ethanedioic acid) mass fraction be 5%~30%, preferably 10%~25%.
It needs to use dispersing agent during acid is heavy, to reduce the reunion between formed lignin particle.Described point
Powder is glycerine or polyethylene glycol 200, and the dosage of dispersing agent accounts for 0.2~1% of lignin gross mass in system.
In step (2), organic acid is added into the lignin black liquor, until pH is when dropping to 8.0~9.0, to wooden
Dispersing agent is added in plain black liquor, then continuously add organic acid until pH drop to 2.5~3.0, obtain solid-liquid mixing system.
Preferably, when system pH drops between 2.5~3.0, stopping plus organic acid continue 1.5~2.5h of stirring, preferably
Then 2h carries out the separation of solid and liquid of step (3) again.
In step (2), first by the lignin black liquor ultrasound, stirring, organic acid and dispersing agent are added.The ultrasound
Ultrasonic power is 28~40KHz, and ultrasonic time is 8~12min, preferably 10min.The stirring uses double-layered stirrer, bottom
Layer is propeller agitator, and upper layer is dentation dispersion impeller, and whole process needs to keep higher mixing speed, and mixing speed is
800~1200rpm.
The propeller agitator blade quantity can be 3 or 4, preferably three blade propeller agitators.The dentation
For dispersion impeller is according to the dispersion flank of tooth, single cog dispersion impeller can be, be also possible to double cog dispersion impeller, preferably double cog disperses
Disk；For being set according to dispersion tooth position, it can be periphery dentation dispersion impeller, be also possible to internal-gear type dispersion impeller, preferably periphery dentation
Dispersion impeller.The pusher agitating paddle of lower layer is conducive to the turbulent flow up and down of whole system, promotes mass transfer, the tooth-like dispersion impeller on upper layer can
To provide high shear force, be conducive to the dispersion of the solid phase lignin of subsequent precipitation.
In step (2), the mode that organic acid is added, which can be, disposably directly to be poured into, and is also possible to be pumped into dropwise, quickly
Addition be conducive to lignin outburst nucleation, quickly form the tiny micro- of submicron order under the action of dentation dispersion impeller high shear
Grain, and make the fine particles of submicron order keep high degree of dispersion under the action of dispersing agent；It is pumped into the mode of organic acid dropwise
Also it can achieve the effect for preparing submicron order lignin fine particles, but be pumped into speed slowly excessively, the production of process can be reduced
Efficiency.
In step (3), washing solvent used is low boiling point organic solvent, to wash away the dispersion of lignin surface residual
Subsequent drying is convenient in agent.The low boiling point organic solvent is preferably the mixed solvent of the mixed solvent of first alcohol and water, second alcohol and water
Or the mixed solvent of acetone and water.More preferable methanol v: water v=8: 2, ethyl alcohol v: water v=8: 2, acetone v: water v=8: 2.
In step (3), drying temperature is 60~80 DEG C, and drying time is 2~6h, is preferably dried in vacuo.Dry temperature,
If excessively high, the discoloration of lignin is easily caused, if too low, drying efficiency is too low, and drying time is too long.
In step (3), using grinding instrument crushed, milling time be 0.5~1h, revolving speed be 7000~
13000rpm。
The preferably spherical grinder of the grinding instrument.
Shown in outside drawing such as Fig. 1 (b) of sub-micron lignin prepared by the present invention, patent CN201710376235.4 is utilized
It is made obtained by the method reported shown in lignin such as Fig. 1 (a), the method institute reported using patent CN201410799742.5
It must be made obtained by the method shown in lignin such as Fig. 1 (c), reported using patent CN201710580422.4 and lignin is made such as
Shown in Fig. 1 (d).Its good fluidity known to sub-micron lignin scanning electron microscope diagram (SEM) prepared in accordance with the present invention, face
Color is shallower.
The infrared spectrogram of sub-micron lignin prepared by the present invention as shown in Fig. 2, scanning electron microscope diagram (SEM) such as
Shown in Fig. 3.By scanning electron microscope diagram it is found that lignin partial size is mainly distributed on 100~800nm.
The utility model has the advantages that compared with the existing technology, the invention has the following advantages that
It 1, will the present invention provides a kind of method of black liquor preparation sub-micron lignin particles generated using paper industry
Physical method and chemical method combine, and obtain good dispersion, sub-micron lignin of light color.By it as reinforcing rubber
Agent is applied in rubber product, can significantly improve mechanical property, thermal stability and the barrier property of rubber.
2, during the present invention prepares sub-micron lignin using the black liquor that paper industry generates, it is not necessarily to temperature control, this section
About certain energy consumption.
Detailed description of the invention
Fig. 1 is the outside drawing of sub-micron lignin product；
Fig. 2 is the infrared spectrogram of sub-micron lignin product；
Fig. 3 is the scanning electron microscope diagram (× 50000) of sub-micron lignin product.
Specific embodiment
Below with reference to example, the present invention is described further.
Embodiment 1:
The lignin suspension for taking 2L paper industry to generate, is pre-processed first, and more tiny fibre is contained in suspension
Dimension, size is small, structural form, and chemical property is inhomogenous, is retained using the polypropylene fibre filter cloth of 300 mesh to its fiber fines,
Obtain lignin black liquor.Black liquor is subjected to ultrasonic treatment 10min, ultrasonic power 28KHz, it is anti-that black liquor is then transferred to glass
It answers in kettle, is mixed and dispersed with bilayer stirring, lower layer's stirring is three blade push type agitating paddles, and upper layer is stainless steel periphery
The diameter of dentation dispersion impeller, lower layer's agitating paddle and upper layer dispersion impeller is suitable, and accounts for about the 0.6~0.7 of glass reactor internal diameter, turns
Velocity modulation is 800rpm, is carried out at room temperature, is not necessarily to temperature control, being then pumped into aqueous oxalic acid dropwise, (wherein, ethanedioic acid is in ethanedioic acid
5%) mass fraction in aqueous solution is.After lignin black liquor pH drops to 8.0, lignin gross mass contained by addition system
0.2% glycerine continues to pump acid to system as dispersing agent, and the speed that sour stream adds can suitably be accelerated, and whole process is protected
High-speed stirred is held, when system pH drops to 2.5, stops stream acid adding, continues to stir 2h.By the lignin suspension after reaction
It takes out, is separated by solid-liquid separation at 7000rpm using ultracentrifuge, time 20min, precipitating methanol aqueous solution (methanol v
: water v=8: 2) being washed, and then that precipitating merging vacuum oven is dry, condition is 60 DEG C, and 6h obtains lignin and slightly produces
Product.Lignin crude product is subjected to pulverization process, the grinding instrument used is spherical grinder, milling time 0.5h, revolving speed
For 4000rpm, grinding obtains sub-micron lignin particles after completing, by scanning electron microscope it is found that sub-micron lignin
Partial size is about 300~800nm, and carries out size distribution detection with Malvern ParticleSizer, finds its d10=310nm, d50=
605nm, d90=790nm.
The sub-micron lignin particles of preparation and montmorillonite 1: 1 are dry-mixed (being 500g), it is filled into rubber, and carry out
Rubber tensile experiment, the results are shown in Table 1, show by the lignin and montmorillonite 1: 1 it is dry-mixed after in filling rubber, with utilization
Wood obtained by technology of preparing provided by CN201710376235.4, CN201410799742.5, CN201710580422.4
Quality is mixed in filling rubber with montmorillonite 1: 1 and is compared, and the tensile strength of rubber increases about 30%~37%.
Embodiment 2:
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 400 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 10min, ultrasonic power 40KHz, it then will be black after filtering ultrasound
Liquid moves into 5L glass reactor, carries out mixing dispersion using Double-layer stirring paddle, and lower layer's stirring is four blade push type agitating paddles,
Upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 1000rpm, carries out at room temperature, is not necessarily to temperature control, is then pumped into acetic acid dropwise
(wherein, mass fraction of the ethanedioic acid in aqueous oxalic acid is 25%), when lignin black liquor pH drops to 9.0 to aqueous solution
Afterwards, the polyethylene glycol of lignin gross mass 1% contained by addition system stirs 10min, then quickly into system as dispersing agent
The acetic acid aqueous solution that mass fraction is 25%, and the pH of real-time detection system is added, whole process keeps high-speed stirred, works as system
When pH drops to that rebound significantly no longer occurs in pH in 3.0, and hour, stop acid adding, continue to stir 2h, lower tank use from
Scheming is separated by solid-liquid separation at 13000rpm, time 20min, precipitating acetone v: the acetone water binary solvent of water v=8: 2
It is washed, then that precipitating merging vacuum oven is dry, condition is 80 DEG C, and 2h obtains lignin crude product.By lignin
Crude product carries out pulverization process, and the grinding instrument used is spherical grinder, milling time 1h, revolving speed 8000rpm, grinding
Obtain sub-micron lignin particles after completing, by scanning electron microscope it is found that sub-micron lignin partial size be about 100~
500nm, and size distribution detection is carried out with Malvern ParticleSizer, find its d10=90nm, d50=225nm, d90=486nm.
The sub-micron lignin particles of preparation and montmorillonite 1: 1 are dry-mixed (being 500g), it is filled into rubber, and carry out
Rubber tensile experiment, the results are shown in Table 1, shows to insert in rubber after lignin and montmorillonite 1: 1 are dry-mixed, with utilization
Wood obtained by technology of preparing provided by CN201710376235.4, CN201410799742.5, CN201710580422.4
Quality is mixed in filling rubber with montmorillonite 1: 1 and is compared, and the tensile strength of rubber increases about 35%~41%.
Embodiment 3:
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 500 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 10min, ultrasonic power 35KHz, it then will be black after filtering ultrasound
Liquid moves into 5L glass reactor, carries out mixing dispersion using Double-layer stirring paddle, and lower layer's stirring is three blade push type agitating paddles,
Upper layer is stainless steel single cog dispersion impeller, and revolving speed is adjusted to 1000rpm, carries out at room temperature, is not necessarily to temperature control, is then pumped into second two dropwise
(wherein, mass fraction of the ethanedioic acid in aqueous oxalic acid is 30%), when lignin black liquor pH drops to 8.5 to aqueous acid
Afterwards, the glycerine for accounting for system lignin gross mass 0.5% is added as dispersing agent, stirs 10min, then quickly adds into system
Enter the aqueous oxalic acid that mass fraction is 30%, and the pH of real-time detection system, whole process keeps high-speed stirred, works as system
When pH drops to that rebound significantly no longer occurs in pH in 2.5, and hour, stop acid adding, continues to stir 2h, lower tank uses super
Fast centrifuge is separated by solid-liquid separation at 10000rpm, time 20min, precipitating methanol v: the methanol-water binary of water v=8: 2
Solvent is washed, and then that precipitating merging vacuum oven is dry, condition is 70 DEG C, and 4h obtains lignin crude product.It will be wooden
Quality crude product carries out pulverization process, and the grinding instrument used is spherical grinder, and milling time 0.8h, revolving speed is
6000rpm, grinding obtains sub-micron lignin particles after completing, by scanning electron microscope it is found that sub-micron lignin grain
Diameter is about 200~650nm, and carries out size distribution detection with Malvern ParticleSizer, finds its d10=182nm, d50=
446nm, d90=712nm.
The sub-micron lignin particles of preparation and montmorillonite 1: 1 are dry-mixed (being 500g), it is filled into rubber, and carry out
Rubber tensile experiment, the results are shown in Table 1, shows to insert in rubber after lignin and montmorillonite 1: 1 are dry-mixed, with utilization
Wood obtained by technology of preparing provided by CN201710376235.4, CN201410799742.5, CN201710580422.4
Quality is mixed in filling rubber with montmorillonite 1: 1 and is compared, and the tensile strength of rubber increases about 33%~39%.
Embodiment 4:
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 500 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 10min, ultrasonic power 35KHz, it then will be black after filtering ultrasound
Liquid moves into 5L glass reactor, carries out mixing dispersion using Double-layer stirring paddle, and lower layer's stirring is three blade push type agitating paddles,
Upper layer is stainless steel peripheral teeth dispersion impeller, and revolving speed is adjusted to 1000rpm, carries out at room temperature, is not necessarily to temperature control, is then pumped into acetic acid dropwise
(wherein, mass fraction of the acetic acid in acetic acid aqueous solution is that 20%), after black liquor pH drops to 8.0, addition accounts for body to aqueous solution
The polyethylene glycol 200 of chain timbers quality gross mass 0.8% stirs 10min as dispersing agent, and is added 20wt%'s in backward system
Acetic acid aqueous solution, and the pH of real-time detection system, whole process keeps high-speed stirred, when system pH drops to 2.7, and one
When rebound significantly no longer occurs in pH in hour, stop acid adding, continues to stir 2h, lower tank is using ultracentrifuge at 10000rpm
It is separated by solid-liquid separation, time 20min, precipitate with ethyl alcohol v: the binary solvent of water v=8: 2 is washed, and then sets precipitating
It is dry to enter vacuum oven, condition is 70 DEG C, and 5h obtains lignin crude product.Lignin crude product is subjected to pulverization process, is made
Grinding instrument is spherical grinder, and milling time 0.8h, revolving speed 6000rpm obtain sub-micron after grinding completion
Lignin particles, by scanning electron microscope it is found that sub-micron lignin partial size is about 250~850nm, and with Malvern grain
It spends instrument and carries out size distribution detection, find its d10=260~410nm, d50=450~640nm, d90=720~1100nm.
The sub-micron lignin particles of preparation and montmorillonite 1: 1 are dry-mixed (being 500g), it is filled into rubber, and carry out
Rubber tensile experiment, the results are shown in Table 1, shows to insert in rubber after lignin and montmorillonite 1: 1 are dry-mixed, with utilization
Wood obtained by technology of preparing provided by CN201710376235.4, CN201410799742.5, CN201710580422.4
Quality is mixed in filling rubber with montmorillonite 1: 1 and is compared, and tensile strength increases about 35%~40%.
Embodiment 5: the performance test of lignin
In order to test the performance of lignin obtained by the present invention, control experiment is designed.Method for preparing rubber: NR is (natural
Rubber) 40g, SBR (butadiene-styrene rubber) 25g, BR (butadiene rubber) 30g, reclaimed rubber 70g, ZnO 5g, SA 2g, CZ 3g, anti-aging agent
A 2g, paraffin 1g, pine tar 1g, N330 or compounded mix 45g, clay 25g, S2.2g.It is above mass parts.By NR, SBR,
BR, reclaimed rubber are kneaded uniformly on a mill, obtain rubber master batch.Other compounding agents are added after open mill is cooling to be kneaded
Refining glue.Rubber compound is molded the test piece that 2mm thickness is made in vulcanization, vulcanization time T90, pressure 10MPa on compression molding instrument.It will
The sub-micron lignin that 1-4 of the embodiment of the present invention is prepared is respectively with montmorillonite with the ratio (being 500g) of mass ratio 1: 1
After mixing, it is applied to rubber as reinforcing agent, stretching experiment is carried out to the rubber being prepared.Montmorillonite is not added, wood is not added
The blank of quality is as 1 group of control；The simple montmorillonite of lignin is not added as reinforcing agent as 2 groups of control；With patent
After lignin and montmorillonite is made with the ratio mixing of mass ratio 1: 1 in CN201710376235.4 the method, as reinforcing agent
Applied to rubber system it is standby during, as compareing 3 groups；Lignin is made with patent CN201410799742.5 the method and covers
After de- soil is with the ratio mixing of mass ratio 1: 1, as reinforcing agent be applied to rubber system it is standby during, as compareing 4 groups；With patent
After lignin and montmorillonite is made with the ratio mixing of mass ratio 1: 1 in CN201710580422.4 the method, as reinforcing agent
Applied to rubber system it is standby during, as compareing 5 groups.The Tensile Test Results of rubber are shown in when not filled/addition different fillers
Table 1.
Table 1
Seen from table 1, the sub-micron lignin that the present invention is prepared is applied to rubber product as rubber reinforcing filler
In, mechanical property, thermal stability and the barrier property of rubber can be significantly improved.
Claims (9)
1. a kind of preparation method of sub-micron lignin, which comprises the following steps:
(1) lignin suspension is filtered, obtains lignin black liquor；
(2) organic acid and dispersing agent are added into the lignin black liquor, obtains solid-liquid mixing system；
(3) solid-liquid mixing system is separated by solid-liquid separation, by obtained solid washing, dry, crushing is wooden to get sub-micron
Element.
2. the method according to claim 1, wherein the lignin suspension is paper industry in step (1)
The lignin suspension of generation, main component have lignin, cellulose and hemicellulose, and wherein content of lignin is 18~25g/
L。
3. described to be filtered into using 300 mesh or more the method according to claim 1, wherein in step (1)
Nylon-type filter cloth is filtered lignin suspension.
4. the method according to claim 1, wherein in step (2), the organic acid be acetic acid aqueous solution or
Aqueous oxalic acid, the mass fraction of solute is 5%~30% in aqueous solution, and the dispersing agent is glycerine or polyethylene glycol
200, the dosage of dispersing agent accounts for 0.2~1% of lignin gross mass in system.
5. the method according to claim 1, wherein being added into the lignin black liquor organic in step (2)
Acid then continuously adds organic acid until under pH until dispersing agent is added into lignin black liquor when pH drops to 8.0~9.0
2.5~3.0 are down to, solid-liquid mixing system is obtained.
6. the method according to claim 1, wherein in step (2), first by the lignin black liquor ultrasound, stir
It mixes, adds organic acid and dispersing agent, the ultrasonic power of the ultrasound is 28~40KHz, and ultrasonic time is 8~12min, described
Stirring uses double-layered stirrer, and bottom is propeller agitator, and upper layer is dentation dispersion impeller, and mixing speed is 800~
1200rpm。
7. the method according to claim 1, wherein washing solvent used is first alcohol and water in step (3)
The mixed solvent of mixed solvent, the mixed solvent of second alcohol and water or acetone and water.
8. the method according to claim 1, wherein the drying is vacuum drying, drying temperature in step (3)
Degree is 60~80 DEG C, and drying time is 2~6h.
9. the method according to claim 1, wherein being crushed, being ground using grinding instrument in step (3)
Time is 0.5~1h, and revolving speed is 7000~13000rpm.
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