CN109054045B - Preparation method of submicron lignin - Google Patents
Preparation method of submicron lignin Download PDFInfo
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- CN109054045B CN109054045B CN201810919662.7A CN201810919662A CN109054045B CN 109054045 B CN109054045 B CN 109054045B CN 201810919662 A CN201810919662 A CN 201810919662A CN 109054045 B CN109054045 B CN 109054045B
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- 238000001035 drying Methods 0.000 claims abstract description 17
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- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
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- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims description 33
- 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 21
- 238000000227 grinding Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
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- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 9
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- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 30
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229920001587 Wood-plastic composite Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011155 wood-plastic composite Substances 0.000 abstract 1
- 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 15
- 229910052901 montmorillonite Inorganic materials 0.000 description 15
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- 238000010298 pulverizing process Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 238000003916 acid precipitation Methods 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000011056 performance test Methods 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
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- 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
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- 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
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- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a preparation method of submicron lignin, which comprises the following steps: (1) filtering the lignin suspension to obtain lignin black liquor; (2) adding organic acid and a dispersing agent into the lignin black liquor to obtain a solid-liquid mixed system; (3) and carrying out solid-liquid separation on the solid-liquid mixed system, washing, drying and crushing the obtained solid to obtain the submicron lignin. The submicron lignin particles prepared by the method are uniformly dispersed and light in color, and have obvious effects on improving the mechanical property, the thermal stability and the barrier property of the wood-plastic composite material.
Description
Technical Field
The invention belongs to the field of high-quality treatment of biomass, and particularly relates to a preparation method of submicron lignin.
Background
The lignin is an amorphous polymer formed by connecting phenyl propane units through ester bonds and carbon-carbon bonds, methoxy groups exist on benzene rings, the content of C is about 60-66%, and the content of hydrogen is low. The structural units are connected by ether bonds or carbon-carbon bonds, and the former is the main connection mode. There are currently three basic structures considered: guaiacyl structure, violaceyl structure and p-hydroxyphenyl structure. The lignin is second to cellulose in quantity on earth, can generate 1500 hundred million tons every year, is an abundant renewable carbon resource, is non-toxic, and is not well utilized yet.
The development of the submicron lignin provides a new way for the high value-added utilization of lignin-based products. The particle size of lignin has a significant impact on its application properties, with submicron lignin particles possessing a larger specific surface area than lignin powders of micron and larger particles. When mixed with different polymers, the submicron particles are capable of intimately interacting with, and uniformly distributing within, the polymer matrix. The lignin submicron particles can improve the mechanical property, the thermal stability and the barrier property of the composite material.
Disclosure of Invention
The invention aims to provide a preparation method of submicron lignin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing submicron lignin, comprising the following steps:
(1) filtering the lignin suspension to obtain lignin black liquor;
(2) adding organic acid and a dispersing agent into the lignin black liquor to obtain a solid-liquid mixed system;
(3) and carrying out solid-liquid separation on the solid-liquid mixed system, washing, drying and crushing the obtained solid to obtain the submicron lignin.
In the step (1), the lignin suspension is a lignin suspension (pH is about 11.5-13.0) produced in the paper industry, and the main components of the lignin suspension comprise lignin, cellulose and hemicellulose, wherein the content of the lignin is 18-25 g/L.
In the step (1), the filtering is to filter the lignin suspension by using a nylon filter cloth with 300 meshes and above. The lignin suspension contains more fine fibers, the size of the lignin suspension is small, the structural form and the chemical property of the lignin suspension are not uniform, and the fine fibers in the lignin suspension can be intercepted by using nylon filter cloth to obtain lignin black liquor. The nylon filter cloth is preferably polypropylene filter cloth.
In the step (2), the organic acid is acetic acid aqueous solution or oxalic acid aqueous solution. Too high concentration of organic acid easily causes local supersaturation, is not beneficial to mass transfer, and too low concentration easily reduces the yield of lignin. The mass fraction of the solute (acetic acid or oxalic acid) in the organic acid is 5-30%, preferably 10-25%.
Dispersants are required during the acid precipitation process to reduce agglomeration between the formed lignin particles. The dispersing agent is glycerol or polyethylene glycol 200, and the using amount of the dispersing agent accounts for 0.2-1% of the total mass of the lignin in the system.
In the step (2), adding organic acid into the lignin black liquor until the pH value is reduced to 8.0-9.0, adding a dispersing agent into the lignin black liquor, and then continuously adding the organic acid until the pH value is reduced to 2.5-3.0 to obtain a solid-liquid mixed system.
Preferably, when the pH value of the system is reduced to 2.5-3.0, the addition of the organic acid is stopped, the stirring is continued for 1.5-2.5 hours, preferably 2 hours, and then the solid-liquid separation in the step (3) is carried out.
In the step (2), the lignin black liquor is subjected to ultrasonic treatment and stirring, and then the organic acid and the dispersing agent are added. The ultrasonic power of the ultrasonic is 28-40 KHz, and the ultrasonic time is 8-12 min, preferably 10 min. The stirring uses double-deck agitator, and the bottom is impulse type agitator, and the upper strata is dentate dispersion impeller, and whole process need keep higher stirring speed, and stirring speed is 800 ~ 1200 rpm.
The propeller agitator blades may be 3 or 4 in number, preferably a three blade propeller agitator. The tooth-shaped dispersion impeller can be a single-sided tooth dispersion impeller or a double-sided tooth dispersion impeller according to the dispersion tooth surface, and preferably the double-sided tooth dispersion impeller; depending on the position of the dispersion teeth, the dispersion plate may be a peripheral toothed dispersion plate, or may be an internal toothed dispersion plate, preferably a peripheral toothed dispersion plate. The push type stirring paddle on the lower layer is beneficial to the upper and lower turbulence of the whole system and promotes mass transfer, and the tooth type dispersion disc on the upper layer can provide high shear force and is beneficial to the dispersion of the solid phase lignin which is subsequently separated out.
In the step (2), the organic acid can be directly poured in at one time or pumped in drop by drop, the quick addition is favorable for the explosive nucleation of lignin, submicron fine particles are quickly formed under the action of high shear of the dentate dispersion disk, and the submicron fine particles are kept highly dispersed under the action of the dispersing agent; the organic acid is pumped dropwise to achieve the effect of preparing submicron lignin fine particles, but the slow pumping speed reduces the production efficiency of the process.
In the step (3), the solvent used for washing is a low-boiling-point organic solvent so as to wash away the residual dispersant on the surface of the lignin, thereby facilitating the subsequent drying. The low-boiling organic solvent is preferably a mixed solvent of methanol and water, a mixed solvent of ethanol and water, or a mixed solvent of acetone and water. More preferred are methanol v/water v 8: 2, ethanol v/water v 8: 2, acetone v/water v 8: 2.
In the step (3), the drying temperature is 60-80 ℃, the drying time is 2-6 h, and vacuum drying is preferred. If the drying temperature is too high, the lignin is liable to be discolored, and if the drying temperature is too low, the drying efficiency is too low, and the drying time is too long.
In the step (3), a grinding instrument is used for grinding, the grinding time is 0.5-1 h, and the rotating speed is 7000-13000 rpm.
The grinding apparatus is preferably a ball mill.
The appearance diagram of the submicron lignin prepared by the invention is shown in figure 1(b), the lignin prepared by the method reported in patent CN201710376235.4 is shown in figure 1(a), the lignin prepared by the method reported in patent CN201410799742.5 is shown in figure 1(c), and the lignin prepared by the method reported in patent CN201710580422.4 is shown in figure 1 (d). The submicron lignin prepared by the method has good fluidity and lighter color as shown in a Scanning Electron Microscope (SEM).
The infrared spectrum of the submicron lignin prepared by the invention is shown in figure 2, and the Scanning Electron Microscope (SEM) is shown in figure 3. The particle size of lignin is mainly distributed in 100-800 nm as shown in scanning electron microscope image.
Has the advantages that: compared with the prior art, the invention has the following advantages:
1. the invention provides a method for preparing submicron lignin particles by using black liquor generated in the paper industry, which combines a physical method and a chemical method to obtain submicron lignin with good dispersibility and light color. The rubber reinforcing agent is applied to rubber products as a rubber reinforcing agent, and can obviously improve the mechanical property, the thermal stability and the barrier property of rubber.
2. The invention does not need temperature control in the process of preparing the submicron lignin by using the black liquor generated in the paper industry, thereby saving certain energy consumption.
Drawings
FIG. 1 is an appearance view of a submicron lignin product;
FIG. 2 is an infrared spectrum of a submicron lignin product;
figure 3 is a scanning electron microscope image (x 50000) of a submicron lignin product.
Detailed Description
The present invention will be further described with reference to examples.
Example 1:
taking 2L of lignin suspension produced in the paper industry, firstly pretreating, wherein the suspension contains more fine fibers, and the fine fibers are small in size, uneven in structural form and chemical properties, and intercepting the fine fibers by using 300-mesh polypropylene filter cloth to obtain lignin black liquor. The method comprises the following steps of carrying out ultrasonic treatment on black liquor for 10min, wherein the ultrasonic power is 28KHz, transferring the black liquor into a glass reaction kettle, mixing and dispersing by double-layer stirring, wherein the lower layer stirring is a three-blade propelling stirring paddle, the upper layer is a stainless steel peripheral toothed dispersion plate, the diameters of the lower layer stirring paddle and the upper layer dispersion plate are equivalent, the diameters of the lower layer stirring paddle and the upper layer dispersion plate are about 0.6-0.7 of the inner diameter of a glass reactor, the rotating speed is adjusted to 800rpm, the black liquor is carried out at room temperature without temperature control, and then, an oxalic acid aqueous solution is gradually pumped into the black liquor (wherein the mass fraction of oxalic acid. When the pH value of the lignin black liquor is reduced to 8.0, glycerol which is 0.2 percent of the total mass of the lignin in the system is added as a dispersing agent, acid is continuously pumped into the system, the acid feeding speed can be properly accelerated, the high-speed stirring is kept in the whole process, when the pH value of the system is reduced to 2.5, the acid feeding is stopped, and the stirring is continuously carried out for 2 hours. And taking out the lignin suspension after the reaction, performing solid-liquid separation at 7000rpm by using an ultracentrifuge for 20min, washing the precipitate by using a methanol water solution (methanol v: water v is 8: 2), and then putting the precipitate into a vacuum drying oven for drying under the conditions of 60 ℃ and 6h to obtain a crude lignin product. The crude product of lignin is crushed by using a grinding instrumentGrinding for 0.5h with a spherical grinder at 4000rpm to obtain submicron lignin particles with particle size of about 300-800 nm by scanning electron microscope, detecting particle size distribution with Malvern particle sizer, and finding out d10＝310nm，d50＝605nm，d90＝790nm。
The prepared submicron lignin particles and montmorillonite are dry-mixed in a ratio of 1: 1 (both 500g), filled into rubber, and a rubber stretching experiment is carried out, and the result is shown in table 1, which shows that the tensile strength of the rubber is increased by about 30-37% compared with the rubber filled with the lignin and montmorillonite mixed in a ratio of 1: 1 prepared by the preparation technology provided by CN201710376235.4, CN201410799742.5 and CN 201710580422.4.
Example 2:
taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 400-mesh polypropylene filter cloth to obtain lignin black liquor. Carrying out ultrasonic treatment on the black liquor for 10min, wherein the ultrasonic power is 40KHz, then transferring the black liquor after ultrasonic filtration into a 5L glass reactor, mixing and dispersing by using a double-layer stirring paddle, stirring the lower layer by using a four-paddle push type stirring paddle, stirring the upper layer by using a stainless steel double-sided tooth dispersion disc at the rotating speed of 1000rpm, carrying out at room temperature without controlling the temperature, then dropwise pumping an acetic acid aqueous solution (wherein the mass fraction of oxalic acid in the oxalic acid aqueous solution is 25%), adding polyethylene glycol accounting for 1% of the total mass of lignin contained in the system as a dispersing agent when the pH of the lignin black liquor is reduced to 9.0, stirring for 10min, then rapidly adding the acetic acid aqueous solution accounting for 25% of the mass fraction into the system, detecting the pH of the system in real time, keeping high-speed stirring in the whole process, stopping adding acid when the pH of the system is reduced to 3.0 and the pH does not obviously return, stirring for 2h, performing solid-liquid separation in a lower tank at 13000rpm by using a centrifugal machine for 20min, washing the precipitate by using an acetone-water binary solvent with the ratio of acetone v to water v being 8: 2, and then drying the precipitate in a vacuum drying oven under the conditions of 80 ℃ and 2h to obtain a lignin crude product. Pulverizing the crude lignin product, and usingThe grinding instrument is a spherical grinding machine, the grinding time is 1h, the rotating speed is 8000rpm, submicron lignin particles are obtained after grinding is finished, the particle size of the submicron lignin is about 100-500 nm as can be seen by a scanning electron microscope, particle size distribution detection is carried out by a Malvern particle sizer, and d is found10＝90nm，d50＝225nm，d90＝486nm。
The prepared submicron lignin particles and montmorillonite are dry-mixed in a ratio of 1: 1 (both 500g), filled into rubber, and subjected to a rubber stretching experiment, and the result is shown in table 1, which shows that the tensile strength of the rubber is increased by about 35-41% compared with the rubber filled with the lignin and montmorillonite mixed in a ratio of 1: 1 prepared by the preparation technology provided by CN201710376235.4, CN201410799742.5 and CN 201710580422.4.
Example 3:
taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 500-mesh polypropylene filter cloth to obtain lignin black liquor. Carrying out ultrasonic treatment on the black liquor for 10min, wherein the ultrasonic power is 35KHz, then transferring the black liquor after ultrasonic filtration into a 5L glass reactor, mixing and dispersing by using a double-layer stirring paddle, stirring the lower layer by using a three-paddle push type stirring paddle, stirring the upper layer by using a stainless steel single-sided tooth dispersion disc at the rotating speed of 1000rpm, carrying out at room temperature without controlling the temperature, then dropwise pumping an oxalic acid aqueous solution (wherein the mass fraction of oxalic acid in the oxalic acid aqueous solution is 30%), adding glycerol accounting for 0.5% of the total mass of lignin of a system as a dispersing agent when the pH of the lignin black liquor is reduced to 8.5, stirring for 10min, then quickly adding the oxalic acid aqueous solution with the mass fraction of 30% into the system, detecting the pH of the system in real time, keeping high-speed stirring in the whole process, stopping adding acid when the pH of the system is reduced to 2.5 and the pH does not return obviously within one hour, stirring for 2h, separating solid and liquid in a tank by using an ultracentrifuge at 10000rpm for 20min, washing the precipitate by using a methanol-water binary solvent with the ratio of methanol v to water v being 8: 2, and drying the precipitate in a vacuum drying oven under the condition of 70 ℃ for 4h to obtain a crude lignin product. Pulverizing lignin crude productProcessing, wherein the grinding instrument is a spherical grinder, the grinding time is 0.8h, the rotating speed is 6000rpm, submicron lignin particles are obtained after grinding is finished, the particle size of the submicron lignin is about 200-650 nm as known by a scanning electron microscope, and particle size distribution detection is carried out by a Malvern particle size analyzer to find d of the submicron lignin particles10＝182nm，d50＝446nm，d90＝712nm。
The prepared submicron lignin particles and montmorillonite are dry-mixed in a ratio of 1: 1 (both 500g), filled into rubber, and subjected to a rubber stretching experiment, and the result is shown in table 1, which shows that the tensile strength of the rubber is increased by about 33-39% compared with the rubber filled with the lignin and montmorillonite mixed in a ratio of 1: 1 prepared by the preparation technology provided by CN201710376235.4, CN201410799742.5 and CN 201710580422.4.
Example 4:
taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 500-mesh polypropylene filter cloth to obtain lignin black liquor. Carrying out ultrasonic treatment on the black liquor for 10min, wherein the ultrasonic power is 35KHz, then transferring the black liquor after ultrasonic filtration into a 5L glass reactor, mixing and dispersing by using a double-layer stirring paddle, stirring the lower layer by using a three-paddle push type stirring paddle, stirring the upper layer by using a stainless steel peripheral tooth dispersion disc at the rotation speed of 1000rpm, carrying out at room temperature without controlling the temperature, then dropwise pumping an acetic acid aqueous solution (wherein the mass fraction of acetic acid in the acetic acid aqueous solution is 20%), when the pH of the black liquor is reduced to 8.0, adding polyethylene glycol 200 accounting for 0.8% of the total mass of lignin of a system as a dispersing agent, stirring for 10min, then adding 20 wt% of the acetic acid aqueous solution into the system, detecting the pH of the system in real time, keeping high-speed stirring in the whole process, when the pH of the system is reduced to 2.7 and the pH does not appear obvious return within one hour, stopping adding acid, continuing stirring for 2h, and carrying out solid-liquid separation in a, the time is 20min, the precipitate is washed by a binary solvent of ethanol v and water v being 8: 2, and then the precipitate is put into a vacuum drying oven for drying under the condition of 70 ℃ and 5h, so as to obtain a crude lignin product. Pulverizing the crude lignin, and grindingThe instrument is a spherical grinding machine, the grinding time is 0.8h, the rotating speed is 6000rpm, submicron lignin particles are obtained after grinding is finished, the particle size of the submicron lignin is about 250-850 nm as can be seen by a scanning electron microscope, particle size distribution detection is carried out by a Malvern particle sizer, and d is found10＝260～410nm，d50＝450～640nm，d90＝720～1100nm。
The prepared submicron lignin particles and montmorillonite are dry-mixed in a ratio of 1: 1 (both 500g), filled into rubber, and subjected to a rubber stretching experiment, and the result is shown in table 1, which shows that the lignin and the montmorillonite are dry-mixed in a ratio of 1: 1 and then filled into the rubber, and compared with the lignin and the montmorillonite mixed in a ratio of 1: 1 and filled into the rubber, which are prepared by the preparation technology provided by CN201710376235.4, CN201410799742.5 and CN201710580422.4, the stretching strength of the mixture is increased by about 35-40%.
Example 5: lignin Performance test
To test the properties of the lignin prepared according to the invention, a control experiment was designed. The preparation method of the rubber comprises the following steps: 40g of NR (natural rubber), 25g of SBR (styrene butadiene rubber), 30g of BR (butadiene rubber), 70g of reclaimed rubber, 5g of ZnO, 2g of SA, 3g of CZ, 2g of anti-aging agent A, 1g of paraffin, 1g of pine tar, 45g of N330 or composite filler, 25g of clay and 2.2g of S2. The above are all parts by mass. And mixing the NR, the SBR, the BR and the reclaimed rubber uniformly on an open mill to obtain the masterbatch. And adding other compounding agents for mixing after the open mill is cooled to obtain the rubber compound. And (3) molding and vulcanizing the rubber compound on a flat vulcanizing instrument to prepare a test piece with the thickness of 2mm, wherein the vulcanization time is T90, and the pressure is 10 MPa. The submicron lignin prepared in the embodiments 1-4 of the invention is respectively mixed with montmorillonite in a mass ratio of 1: 1 (500 g), and then the mixture is used as a reinforcing agent to be applied to rubber, and the prepared rubber is subjected to a tensile test. Blank without montmorillonite and lignin is used as a reference group 1; taking simple montmorillonite without lignin as reinforcing agent as a control group 2; mixing lignin and montmorillonite prepared by the method of patent CN201710376235.4 in a mass ratio of 1: 1, and applying the mixture as a reinforcing agent in the rubber preparation process as a contrast group 3; mixing lignin and montmorillonite prepared by the method of patent CN201410799742.5 in a mass ratio of 1: 1, and applying the mixture as a reinforcing agent in the rubber preparation process as a contrast group 4; the lignin prepared by the method of patent CN201710580422.4 and montmorillonite are mixed according to the mass ratio of 1: 1, and then the mixture is used as a reinforcing agent to be applied to the rubber preparation process and is used as a contrast group 5. The results of the tensile tests on the rubbers without/with different fillers are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the submicron lignin prepared by the method is applied to rubber products as a rubber reinforcing agent, the mechanical property, the thermal stability and the barrier property of rubber can be obviously improved.
Claims (7)
1. A preparation method of submicron lignin for rubber reinforcing agent is characterized by comprising the following steps:
(1) filtering the lignin suspension to obtain lignin black liquor;
(2) firstly, ultrasonically stirring the lignin black liquor, then adding organic acid into the lignin black liquor until the pH value is reduced to 8.0-9.0, adding a dispersing agent into the lignin black liquor, then continuously adding the organic acid until the pH value is reduced to 2.5-3.0, wherein the organic acid is an acetic acid aqueous solution or an oxalic acid aqueous solution, and the dispersing agent is glycerol or polyethylene glycol 200, so as to obtain a solid-liquid mixed system; the mass fraction of solute in the organic acid aqueous solution is 5% -30%, and the dosage of the dispersant accounts for 0.2-1% of the total mass of lignin in the system;
(3) and (3) carrying out solid-liquid separation on the solid-liquid mixed system, washing and drying the obtained solid, and crushing the solid by using a grinding instrument to obtain the submicron lignin.
2. The method according to claim 1, wherein in the step (1), the lignin suspension is a lignin suspension produced in the paper industry, and the main components are lignin, cellulose and hemicellulose, wherein the content of the lignin is 18-25 g/L.
3. The method as claimed in claim 1, wherein in the step (1), the filtering is performed by filtering the lignin suspension by using a nylon-based filter cloth with a size of 300 meshes or more.
4. The method according to claim 1, wherein in the step (2), the ultrasonic power of the ultrasonic wave is 28 to 40KHz, the ultrasonic time is 8 to 12min, the stirring uses a double-layer stirrer, the bottom layer is a propelling stirrer, the upper layer is a dentate dispersion plate, and the stirring speed is 800 to 1200 rpm.
5. The method according to claim 1, wherein in the step (3), the solvent used for washing is a mixed solvent of methanol and water, a mixed solvent of ethanol and water, or a mixed solvent of acetone and water.
6. The method according to claim 1, wherein in the step (3), the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 2-6 h.
7. The method of claim 1, wherein in the step (3), the grinding time is 0.5-1 h, and the rotation speed is 7000-13000 rpm.
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