CN110092917B - Lignin metal salt and preparation method and application thereof - Google Patents
Lignin metal salt and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lignin metal salt and a preparation method thereof, which comprises the steps of carrying out solid-liquid separation on a lignin suspension to obtain lignin black liquor; then adding metal salt and a dispersing agent, and fully stirring to obtain a solid-liquid mixing system; and finally, carrying out solid-liquid separation, and washing, drying and crushing the obtained solid to obtain the submicron or nanometer lignin metal salt. The invention also discloses application of the prepared lignin metal salt as a reinforcing agent added into rubber and wood-plastic composite materials. The invention utilizes black liquor generated in paper industry or biological refining to prepare submicron or nanometer lignin metal salt, combines physical method and chemical method, and obtains submicron or nanometer lignin metal salt with good dispersity and uniform granularity. The modified polyurethane elastomer can be added into rubber and wood-plastic composite materials, and can obviously enhance the mechanical property, the thermal stability and the barrier property of rubber and wood-plastic composite products.
Description
Technical Field
The invention belongs to the field of high-valued treatment and application of biomass, and particularly relates to lignin metal salt and a preparation method and application thereof.
Background
Lignin (lignin) is the second most abundant natural polymer in the plant kingdom next to cellulose and only contains aromatic ring structures, and it is estimated that the new increase in lignin biosynthesis worldwide per year is about 6 × 1014t. Lignin is linked by phenyl-propane monomers through chemical bonds such as alkyl-alkyl and alkyl-aryl. According to the number and position of methoxyl, the monomers can be divided into p-hydroxyphenyl type (H), guaiacyl type (G) and syringyl type (S), and the basic structural units are shown in figure 1. 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 carbon content is about 60-66%, and the hydrogen content is low. The structural units are connected by ether bonds or carbon-carbon bonds, and the former is the main connection mode. Although the molecular structure of lignin is complex, the lignin still has the advantages that the molecular structure contains various functional groups (various active functional groups such as aromatic group, phenolic hydroxyl group, alcoholic hydroxyl group, carboxyl group, methoxyl group, conjugated double bond and the like) and natural renewable, biodegradable, nontoxic and the like, and the lignin is derived from byproducts of the paper industry, so that the lignin has the advantage of low cost. Therefore, lignin is considered to be an excellent renewable biomass raw material, and has been attracting much attention for the high-value utilization in the field of materials.
Disclosure of Invention
The invention aims to provide lignin metal salt and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the lignin metal salt comprises the following steps:
(1) carrying out solid-liquid separation on the lignin suspension to obtain lignin black liquor;
(2) adding metal salt and a dispersing agent into the lignin black liquor obtained in the step (1), and fully stirring to obtain a solid-liquid mixed system;
(3) and (3) carrying out solid-liquid separation on the solid-liquid mixed system obtained in the step (2), and washing, drying and crushing the obtained solid to obtain the submicron or nanometer lignin metal salt.
Specifically, in the step (1), the lignin suspension is produced in the paper industry or biorefinery, the pH value is 11-13, the main components comprise lignin, cellulose, hemicellulose, polysaccharide and ash, and the content of the lignin is 10-300 g/L;
the solid-liquid separation method is filtration or centrifugation, and the lignin suspension is filtered by using 300-mesh or above nylon filter cloth and filter bags. 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 and filter bags to obtain lignin black liquor. The nylon filter cloth is preferably polypropylene filter cloth and filter bags.
In the step (2), the metal salt comprises one or more of sulfates, chlorides and nitrates of iron, cobalt, nickel, zinc, manganese, copper, calcium and the like, and metal oxides and hydroxides; the consumption of the metal salt is 0.1-50% of the total mass of the lignin in the lignin black liquor.
The dispersing agent is any one of ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, sodium pyrophosphate, sodium hexametaphosphate, sodium polyacrylate and the like; the dosage of the dispersant is 0.1-5% of the total mass of lignin in the lignin black liquor. Because the lignin particles are easy to agglomerate, the addition of the dispersing agent can effectively inhibit the agglomeration of the particles.
The metal salt is added in the form of a metal salt solid, a metal salt aqueous solution or a metal salt dispersion; the concentration of the metal salt aqueous solution or the metal salt dispersion liquid is 2-40 wt%, and the solvent of the metal salt dispersion liquid is any one or a mixture of methanol, ethanol and acetone.
Further, in the step (2), the lignin black liquor is firstly subjected to ultrasonic treatment for 3-30 min under 20-50 KHz, then metal salt and a dispersing agent are added under a stirring state, a double-layer stirrer is used for stirring, a push-type stirrer is used as a bottom layer, a tooth-shaped dispersion disc is used as an upper layer, and the stirring speed is 200-2000 rpm.
After adding the metal salt and the dispersing agent, heating the system to 40-60 ℃, and continuously stirring for 2-3 h.
In the step (3), one or more mixed solvents of water, methanol, ethanol and acetone are used for washing; the drying adopts a vacuum drying mode, the drying temperature is 40-80 ℃, the drying time is 2-24 hours, and preferably the drying is carried out at 60-70 ℃ for 6-8 hours; the crushing is carried out by adopting a crusher, and then the ball mill is used for grinding.
The lignin metal salt prepared by the preparation method is also in the protection scope of the invention.
The lignin has both the rigid basic structure of aromatic rings and flexible side chains, contains a plurality of functional groups with reactivity, and is a fine granular sub-polymer with larger specific surface area. Therefore, the modified polypropylene can be used as a reinforcing agent to be added into rubber and wood-plastic composite materials to realize the modification function. The development of the submicron or nanometer lignin metal salt provides a new way for the high value-added utilization of lignin-based products. The particle size of the lignin metal salt has a remarkable influence on the application performance, and compared with lignin metal salt powder with micron and larger particles, the submicron or nanometer lignin metal salt has larger specific surface area. The introduction of metal ions changes the strength, rigidity and particle size of lignin, and in the salt forming process, a dispersing agent is added to form submicron or nanometer lignin metal salt, so that the interface effect between rubber, wood-plastic composite materials and inorganic/organic fillers can be enhanced, a system forms a firm network, the dispersibility and compatibility of the fillers in the rubber and wood-plastic composite materials are promoted, and the mechanical property, the thermal stability and the barrier property of the rubber and wood-plastic composite materials are further improved.
Has the advantages that:
1. the invention provides a method for preparing submicron or nanometer lignin metal salt by using black liquor generated in paper industry or biorefinery, which combines a physical method and a chemical method to obtain the submicron or nanometer lignin metal salt with good dispersity and uniform granularity. The modified polyurethane elastomer can be added into rubber and wood-plastic composite materials, and can obviously enhance the mechanical property, the thermal stability and the barrier property of rubber and wood-plastic composite products.
2. The invention utilizes the black liquor produced in the paper industry or biological refining to prepare the submicron or nanometer lignin metal salt, does not need to adjust the pH value of the black liquor, can directly add the metal salt, saves the production cost, improves the production efficiency, and reduces the waste liquor treatment cost and the environmental pollution.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 shows the structural formulas of p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S) as basic lignin units.
FIG. 2 is an appearance diagram of the iron lignin salt product prepared in example 1.
FIG. 3 is an infrared spectrum of the ferric lignin salt product prepared in example 1.
FIG. 4 is an X-ray diffraction spectrum of the iron lignin salt product prepared in example 1.
Detailed Description
The invention will be better understood from the following examples.
Example 1
Taking 3L 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 15min, wherein the ultrasonic power is 30KHz, 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, then adding an iron chloride solution (the mass fraction of iron chloride is 5%), then adding ethylene glycol accounting for 0.5% of the total mass of lignin contained in the system, heating to 50 ℃, and continuing stirring for 2. And (3) after the heat preservation is finished, slowly cooling to room temperature, carrying out solid-liquid separation on the lignin metal salt solid-liquid mixed system after the reaction by using an ultracentrifuge at 8000rpm for 20min, washing the precipitate by using a methanol/water solution (methanol v: water v ═ 6:4), and then drying the precipitate in a vacuum drying oven under the conditions of 60 ℃ and 8h to obtain the crude lignin iron salt. And (2) crushing the crude lignin iron salt product, wherein the used grinding instrument is a spherical grinding machine, the grinding time is 2h, the rotating speed is 600rpm, and submicron or nanometer lignin iron salt particles are obtained after grinding is finished.
Fig. 2 is an appearance diagram of the prepared ferric lignin salt product. According to the results of scanning electron microscopy, the particle size distribution of the nano iron ligninsulinate is determined by a particle size distribution measuring instrument with a Malvern particle size analyzer, and d 10-25 nm, d 50-65 nm and d 90-105 nm are found.
Fig. 3 is an infrared spectrum of the obtained lignin iron salt product, which shows that: compared with lignin, in the salifying process, lignin iron salt is subjected to the weakening of a C-H stretching vibration peak on a benzene ring and the appearance of an Fe-O stretching vibration peak along with the disappearance of a methyl and methylene C-H stretching vibration peak along with the disappearance of the methyl and methylene C-H stretching vibration peaks, which shows that the coordination of the lignin and iron salt is successful, and the lignin iron salt is successfully generated.
Fig. 4 is an X-ray diffraction spectrum of the obtained lignin iron salt product, and it can be seen that: compared with lignin, in the salifying process of the lignin iron salt, the intensity of the amorphous characteristic diffraction peak of the lignin shows a remarkably reduced trend, the lignin is used as a matrix, other characteristic diffraction peaks do not obviously appear in the lignin iron salt, and the amorphous characteristic diffraction peak of the lignin is still displayed on the whole.
The rubber preparation formula comprises: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent and 1 part of paraffin. Adding the prepared nano iron lignin salt, carbon black and other processing aids into an open mill in proportion, uniformly mixing to obtain a rubber compound, measuring the positive vulcanization time t90 of the rubber compound at 180 ℃ by a vulcanizer, vulcanizing and molding the rubber compound in a flat vulcanizing agent according to t90, and then carrying out a rubber tensile experiment. The tensile property test was based on GB/T1040-. The result shows that compared with the lignin/carbon black prepared by the preparation technology provided by CN107722396A, the tensile strength of the rubber is increased by about 42-48%. The selected rubber is N330.
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 20min, 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, wherein the lower layer is a four-paddle push type stirring paddle, the upper layer is a stainless steel double-sided tooth dispersion disc, the rotating speed is adjusted to 900rpm, and then dropwise pumping cobalt chloride solution (the mass fraction of cobalt chloride is 5%). Then, glycerol accounting for 0.4 percent of the total mass of the lignin in the system is added, the temperature is raised to 55 ℃, and the stirring is continued for 2 hours. And (3) after the heat preservation is finished, slowly cooling to room temperature, putting the lignin metal salt solid-liquid mixed system after the reaction into a tank, performing solid-liquid separation by using a centrifugal machine at 12000rpm for 15min, and precipitating by using ethanol v: washing the precipitate with an ethanol/water mixed solvent with the ratio of water v to water 2, and drying the precipitate in a vacuum drying oven at 65 ℃ for 6 hours to obtain a crude product of the lignin cobalt salt. And (2) crushing the rough product of the lignin cobalt salt, wherein a grinding instrument is a spherical grinding machine, the grinding time is 3h, the rotating speed is 500rpm, submicron or nanometer lignin cobalt salt particles are obtained after grinding is finished, the particle size of the submicron lignin cobalt salt is about 200-550 nm as known by a scanning electron microscope, and particle size distribution detection is carried out by a Malvern particle size analyzer, so that d10 is 205nm, d50 is 365nm, and d90 is 545 nm.
The rubber preparation formula comprises: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent and 1 part of paraffin. Adding the prepared submicron lignin cobalt salt, carbon black and other processing aids into an open mill in proportion, uniformly mixing to obtain a mixed rubber, measuring the positive vulcanization time t90 of the mixed rubber at 180 ℃ by a vulcanizer, vulcanizing and molding the mixed rubber in a flat vulcanizing agent according to t90, and then carrying out a rubber tensile experiment. The tensile property test was based on GB/T1040-. The results show that the tensile strength of the rubber is increased by about 16-25% compared with the lignin/carbon black prepared by the preparation technology provided by CN 107722396A. The selected rubber is N330.
Example 3
Taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 300-mesh polypropylene filter cloth to obtain lignin black liquor. The black liquor is subjected to ultrasonic treatment for 15min, the ultrasonic power is 40KHz, the black liquor after ultrasonic filtration is moved into a 5L glass reactor, a double-layer stirring paddle is used for mixing and dispersing, the lower layer is a four-paddle push type stirring paddle, the upper layer is a stainless steel double-sided tooth dispersion disc, the rotating speed is adjusted to 1000rpm, and then a nickel chloride solution (the mass fraction of nickel chloride is 5%) is pumped dropwise. Then, polyethylene glycol with the total mass of 0.4 percent of lignin contained in the system is added, the temperature is raised to 50 ℃, and the stirring is continued for 2 hours. And (3) after heat preservation is finished, slowly cooling to room temperature, putting the lignin metal salt solid-liquid mixed system after reaction into a tank, performing solid-liquid separation at 11000rpm by using a centrifugal machine for 20min, and precipitating by using ethanol v: washing the precipitate with a mixed solvent of ethanol and water with a ratio of water v to water v being 7:3, and drying the precipitate in a vacuum drying oven at the temperature of 60 ℃ for 7 hours to obtain the crude product of the lignin nickel salt. The method comprises the steps of crushing a lignin nickel salt crude product, wherein a grinding instrument used is a spherical grinding machine, the grinding time is 3 hours, the rotating speed is 500rpm, submicron or nanometer lignin nickel salt particles are obtained after grinding is completed, the particle size of the submicron lignin nickel salt is about 150-520 nm as known by a scanning electron microscope, particle size distribution detection is carried out by a Malvern particle size analyzer, and d 10-155 nm, d 50-320 nm and d 90-510 nm are found.
The rubber preparation formula comprises: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent and 1 part of paraffin. Adding the prepared submicron lignin nickel salt, carbon black and other processing aids into an open mill in proportion, uniformly mixing to obtain a rubber compound, measuring the positive vulcanization time t90 of the rubber compound at 180 ℃ by a vulcanizer, vulcanizing and molding the rubber compound in a flat vulcanizing agent according to t90, and then carrying out a rubber tensile experiment. The tensile property test was based on GB/T1040-. The results show that the submicron lignin nickel salt/carbon black has about 18% 28% increased tensile strength of rubber compared to the lignin/carbon black prepared by the preparation technology provided by CN 107722396A. The selected rubber is N330.
Example 4
Taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 300-mesh polypropylene filter cloth to obtain lignin black liquor. The black liquor is subjected to ultrasonic treatment for 15min, the ultrasonic power is 40KHz, the black liquor after ultrasonic filtration is moved into a 5L glass reactor, a double-layer stirring paddle is used for mixing and dispersing, the lower layer is a four-paddle push type stirring paddle, the upper layer is a stainless steel double-sided tooth dispersion disc, the rotating speed is adjusted to 1000rpm, and then zinc chloride solution (the mass fraction of zinc chloride is 4%) is pumped dropwise. Then, ethylene glycol with the total mass of 0.5 percent of lignin contained in the system is added, the temperature is raised to 45 ℃, and the stirring is continued for 3 hours. And (3) after heat preservation is finished, slowly cooling to room temperature, putting the lignin metal salt solid-liquid mixed system after reaction into a tank, performing solid-liquid separation at 10000rpm by using a centrifugal machine for 20min, and precipitating by using ethanol v: washing the precipitate with a 6:4 ethanol/water mixed solvent, and drying the precipitate in a vacuum drying oven at 60 ℃ for 6 hours to obtain the crude product of the zinc lignin salt. The method comprises the steps of crushing a zinc lignin salt crude product, wherein a grinding instrument used in the method is a spherical grinder, the grinding time is 2 hours, the rotating speed is 800rpm, submicron or nanometer zinc lignin salt particles are obtained after grinding is completed, the particle size of the submicron zinc lignin salt particles is about 40-180 nm as known by a scanning electron microscope, particle size distribution detection is carried out by a Malvern particle size analyzer, and d 10-45 nm, d 50-120 nm and d 90-175 nm are found.
The rubber preparation formula comprises: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulfur, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent and 1 part of paraffin. Adding the prepared submicron lignin zinc salt, carbon black and other processing aids into an open mill in proportion, uniformly mixing to obtain a rubber compound, measuring the positive vulcanization time t90 of the rubber compound at 180 ℃ by a vulcanizer, vulcanizing and molding the rubber compound in a flat vulcanizing agent according to t90, and then carrying out a rubber tensile experiment. The tensile property test was based on GB/T1040-. The results show that compared with the lignin/carbon black prepared by the preparation technology provided by CN107722396A, the sub-micron lignin zinc salt/carbon black has the advantage that the tensile strength of the rubber is increased by about 22-30%. The selected rubber is N330.
Example 5
Performance test of lignin metal salt:
in order to test the properties of the lignin metal salt prepared by the invention, a control experiment is 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 ZnO5g, 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 matching machines 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 nano and submicron lignin iron, cobalt, nickel and zinc salts prepared in the embodiments 1-4 of the invention are respectively mixed with carbon black according to the 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. The tensile property test was based on GB/T1040-. Blank without adding carbon black, lignin and lignin metal salt is used as a control group 1; pure lignin without carbon black was used as control group 2; the lignin prepared by the method of patent CN107722396A and carbon black are mixed according to the mass ratio of 1:1, and then the mixture is used as a reinforcing agent in the rubber preparation process as a control group 3. The results of the tensile tests on the rubbers without/with different fillers are shown in Table 1.
Example 6
Taking 3L 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 15min, wherein the ultrasonic power is 30KHz, 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, then adding an iron chloride solution (the mass fraction of iron chloride is 5%), then adding ethylene glycol accounting for 0.5% of the total mass of lignin contained in the system, heating to 50 ℃, and continuing stirring for 2. And (3) after the heat preservation is finished, slowly cooling to room temperature, carrying out solid-liquid separation on the lignin metal salt solid-liquid mixed system after the reaction by using an ultracentrifuge at 8000rpm for 20min, washing the precipitate by using a methanol/water solution (methanol v: water v ═ 6:4), and then drying the precipitate in a vacuum drying oven under the conditions of 60 ℃ and 8h to obtain the crude lignin iron salt. And (2) crushing the crude product of the lignin iron salt, wherein a grinding instrument used is a spherical grinding machine, the grinding time is 2h, the rotating speed is 600rpm, submicron or nanometer lignin iron salt particles are obtained after grinding is completed, and according to a scanning electron microscope, the particle size of the nanometer lignin iron salt is about 20-110 nm, and particle size distribution detection is carried out by using a Malvern particle size analyzer, so that d10 is 25nm, d50 is 65nm, and d90 is 105 nm.
Polyvinyl chloride (PVC) formulation: adding lignin/lignin metal salt and PVC into a small high-speed mixer according to the mass fractions of 30% and 60%, then sequentially adding a calcium-zinc stabilizer CZ866 accounting for 3% of the mass fraction of the PVC, diisooctyl phthalate (DOP) 5%, Polyethylene (PE) wax 1% and calcium stearate 0.5%, and uniformly mixing in the high-speed mixer. Mixing the mixed sample in a 180 ℃ double-roll mixing mill for 5min, and discharging the sheet. And after cooling, cutting into small pieces, laminating, hot-pressing for 5min on a flat vulcanizing machine at 200 ℃ by using a three-plate frame die under the pressure of 20MPa, then cold-pressing for 5min under the same pressure, pressing into sheets with the thicknesses of 2mm and 4mm respectively, and then cutting into dumbbell-shaped and V-shaped notch impact sample strips respectively. Then, a mechanical property experiment is carried out on a CMT-7503 type universal testing machine, the stretching speed is 5mm/min, and the constant force attenuation is 80 percent; the bending rate is 2mm/min, and the constant force attenuation is 10%. The Izod impact test was performed on an impact tester model Zwick roller 5133.300. The blank without lignin and lignin metal salt is used as a control group 4, the lignin is used as a control group 5, and the mechanical property test results of PVC without filler/with different fillers are shown in Table 2. The tensile property and the bending property are respectively tested based on GB/T1447-. The results show that compared with lignin, the nano ferric ligninolate has tensile strength and bending strength increased by 18-25% and 14-22% respectively, and impact strength increased by 28-36%.
Example 7
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 20min, 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, wherein the lower layer is a four-paddle push type stirring paddle, the upper layer is a stainless steel double-sided tooth dispersion disc, the rotating speed is adjusted to 900rpm, and then dropwise pumping cobalt chloride solution (the mass fraction of cobalt chloride is 5%). Then, glycerol accounting for 0.4 percent of the total mass of the lignin in the system is added, the temperature is raised to 55 ℃, and the stirring is continued for 2 hours. And (3) after the heat preservation is finished, slowly cooling to room temperature, putting the lignin metal salt solid-liquid mixed system after the reaction into a tank, performing solid-liquid separation by using a centrifugal machine at 12000rpm for 15min, and precipitating by using ethanol v: washing the precipitate with an ethanol/water mixed solvent with the ratio of water v to water 2, and drying the precipitate in a vacuum drying oven at 65 ℃ for 6 hours to obtain a crude product of the lignin cobalt salt. And (2) crushing the rough product of the lignin cobalt salt, wherein a grinding instrument is a spherical grinding machine, the grinding time is 3h, the rotating speed is 500rpm, submicron or nanometer lignin cobalt salt particles are obtained after grinding is finished, the particle size of the submicron lignin cobalt salt is about 200-550 nm as known by a scanning electron microscope, and particle size distribution detection is carried out by a Malvern particle size analyzer, so that d10 is 205nm, d50 is 365nm, and d90 is 545 nm.
Polyvinyl chloride (PVC) formulation: adding lignin or lignin metal salt and PVC into a small high-speed mixer according to the mass fractions of 30% and 60%, then sequentially adding a calcium-zinc stabilizer CZ866 with the mass fraction of PVC being 3%, diisooctyl phthalate (DOP) 5%, Polyethylene (PE) wax 1% and calcium stearate 0.5%, and uniformly mixing in the high-speed mixer. Mixing the mixed sample in a 180 ℃ double-roll mixing mill for 5min, and discharging the sheet. And after cooling, cutting into small pieces, laminating, hot-pressing for 5min on a flat vulcanizing machine at 200 ℃ by using a three-plate frame die under the pressure of 20MPa, then cold-pressing for 5min under the same pressure, pressing into sheets with the thicknesses of 2mm and 4mm respectively, and then cutting into dumbbell-shaped and V-shaped notch impact sample strips respectively. Then, a mechanical property experiment is carried out on a CMT-7503 type universal testing machine, the stretching speed is 5mm/min, and the constant force attenuation is 80 percent; the bending rate is 2mm/min, and the constant force attenuation is 10%. The Izod impact test was performed on an impact tester model Zwick roller 5133.300. The blank without lignin and lignin metal salt is used as a control group 4, the lignin is used as a control group 5, and the mechanical property test results of PVC without filler/with different fillers are shown in Table 2. The tensile property and the bending property are respectively tested based on GB/T1447-. The results show that compared with lignin, the submicron lignin cobalt salt increases the tensile strength and the bending strength of PVC by about 12-20% and 10-18% respectively, and increases the impact strength by 26-35%.
Example 8
Taking 3L of lignin suspension produced in the paper industry, and intercepting fine fibers of the lignin suspension by using 300-mesh polypropylene filter cloth to obtain lignin black liquor. The black liquor is subjected to ultrasonic treatment for 15min, the ultrasonic power is 40KHz, the black liquor after ultrasonic filtration is moved into a 5L glass reactor, a double-layer stirring paddle is used for mixing and dispersing, the lower layer is a four-paddle push type stirring paddle, the upper layer is a stainless steel double-sided tooth dispersion disc, the rotating speed is adjusted to 1000rpm, and then a nickel chloride solution (the mass fraction of nickel chloride is 5%) is pumped dropwise. Then, polyethylene glycol with the total mass of 0.4 percent of lignin contained in the system is added, the temperature is raised to 50 ℃, and the stirring is continued for 2 hours. And (3) after heat preservation is finished, slowly cooling to room temperature, putting the lignin metal salt solid-liquid mixed system after reaction into a tank, performing solid-liquid separation at 11000rpm by using a centrifugal machine for 20min, and precipitating by using ethanol v: washing the precipitate with a mixed solvent of ethanol and water with a ratio of water v to water v being 7:3, and drying the precipitate in a vacuum drying oven at the temperature of 60 ℃ for 7 hours to obtain the crude product of the lignin nickel salt. The method comprises the steps of crushing a lignin nickel salt crude product, wherein a grinding instrument used is a spherical grinding machine, the grinding time is 3 hours, the rotating speed is 500rpm, submicron or nanometer lignin nickel salt particles are obtained after grinding is completed, the particle size of the submicron lignin nickel salt is about 150-520 nm as known by a scanning electron microscope, particle size distribution detection is carried out by a Malvern particle size analyzer, and d 10-155 nm, d 50-320 nm and d 90-510 nm are found.
Polyvinyl chloride (PVC) formulation: adding lignin or lignin metal salt and PVC into a small high-speed mixer according to the mass fractions of 30% and 60%, then sequentially adding a calcium-zinc stabilizer CZ866 with the mass fraction of PVC being 3%, diisooctyl phthalate (DOP) 5%, Polyethylene (PE) wax 1% and calcium stearate 0.5%, and uniformly mixing in the high-speed mixer. Mixing the mixed sample in a 180 ℃ double-roll mixing mill for 5min, and discharging the sheet. And after cooling, cutting into small pieces, laminating, hot-pressing for 5min on a flat vulcanizing machine at 200 ℃ by using a three-plate frame die under the pressure of 20MPa, then cold-pressing for 5min under the same pressure, pressing into sheets with the thicknesses of 2mm and 4mm respectively, and then cutting into dumbbell-shaped and V-shaped notch impact sample strips respectively. Then, a mechanical property experiment is carried out on a CMT-7503 type universal testing machine, the stretching speed is 5mm/min, and the constant force attenuation is 80 percent; the bending rate is 2mm/min, and the constant force attenuation is 10%. The Izod impact test was performed on an impact tester model Zwick roller 5133.300. The blank without lignin and lignin metal salt is used as a control group 4, the lignin is used as a control group 5, and the mechanical property test results of PVC without filler/with different fillers are shown in Table 2. The tensile property and the bending property are respectively tested based on GB/T1447-. The result shows that compared with lignin, the submicron lignin nickel salt has the advantages that the tensile strength and the bending strength of PVC are respectively increased by about 15-23 percent and 12-20 percent, and the impact strength is increased by 28-36 percent.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the submicron or nanometer lignin iron, cobalt, nickel and zinc salt prepared by the method provided by the invention has excellent performance when being applied to rubber and PVC composite materials as reinforcing agents. In view of the material specificity and functionality of the lignin metal salt, and the compatibility and interoperability with other polymer media, the lignin metal salt is applied to rubber and wood-plastic composite materials as a reinforcing agent, and is expected to remarkably improve the mechanical property, thermal stability and barrier property of rubber and wood-plastic composite products.
The present invention provides a lignin metal salt, and a method for preparing the same, and a method for implementing the technical scheme, wherein the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. The preparation method of the lignin metal salt is characterized by comprising the following steps:
(1) carrying out solid-liquid separation on the lignin suspension to obtain lignin black liquor;
(2) adding metal salt and a dispersing agent into the lignin black liquor obtained in the step (1), and fully stirring to obtain a solid-liquid mixed system;
(3) carrying out solid-liquid separation on the solid-liquid mixed system obtained in the step (2), and washing, drying and crushing the obtained solid to obtain submicron or nanometer lignin metal salt;
in the step (1), the lignin suspension is produced in the paper industry or biorefinery, the pH value is 11-13, the main components comprise lignin, cellulose, hemicellulose, polysaccharide and ash, and the content of the lignin is 10-300 g/L;
the solid-liquid separation method is filtration or centrifugation, and the lignin suspension is filtered by using 300-mesh or above nylon filter cloth and filter bags;
in the step (2), after the metal salt and the dispersing agent are added, the system is heated to 40-60 ℃ and continuously stirred for 2-3 h.
2. The method for preparing lignin metal salt according to claim 1, wherein in step (2), the metal salt comprises one or more of the combination of iron, cobalt, nickel, zinc, manganese, copper, calcium sulfate, chloride, nitrate; the consumption of the metal salt is 0.1-50% of the total mass of the lignin in the lignin black liquor.
3. The method for preparing lignin metal salt according to claim 1, wherein in step (2), the dispersant is any one of ethylene glycol, polyethylene glycol, glycerol, polyvinyl alcohol, sodium pyrophosphate, sodium hexametaphosphate, and sodium polyacrylate; the dosage of the dispersant is 0.1-5% of the total mass of lignin in the lignin black liquor.
4. The method for preparing lignin metal salt according to claim 1, wherein in step (2), the metal salt is added in the form of metal salt solid, metal salt aqueous solution or metal salt dispersion; the concentration of the metal salt aqueous solution or the metal salt dispersion liquid is 2-40 wt%, and the solvent of the metal salt dispersion liquid is any one or a mixture of methanol, ethanol and acetone.
5. The method for preparing lignin metal salt according to claim 1, wherein in the step (2), the lignin black liquor is first treated with ultrasonic wave at 20-50 KHz for 3-30 min, then the metal salt and the dispersant are added under stirring, a double-layer stirrer is used for stirring, the bottom layer is a push type stirrer, the upper layer is a toothed dispersion plate, and the stirring speed is 200-2000 rpm.
6. The method for preparing lignin metal salt according to claim 1, wherein in the step (3), the washing uses one or more mixed solvents of water, methanol, ethanol and acetone; the drying adopts a vacuum drying mode, the drying temperature is 40-80 ℃, and the drying time is 2-24 hours; the crushing is carried out by adopting a crusher, and then the ball mill is used for grinding.
7. The lignin metal salt prepared by the preparation method of any one of claims 1 to 6.
8. The use of the lignin metal salt of claim 7 as a reinforcing agent added to rubber, wood-plastic composites.
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| KR102283601B1 (en) * | 2020-02-10 | 2021-07-30 | 한국타이어앤테크놀로지 주식회사 | Rubber composition for tire and tire manufactured by using the same |
| CN111944189B (en) * | 2020-08-14 | 2022-05-31 | 河南师范大学 | Lignin-iron-containing PE film material and synthetic method thereof |
| CN112920424B (en) * | 2021-04-08 | 2022-05-24 | 长沙理工大学 | Polypropylene composition based on esterified lignin metal salt nucleating agent |
| CN113817237B (en) * | 2021-11-02 | 2023-08-11 | 赛轮集团股份有限公司 | Co-precipitated rubber of hydroxymethylated lignin modified cobalt neodecanoate/natural rubber, preparation method and application |
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