CN107903403B - Method for separating and extracting lignin in papermaking black liquor by magnetic emulsion liquid membrane - Google Patents
Method for separating and extracting lignin in papermaking black liquor by magnetic emulsion liquid membrane Download PDFInfo
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Abstract
The invention provides a method for separating and extracting lignin in papermaking black liquor by a magnetic emulsion liquid membrane. Oleic acid-coated ferroferric oxide (Fe)3O4) The nanometer solid particles are used as a stabilizer, an organic solvent and a carrier are mixed into an oil film, and the particle stabilizer is dispersed in the oil filmForming an oil phase, shearing and emulsifying the oil phase and the water phase to obtain a required stable water-in-oil type emulsion, adding the stable water-in-oil type emulsion into the supernatant of the black liquor, stirring to form a water-in-oil-in-water composite emulsion, enriching lignin into the inner water phase through a carrier under the action of a driving force of concentration difference, performing demulsification after extraction, recovering an emulsifier and an oil film, and recycling. Simple steps, convenient operation and strong practicability.
Description
Technical Field
The invention belongs to the technical field of papermaking, and particularly relates to a preparation method of a magnetic emulsion liquid membrane and a method for separating and extracting lignin in black liquor.
Background
Lignin is a natural polyhydroxy aromatic compound, a polyphenol compound, is used as a bonding substance of cellulose and hemicellulose in plants and is a renewable resource. As a degradable natural polymer material with excellent performance, the lignin can be used for producing phenolic platform compounds such as benzene, phenol substitutes and aromatic acid or polymer material products such as fillers, binders, rubber, antioxidants, antibacterial agents and the like, can be used as a raw material for preparing engineering plastics such as carbon fibers and graphene, and has extremely high additional value. Generally, the lignin content in the papermaking wood fiber raw material is 20% -30%, most of lignin is degraded and dissolved out in the pulping cooking process to realize fiber dissociation, and the dissolved lignin and organic carbohydrate degradation product form black liquor. Pulping black liquor generated in the paper making process is generally burnt after being evaporated and concentrated by alkali recovery, and lignin resources are wasted. Therefore, the research of separating and extracting the lignin in the black liquor is attracting more and more attention, and has important significance for developing the biomass energy industry. At present, the extraction of lignin at home and abroad mainly adopts the following methods: (1) the biological treatment method has the advantages of low cost, mild conditions, difficult secondary pollution and the like, but the degradation of lignin by microorganisms is not thorough, and toxic substances contained in the black liquor are not beneficial to the growth of the microorganisms; (2) the physical and chemical methods generally include acid precipitation, flocculation, membrane separation, adsorption, and electrochemical methods. Considering the requirements on equipment, environment, product purity and the like, the extraction method which is green and environment-friendly and has high extraction rate is developed, and has very important scientific research and practice significance.
The Emulsion Liquid Membrane (ELM) is a very effective processor for medium and low concentration impurities, and has attracted attention due to its characteristics of high selectivity, low consumption, high efficiency, low usage of toxic organic solvent, and good performance. Although the ELM has a plurality of excellent characteristics, the problems that the stability of an emulsion liquid membrane is easily influenced, demulsification is difficult after extraction is finished, an oil phase is difficult to recycle and the like all cause that the ELM is not widely produced and used. On the one hand, the stability of the emulsion membrane directly affects the effectiveness of the extraction process (positive correlation); on the other hand, emulsion membrane stability in turn affects the recycling of the oil phase (negative correlation). The conventional demulsification method influences the quality of the oil phase, so that the repeated use of the oil phase is influenced. The technical problem to be solved urgently is to provide an emulsion liquid membrane with high stability, easy demulsification and high recycling rate.
Disclosure of Invention
In order to overcome the defects, the invention provides the emulsion liquid membrane which has high stability, is easy to break emulsion and has high extraction rate of lignin in the papermaking black liquor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for separating and extracting lignin in papermaking black liquor by a magnetic emulsion liquid membrane comprises the following steps:
dispersing the carrier in an oily solvent to obtain an oil film;
nano Fe modified by oleic acid3O4Dispersing the particles in an oil film to obtain an oil phase;
adding the oil phase into an alkaline aqueous solution, and emulsifying to obtain a water-in-oil type emulsion;
carrying out acid precipitation and separation on black liquor to be treated, and collecting supernatant as an external water phase;
dripping the water-in-oil emulsion into an external water phase to extract lignin;
and after extraction is finished, layering, collecting the lower-layer water phase to detect the lignin extraction rate, and performing emulsion breaking on the emulsion to collect the magnetic particles, the oil film and the lignin.
The final enriched lignin is present in the inner water phase of the water-in-oil emulsion in the present application, and the purpose of collecting the lower water phase is to detect the lignin content of the lower water phase (i.e. the lignin content in the outer water phase), so as to calculate the extraction rate of the lignin.
In the present application, the "oil film" is composed of an oily solvent and a carrier.
Preferably, the volume ratio of the oil film to the water phase is 1-2: 1.
Preferably, the oleic acid modified nano Fe3O4The solid particles are contained in an amount of 0.5 to 2.0% by mass based on the oily solvent.
Preferably, the carrier is contained in an amount of 3 to 10% by mass relative to the oily solvent.
Preferably, the carrier is: tributyl phosphate (TBP) and/or trialkyl phosphine oxide extractant (Cyanex 923).
Preferably, the black liquor to be treated is black liquor obtained by pulping and papermaking cooking.
Preferably, the step of extracting lignin comprises: dropwise adding the emulsion liquid film into the external water phase according to the emulsion-water volume ratio of 1:3-1:15, stirring at the speed of 150-300r/min to form a water-in-oil-in-water composite emulsion, ensuring the stability of the emulsion at low speed, and extracting for 2-5 min.
Preferably, the method for collecting the magnetic particles and the oil film comprises the following steps: and placing a magnet below the emulsion for 5min to separate the magnetic particles from the oil-water interface, so as to break emulsion, and collecting the magnetic particles and an oil film to perform a re-emulsification process.
Preferably, the oily solvent is vegetable oil or kerosene.
The invention also provides oleic acid modified nano Fe3O4The application of the particles in extracting lignin from papermaking black liquor.
The invention has the advantages of
(1) The emulsion liquid membrane can quickly and efficiently extract lignin from black liquor, and has high extraction rate;
(2) the emulsion liquid film of the invention uses magnetic nano Fe3O4The particles and the vegetable oil are used as main raw materials, so that the use of kerosene, organic solvents and the like is avoided, and the method is simple and easy to obtain, low in cost and environment-friendly;
(3) the invention adopts magnetic nano Fe3O4The particles are emulsifier which has the function of demulsifier; the emulsion liquid film has the advantages of high stability and easy demulsification;
(4) the emulsion liquid film can be demulsified by magnetic attraction after being used, so that the use of chemicals and the resource consumption are avoided, the method is simple and easy to implement, and the quality of the oil film is not influenced;
(5) the extraction method provided by the invention has the advantages of simple process, high extraction rate, high recovery rate and low cost, and avoids excessive use of chemicals and resource consumption.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
An emulsion liquid membrane is a water-in-oil-in-water composite emulsion, which is obtained by mixing a water-in-oil emulsion prepared by a magnetic particle emulsifier with black liquor;
the oil film is an oily solvent and a carrier;
the oil phase is a mixture of a particle emulsifier and an oil film;
the water phase is an alkaline aqueous solution;
the volume ratio of the oil film to the water phase is 1-2:1, the emulsion stability is reduced when the volume ratio of the oil film is too high, and the emulsion is converted into an oil-in-water emulsion when the volume ratio of the oil film is too low;
the mass content of the emulsifier relative to the oily solvent is 0.5-2.0%, excessive flocculation of particles can be caused by too high content of the emulsifier, so that the stability of the emulsion is influenced, and incomplete emulsification can be caused by too low content of the emulsifier;
the mass content of the carrier relative to the oily solvent is 3-10%, and the excessive carrier content can influence the adsorption energy of the particle emulsifier at an oil-water interface and further influence the emulsion stability; too low a carrier content can reduce extraction efficiency;
the emulsifier is as follows: oleic acid modified nano Fe3O4The solid particles are in the form of solid particles,
the carrier is as follows: tributyl phosphate (TBP) and/or trialkyl phosphine oxide extractant (Cyanex 923).
The emulsion liquid membrane is used for separating and extracting lignin in the papermaking black liquor, the emulsifier and the oil membrane of the used emulsion ELM can be recycled, the demulsification process is simple, and the influence on the quality of the oil membrane is low.
In the invention:
the oleic acid modified nano Fe3O4The solid particles can improve the stability of the emulsion liquid film so as to improve the extraction rate of lignin, and also play a role in demulsification. After extraction, the magnetic nanoparticles are desorbed at the oil-water interface under the action of magnetic force to break emulsion, so that the use of chemicals and resource consumption are avoided, the method is simple and easy, and the quality of the emulsion liquid film is not influenced. In addition, experiments show that the recycled modified nano Fe3O4The solid particles can not obviously influence the stability of the emulsion and the extraction rate of the lignin, so the solid particles can be repeatedly used;
the oleic acid modified nano Fe3O4The solid particles can be obtained by a commercially available method of preparation by the existing method; one preparation method comprises the following steps: FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred into a 250mL three-neck flask to be stirred until the color of brick red is achieved; heating in water bath to 50 deg.C, and adjusting pH to 11.0-12.0; raising the temperature to 65 ℃, and stirring until the color is black; adding oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2 hours, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the particles in a vacuum drying oven at 60 ℃ overnight;
the water phase is alkaline water phase, can react with phenols to generate phenate, can not transfer mass back to the external water phase, and can be NH3.H2O solution, NaOH aqueous solution and NaHCO3Aqueous or other alkaline solutions;
the carrier can effectively enrich lignin in an internal water phase, so that the lignin can be efficiently extracted, and can be tributyl phosphate (TBP) or/and trialkyl phosphine oxide extractant (Cyanex 923);
the oily solvent can be vegetable oil, kerosene, etc.; for environmental protection and further cost reduction, vegetable oils such as corn oil, soybean oil, rapeseed oil or sunflower oil are preferred. The different vegetable oils can be replaced with each other, and the extraction effect is not obviously affected.
The above-mentioned emulsion film, preferably,
the volume ratio of the oil film to the water phase is 2:1,
the mass content of the emulsifier relative to the oily solvent is 1.0 percent,
the mass content of the carrier with respect to the oily solvent was 5%.
The preparation method of the emulsion liquid membrane comprises the following steps:
uniformly dispersing an emulsifier and a carrier in an oily solvent, emulsifying by using a high-speed shearing emulsifying machine, and dropwise adding a water phase, so that a stable water-in-oil emulsion is more easily formed;
the shearing and emulsifying speed is 10000-;
the invention also provides a method for separating and extracting lignin in black liquor by adopting the magnetic emulsion liquid membrane, which comprises the following steps:
using H for black liquor2SO4Or adjusting pH value to 2-6 with HCl, performing acid precipitation, centrifuging, and collecting supernatant as external water phase;
dropwise adding the emulsion liquid film into the external water phase according to the emulsion-water volume ratio of 1:3-1:15, stirring at the speed of 150-300r/min to form a water-in-oil-in-water composite emulsion, ensuring the stability of the emulsion at low speed, and extracting for 2-5 min;
standing after extraction is finished, and collecting a lower-layer water phase after emulsion is layered, wherein the lignin to be extracted exists in an inner water phase;
the method further comprises the following steps:
collecting the upper emulsion phase while collecting the lower aqueous phase; demulsifying the upper emulsion, and collecting the magnetic particles and the oil film; the collected magnetic particles are oleic acid modified nano Fe3O4Particles, wherein the main components of the collected oil film are a carrier and an oily solvent;
in the invention, the black liquor is black liquor obtained by pulping and papermaking cooking.
The principle of the invention is as follows:
oleic acid-coated ferroferric oxide (Fe)3O4) The preparation method comprises the following steps of taking nano solid particles as a stabilizer, mixing an organic solvent and a carrier to form an oil film, dispersing the stabilizer in the oil film to form an oil phase, shearing and emulsifying the stabilizer and a water phase solvent to obtain a stable water-in-oil type emulsion, adding the stable water-in-oil type emulsion into a supernatant of black liquor, stirring to form a water-in-oil-in-water composite emulsion, enriching lignin into an inner water phase through the carrier under the action of a concentration difference driving force, performing demulsification after extraction, recovering an emulsifier and the oil film, and recycling the.
Example 1
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in a water bath, and adjusting the pH value to 11.0-12.0 by using NaOH; stirring to black (over 2h) at an elevated temperature of 65 ℃; adding oleic acid with the mass being 2 times that of the black precipitate, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2 hours, and repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid; drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e. nano-Fe)3O4Modified particles).
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of carrier TBP in 100 parts of rapeseed oil, and performing ultrasonic dispersion for 15min to uniformly disperse the modified particles and the rapeseed oil to obtain an oil phase. And (3) dropwise adding the oil phase into 0.5mol/L NaOH aqueous solution according to the volume ratio of 1:1 of oil to water, and emulsifying for 5min by using a high-speed shearing emulsifying machine for 10,000/min to obtain the water-in-oil emulsion. Wherein the high-speed shearing emulsifying machine is an IKA T18 high-speed shearing emulsifying machine, and the parts are parts by mass (the same below).
The black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, and collecting supernatant as an external water phase; dropwise adding the water-in-oil emulsion into the external water phase according to the emulsion-water volume ratio of 1:5, and uniformly stirring at a speed of 200r/min for 2min to extract lignin; after the stirring is finishedImmediately layering, respectively collecting the lower water phase to determine lignin content and emulsion breaking. And (3) placing a magnet below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, collecting the magnetic particles and the oil film, and purifying to perform a re-emulsification process on the particle emulsifier and the oil film.
And (3) detecting the extraction effect of the prepared emulsion liquid film on lignin:
the extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 83.7% according to a lignin standard curve, and the extraction rate is calculated to be 65.0% by comparing with the supernatant which is not purified. Collecting magnetic particle emulsifier and oil film, purifying, and recycling for 5 times to reduce extraction rate to 60.0%.
Example 2
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); heating in water bath to 50 deg.C with NH3.H2And adjusting the pH value to 11.0-12.0 by using O. Raising the temperature to 65 ℃, and stirring until the mixture turns black (taking 2 hours); adding 5 times of oleic acid, continuously stirring, heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid; drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles).
1.0 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the obtained water-in-oil emulsion dropwise into the external water phase according to the emulsion water volume ratio of 1:5, stirring at 150r/min at constant speed to form water-in-oil-in-water composite emulsion, stirring for 4min, and extracting lignin; and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
Here, the high-speed shearing emulsifier was IKA T18 high-speed shearing emulsifier (the same applies hereinafter).
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, the extracted lignin is dried, part of the dried lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, and the proportion of the lignin in the solid matter is calculated to be 85% according to a lignin standard curve; the extraction yield was calculated to be 78% compared to the unpurified supernatant. The magnetic particle emulsifier and the oil film are collected for recycling, milk making and separation extraction, the recycling is more than 3 times, the particle emulsifier is unchanged, and only a small amount of carriers are dissolved in water to influence the extraction effect.
Example 3
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; stirring to black (over 2h) at an elevated temperature of 65 ℃; then adding 3 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles).
2.0 parts of nano Fe3O4Dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles and the carrier Cyanex923 to obtain an oil phase; then dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at 150r/min for 5min at constant speed, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 3min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the content of the lignin in a solid is calculated to be 89.0% according to a lignin standard curve, and the extraction rate is 54% by comparing with the supernatant which is not purified. The recovered solid particles have no obvious influence on the extraction effect after being recycled for 5 times, and the extraction rate is reduced to 34 percent after the oil film is recycled for 5 times.
Example 4
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuing stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation cleaning on the black precipitate by using deionized water and acetoneRemoving redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 10 parts of carrier TBP in 100 parts of oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles and the carrier TBP to obtain an oil phase. Dropwise adding the oil phase into 0.5mol/L NaOH solution according to the volume ratio of 1:1 of oil to water, and emulsifying for 5min by using a high-speed shearing emulsifying machine for 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 91.8% according to a lignin standard curve, and the extraction rate is calculated to be 66% by comparing with the supernatant which is not purified. When the recovered oil film is recycled for 6 times, the extraction efficiency is reduced to 55 percent.
Example 5
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O, raising the temperature to 65 ℃, and stirring until the color is black (taking 2 hours); then add 5 times oleic acid, continue stirring and literHeating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain the oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles);
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in the oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles and the oil phase to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 2:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the pH value of the black liquor after alkali cooking is changed into 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the obtained water-in-oil emulsion dropwise into the external water phase according to the emulsion water volume ratio of 1:5, stirring at 150r/min for 4min at constant speed, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 90.6% according to a lignin standard curve, and the extraction rate is calculated to be 78% by comparing with the supernatant which is not purified. The recovered particle emulsifier is recycled for 4 times, and has no obvious influence on the extraction rate, but the loss of the carrier in the oil film reduces the extraction effect along with the increase of the recycling times, and the extraction rate is reduced to 66 percent after the oil film is recycled for 3 times.
Example 6
FeCl3.6H2O and FeSO4.7H2According to the molar ratio of O2:1 was dispersed in 100mL deionized water and transferred to a 250mL three-necked flask and stirred to brick red (half an hour in time); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:10, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is 56% by comparing with the supernatant which is not purified. The recovered granular emulsifier still has an extraction rate of 50.5% after being recycled for 3 times.
Example 7
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.3 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 50% by comparing with the supernatant which is not purified. The recovery rate of the oil film is reduced to 42 percent after the oil film is recycled for 3 times.
Example 8
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles);
0.5 part of nano Fe3O4And dispersing the modified particles and 8 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 70% by comparing with the supernatant which is not purified. After the recovered particle emulsifier is recycled for 3 times, the extraction rate of 81.5 percent still exists, and after the oil film is recycled for 5 times, the extraction rate is reduced to 59 percent.
Example 9
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:23.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 53% compared with the extraction rate of the unpurified supernatant. The recovery rate of the oil film is reduced to 41 percent after the oil film is recycled for 4 times.
Example 10
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 5 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 5:23.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, performing centrifugal separation, collecting supernatant as external water phase, adding the water-in-oil emulsion into the external water phase dropwise according to the emulsion water volume ratio of 1:5, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 67% compared with the supernatant which is not purified. The recovery of oil film after recycling 4 times, the extraction rate reduced to 53%.
Example 11
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4Performing acid precipitation, centrifuging, collecting supernatant as external water phase, adding water-in-oil emulsion dropwise into the external water phase at emulsion water volume ratio of 1:15, and uniformly stirring at 300r/minStirring for 5min to extract lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 53% compared with the extraction rate of the unpurified supernatant. The recovery rate of the oil film is reduced to 40% after 3 times of recycling.
Example 12
FeCl3.6H2O and FeSO4.7H2O is dispersed in 100mL of deionized water according to the molar ratio of 2:1 and transferred to a 250mL three-neck flask to be stirred to be brick red (the time is half an hour); then heating to 50 ℃ in water bath, and using NH3.H2Adjusting the pH value to 11.0-12.0 by O; then raising the temperature to 65 ℃, and stirring until the mixture turns black (the time is 2 hours); then adding 5 times of oleic acid, continuously stirring and heating to 65 ℃, adjusting the pH value to 6.0-7.0, reacting for 2h, repeatedly performing magnetic decantation and cleaning on the black precipitate by using deionized water and acetone to remove redundant oleic acid, and drying the obtained particles in a vacuum drying oven at 60 ℃ overnight to obtain oleic acid modified nano Fe3O4Particles (i.e., nano-Fe)3O4Modified particles). (ii) a
0.5 part of nano Fe3O4And dispersing the modified particles and 3 parts of a carrier Cyanex923 in 100 parts of an oil phase, and performing ultrasonic dispersion for 30min to uniformly disperse the modified particles to obtain the oil phase. Dropwise adding the oil phase into 0.5mol/L NH according to the oil-water volume ratio of 1:13.H2Emulsifying the O solution for 5min by using a high-speed shearing emulsifying machine at 15,000/min to obtain a water-in-oil type emulsion;
the black liquor after alkali cooking is treated with 0.1mol/L H2SO4By carrying out an acidSeparating, centrifuging, collecting supernatant as external water phase, adding water-in-oil emulsion into the external water phase dropwise according to emulsion water volume ratio of 1:3, stirring at uniform speed of 300r/min for 5min, and extracting lignin;
and immediately layering after stirring, and respectively collecting the lower water phase for measuring the lignin content and the emulsion phase for demulsification. Placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
The extraction rate and purity of lignin are determined by an ultraviolet-visible spectrophotometer, firstly, a 3, 5-dinitrosalicylic acid (DNS) solution is prepared, after the extracted lignin is dried, a part of the lignin is dissolved by the DNS solution and diluted by water to a constant volume, the light absorption value is determined at 520nm, the proportion of the lignin in a solid is calculated to be 92.7% according to a lignin standard curve, and the extraction rate is calculated to be 67% compared with the supernatant which is not purified. The recovery rate of the oil film is reduced to 50% after 3 times of recycling.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (6)
1. Oleic acid modified nano Fe3O4The application of the particles in extracting lignin from papermaking black liquor is characterized in that the extraction method comprises the following steps: mixing an oily solvent and a carrier to obtain an oil film;
nano Fe modified by oleic acid3O4Dispersing the particles in an oil film to obtain an oil phase;
adding the oil phase into an alkaline aqueous solution, and emulsifying to obtain a water-in-oil type emulsion;
carrying out acid precipitation and separation on black liquor to be treated, and collecting supernatant as an external water phase;
dripping the water-in-oil emulsion into an external water phase to extract lignin;
after extraction is finished, layering, collecting a lower-layer water phase to detect the lignin extraction rate, performing emulsion breaking on the emulsion, and collecting magnetic particles, an oil film and lignin; the carrier is as follows: tributyl phosphate or/and trialkyl phosphine oxide extracting agent;
the oily solvent is vegetable oil or kerosene;
the black liquor to be treated is black liquor obtained by pulping and papermaking cooking.
2. Use according to claim 1, wherein the volume ratio of oil film to aqueous phase is 1-2: 1.
3. The use of claim 1, wherein the oleic acid-modified nano-Fe3O4The solid particles are contained in an amount of 0.5 to 2.0% by mass based on the oily solvent.
4. Use according to claim 1, wherein the carrier is present in an amount of 3 to 10% by mass relative to the oily solvent.
5. The use according to claim 1, wherein the step of extracting lignin comprises: dropwise adding the water-in-oil emulsion into the external water phase according to the emulsion-water volume ratio of 1:3-1:15, stirring at the speed of 150-300r/min to form a water-in-oil-in-water composite emulsion, ensuring the stability of the emulsion at low speed, and extracting for 2-5 min.
6. The use according to claim 1, wherein the method of collecting the magnetic particles and the oil film is: placing the magnetic particles below the emulsion for 5min to separate and demulsify the magnetic particles from the oil-water interface, and collecting the magnetic particles and the oil film for re-emulsification.
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